Polarography

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Copyright 2006, 2002, New Age International (P) Ltd., Publishers
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Dedi cated to fond memory of
brother Sh. P.K. Zutshi who
passed away on 3rd August 2001
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PREFACE TO THE SECOND EDITION
The foundati on of Pol arography was l ai d by Late Professor Jarosl ov Heyrovsky i n
1922. The theory and practi cal i mpl i cati ons were further extended by Professors : Jarosl ov
Kuta, B. Kucer a, VI cek, Kal ousek Swi tch, R. Bri di cka, I .M. Kol thoff, P. Zuman, L.
Mei tes, J. OM Bockri s and other di sti ngui shed el ectrochemi sts.
Si gni fi cant progress has been made i n thi s fi el d, si nce then and I have been moti vated
to br i ng out thi s book whi ch cover s both the fundamental s as wel l as the r ecent
devel opments.
Thi s vol ume i s i ntended as a text book and i ncl udes questi ons and chemi cal exampl es.
The book can be used i n formal courses at the seni or under graduate l evel s.
The probl ems fol l owi ng each chapter have al so been i ncl uded al ong wi th some general
questi ons.
Some more topi cs have been added i n thi s second edi ti on. Thi s has hel ped to cover
the courses prescri bed i n other north I ndi an uni versi ti es of the country.
The chapter on corrosi on has been gi ven speci al attenti on and as such the chapter
has been di vi ded i n two A and B.
The detai l s of l aboratory procedure, such as the desi gn of cel l s and the constructi on
of el ectrodes has al so been attended.
The mai n feature l i es i n the i mportant devel opments resul ti ng from pol arographi c
anal ysi s i n the study of organi c systems by el ectrochemi cal method.
The l evel at whi ch the fundamental pri nci pl es pertai ni ng to the methods descri bed
i n thi s text are presented and woul d hel p i n understandi ng the essenti al pri nci pl es
underl yi ng the appl i cati ons of the methods descri bed i n the text.
I n addi ti on to the treatment of the fundamental pri nci pl es, some chapters do certai n
exampl es descri bi ng the appl i cati ons of the methods descri bed i n the text.
Apart from the general coverage, i mportance i s gi ven to the study of organi c systems
by el ectrochemi cal methods. The el ectro-organi c synthesi s i nvol vi ng di rect and i ndi rect
el ectrode reacti ons has al so been descri bed i n thi s text. The matter provi ded i n thi s area
of el ectrochemi stry has been descri bed mai nl y under categori es l i ke : Theory, Methods
and I nstrumentati on.
The i ncenti ve to prepare thi s work for publ i cati on has been provi ded by the members
of my fami l y. I wi sh to express my si ncere thanks to my brothers and my ni ece for thei r
i nterest and constant encouragement to compl ete thi s work. For bri ngi ng out the second
edi ti on as wel l as to i ncl ude few more chapters has been gi ven by one of my students
: Prof. P.S. Verma of the Dept., Uni versi ty of Rajasthan, Jai pur.
Kamala Zutshi
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PREFACE TO THE FIRST EDITION
The foundati on of Pol arography was l ai d by Late Professor Jarosl ov Heyrovsky i n 1922.
The theory was further extended by Professors : Jarosl ov Kuta, B. Kucera, Vl cek, Kal ousek
Swi tch, R. Br i di cka, I .M. Kol thoff P. Zuman, J.O.M Bockr i s, L. Mci tes and other
di sti ngui shed sci enti sts.
Si gni fi cant progress has been made i n thi s fi el d i n recent ti mes and thi s has
moti vated me to bri ng out thi s book whi ch covers both the fundamental s as wel l as the
recent devel opments.
The book has been wri tten to serve mai nl y the postgraduate students of the vari ous
I ndi an uni versi ti es.
The contents of the cur r ent r esear ch and moder n textbooks i n thi s ar ea of
El ectrochemi stry i ndi cate beyond doubt that students of el ectrochemi stry must have a
worki ng knowl edge of vari ous methods i n thi s fi el d. I t i s al so necessary to understand
the basi c pri nci pl es and l i mi tati ons of these experi mental methods i n order to proceed
for good research, unl ess the students have al ready had an i ntroductory el ectrochemi stry
cour se.
The l evel at whi ch the fundamental pri nci pl es pertai ni ng to the methods descri bed
i n thi s text are presented, shal l hel p i n understandi ng the essenti al pri nci pl es underl yi ng
the appl i cati ons of the methods descri bed i n the text.
I n addi ti on to the treatment of the fundamental pri nci pl es, some chapters do contai n
exampl es descri bi ng the appl i cati ons of these methods, though the coverage may not
be very detai l ed.
The mai n feature l i es i n the i mportant devel opments resul ti ng from pol arographi c
anal ysi s i n the study of organi c systems by el ectrochemi cal methods. As a whol e the
text has been detai l ed as: The methods and i nstrumentati on, Vari ous types of el ectrodes
and thei r worki ng. Non aqueous systems, I norgani c systems as wel l as the El ectrode
pr ocesses.
Apart from the general coverage, i mportance i s gi ven to the study of organi c systems
by el ectrochemi cal methods. The el ectro organi c synthesi s i nvol vi ng di rect and i ndi rect
el ectrode reacti ons has al so been descri bed i n thi s text. The matter provi ded i n thi s
ar ea of el ectr ochemi str y has been descr i bed mai nl y under categor i es l i ke: Theor y,
Methods and I nstrumentati on.
The i ncenti ve to prepare thi s work for publ i cati on has been provi ded by the members
of my fami l y. I wi sh to express my si ncere thanks to my brothers and my ni ece for thei r
i nterest and constant encouragement to compl ete thi s work.
Kamala Zutshi
Jai pur , I ndi a
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CONTENTS
PARTI : POLAROGRAPHY
1. POLAROGRAPHY 3
1.1 I ntroducti on and Basi c Pri nci pl es 3
1.2 Pol arographs and thei r Appl i cati ons 5
1.3 The Pol arographi c Cel l s and the Experi mental Set Up 5
1.4 The Hal f-wave Potenti al and i ts Si gni fi cance 6
1.4.1 Si gni fi cance of Hal f-wave Potenti al s 7
1.4.2 I nfl uence of I oni c Str ength on Hal f-wave Potenti al s 7
1.4.3 Factors whi ch Affect the Hal f-wave Potenti al s 8
References 10
2. THE ELECTRODES 11
2.1 Mercury El ectrodes 11
2.1.1 Droppi ng Mercury El ectrode 12
2.1.2 Fl ow of Mercury from Capi l l ari es 12
2.1.3 Advantages of DME 14
2.1.4 Hangi ng Mercury Drop El ectrode 15
2.2 Carbon El ectrodes 17
2.2.1 Carbon Paste El ectrodes 17
2.2.2 Gl assy Carbon El ectrode 19
2.3 Pol arographi c Cel l s and Saturated Cal omel El ectrode 19
2.4 Mercury Pool El ectrode 22
References 22
3. THE TECHNIQUE 23
3.1 Pol arographi c Ci rcui t 23
3.2 The Si gni fi cance of Di ffusi on i n Cl assi cal Pol arography 23
3.3 Sol vents and Supporti ng El ectrol ytes 28
3.3.1 Recommended Sol vents and El ectrol ytes 30
3.4 Pol arographi c Maxi ma 31
3.4.1 Maxi ma of the Fi rst Ki nd 31
3.4.2 Suppressi on of Maxi ma of the Fi rst Ki nd 32
3.4.3 Pol ari ty of Maxi ma of the Fi rst Ki nd 32
(xi i )
3.4.4 Streami ng of El ectrol yte and Maxi ma of the Fi rst Ki nd 34
3.4.5 Maxi ma of the Second Ki nd 35
3.4.6 Suppressi on of Maxi ma of the Second Ki nd 35
3.4.7 Streami ng of El ectrol yte wi th Maxi ma of the Second Ki nd 36
3.4.8 I nterpretati on of Maxi ma of the Second Ki nd 36
3.4.9 Practi cal Appl i cati ons of Pol arographi c Maxi ma 37
3.5 Pol ar ogr aphy i n Non-aqueous Sol vents 37
3.5.1 Sol vents that are Frequentl y Used 38
References 40
4. THEORY OF CURRENT POTENTIAL CURVES 42
4.1 The I l kovi c Equati on 42
4.1.1 Consequences of I l kovi c Equati on 44
4.2 Reversi bl e and I rreversi bl e El ectrode Processes 46
4.3 Reversi bl e Pol arographi c Wave 48
4.3.1 Cathodi c Wave 49
4.3.2 Anodi c Wave 52
4.3.3 Cathodi c-Anodi c Waves 53
4.4 Coupl ed Chemi cal Reacti on and Chemi cal Reversi bi l i ty 55
References 57
5. TYPES OF CURRENTS 58
5.1 Mass Transfer and El ectrochemi cal Processes 58
5.2 Di ffusi on Current 58
5.2.1 Di ffusi on to Stati onary El ectrodes 59
5.2.2 Di ffusi on-Control l ed Current 60
5.2.3 Li near Di ffusi on to a Growi ng Droppi ng El ectrode 61
5.2.4 Di ffusi on Coeffi ci ent 61
5.2.5 Spheri cal Di ffusi on 63
5.3 I nfl uence of Vi scosi ty and of Compl ex
Formati on on Di ffusi on Current 64
5.4 Factors Affecti ng the Di ffusi on Current 64
5.4.1 The Li mi ti ng Current 67
5.4.2 The Resi dual Current 67
5.4.3 Mi grati on Current 68
5.4.4 Ki neti c Currents 71
5.4.5 Catal yti c Currents 73
5.5 Adsorpti on Waves 74
References 76
6. POLARIZATION 77
6.1 Pol ari zati on of the Droppi ng Mercury
El ectrode and Depol ari zati on Processes 77
6.2 Reducti on of Hydr ogen I ons and Hydr ogen Over Vol tage 78
(xi i i )
6.3 Doubl e Layer 80
6.4 Reducti on of Cati ons 81
References 82
7. AMPEROMETRIC TITRATIONS 83
7.1 Types of Amperometri c Ti trati ons 83
7.1.1 Theory of Amperometri c Ti trati on Curves 83
7.2 Ki nds of Amperometri c Ti trati ons 84
7.2.1 Redox Ti trati ons 85
7.2.2 Compl exometri c and Chel ometri c Ti trati ons 85
7.2.3 Compensati on and Di ffusi on-Layer Ti trati ons 86
7.3 Amperometri c Ti trati ons wi th Two Pol ari zed El ectrodes 86
7.4 Apparatus and Techni ques 87
7.4.1 The Worki ng El ectrode : Reference El ectrode 88
7.5 Two Worki ng El ectrodes 88
7.6 Chronoamperometry 89
References 91
8. POLAROGRAPHY OF METAL COMPLEXES 92
8.1 Reversi bl e, Di ffusi on-control l ed Systems
Determi nati on of Formul ae and Stabi l i ty
Constants of Compl exed Metal I ons 92
8.2 Determi nati on of Stabi l i ty Constants and
Coordi nati on Numbers of Metal Compl exes 93
8.2.1 Cal cul ati on of I ndi vi dual Compl ex
Stabi l i ty Constants 96
8.3 Mi xed Li gand Systemsthe Method of Schaap
and McMasters 96
References 97
9. POLAROGRAPHY OF ORGANIC COMPOUNDS 98
9.1 Structural Effects 99
9.2 Nature of El ectroacti ve Group 100
9.3 Steri c Effects 101
9.4 Substi tuent Effects 102
References 104
PARTII : ALLIED TECHNIQUES
10. MISCELLANEOUS POLAROGRAPHIC METHODS :
PRINCIPLES, THEORY TECHNIQUES AND
ANALYTICAL APPLICATIONS 107
10.1 Squar e Wave Pol ar ogr aphy 107
10.2 Al ternati ng Current Pol arography 114
10.2.1 The Techni que and I nstr umentati on 117
(xi v)
10.3 Coul ometr y 119
10.3.1 Coul ometry wi th Large Area Mercury El ectrodes 120
10.3.2 Coul ometry wi th a Droppi ng Mercury El ectrode 120
10.3.3 Determi nati on of n by Anal ysi s of the Decrease
i n Li mi ti ng Current 121
10.3.4 Determi nati on of n by El ectrol ysi s at
Constant-Current 122
10.4 Coul ometry i n Pol arographi c Anal ysi s 123
10.5 Control l ed-potenti al El ectrol ysi s 123
10.6 Chronopotenti ometry 126
10.7 Theory of Reversi bl e Processes 127
10.7.1 I rreversi bl e Processes 128
10.8 Experi mental Methods 129
10.8.1 Apparatus 130
10.8.2 Cel l s and El ectrodes 130
10.9 The Techni ques 130
10.9.1 Measurement of Transi ti on Ti mes 131
10.10 Appl i cati ons 131
10.10.1 Concentrati on Measurements 131
10.10.2 El ectrode Ki neti cs 131
10.10.3 El ectrode Pretreatment 131
10.10.4 Di fferenti al and A.C. Chronopotenti ometry 131
10.10.5 Thi n-Layer Chronopotenti ometry 132
10.10.6 Chemi cal Ki neti cs 132
10.11 Adsor pti on 132
10.12 Appl i cati ons 132
References 133
11. ADVANCES IN D.C. POLAROGRAPHY 135
11.1 Devel opments i n D.C. Pol arography 135
11.1.1 Pri nci pl e of Potenti ostati c
(Control l ed-Potenti al ) El ectrol ysi s 135
11.2 Ti me-deri vati ve D.C. Pol arography 136
11.2.1 Di rect Proporti onal i ty of Fi rst Deri vati ve
Peak Hei ghts to i
d
139
11.2.2 Rel ati ve Si gnal Level s i n Regul ar and i n Fi rst,
Second, and Thi rd Deri vati ve D.C. Pol arography 139
11.2.3 Cri teri on for Rel ati ve Resol vi ng Power of Vari ous
Methods of Pol arography 139
11.2.4 Geometri cal Overl appi ng for Successi ve Waves 140
11.2.5 Mathemati cal Resol uti on of Overl apped Fi rst
Deri vati ve d.c. Pol arograms 141
11.2.6 Mathemati cal Resol uti on of Regul ar Pol arography
Compared to Fi rst Deri vati ve d.c. Pol arography 142
11.2.7 D.C. Pol ar ogr aphy i n Non-aqueous Sol vents and
Parti cul arl y i n Sol vent Extracts 143
(xv)
11.3 Theory, Pri nci pl es and Appl i cati ons 143
11.3.1 Si ngl e Sweep Methods 144
11.3.2 El ectrol yti c Current 146
11.3.3 Ki neti c Currents 149
11.3.4 Types and Forms of Vol tage Sweeps 149
11.4 Mul ti -sweep Methods 149
11.5 Apparatus for Appl i ed Vol tage Osci l l ographi c Pol arography 150
11.6 Control l ed Current Osci l l ographi c Pol arography 150
11.7 Pul se Pol arography 152
11.8 Stri ppi ng Anal ysi s 153
References 160
12. VOLTAMMETRIC METHODS 162
12.1 Vol tammetry 162
12.1.1 Coul ometri c Methods 163
12.1.2 Vol tammetri c Methods 164
12.2 Large-ampl i tude Pul se Vol tammetry (LAPV) 167
12.3 Di fferenti al and Deri vati ve Vol tammetry 170
References 172
13. CONTROLLED POTENTIAL ELECTROLYSIS 173
13.1 El ectro-organi c Synthesi s and the Techni que 173
13.1.1 Pure El ectron Transfer 173
13.1.2 Conversi on of Functi onal Groups 174
13.1.3 Substi tuti on Reacti ons 174
13.1.4 Addi ti on Reacti ons 174
13.1.5 El i mi nati on Reacti ons 175
13.1.6 Coupl i ng Reacti ons 175
13.1.7 Cycl i zati on (I ntramol ecul ar and I ntermol ecul ar) 175
13.2 El ectrochemi cal Acti vi ty i n Heterocycl i c Systems 176
13.2.1 Ri ng Cl osure Reacti ons 176
13.3 Experi mental Techni que 177
13.4 Ci rcui t for Potenti ostati c Method 178
13.4.1 Pol ari zati on Study 179
13.5 Current Effi ci ency 184
References 185
14. CORROSION 186
Part A : Principles and Control
14.1 Corrosi on and Control 186
14.1.1 I on Sel ecti ve El ectrodes 187
14.1.2 Operati onal Ampl i fi ers 189
14.1.3 Potenti ostat 189
14.1.4 Gal vanostat 190
(xvi )
14.1.5 Pol arography 190
14.1.6 Pul se Pl ati ng Sources 190
14.1.7 Mi cro Processor Based I nstrumentati on 191
14.1.8 Damage and Contr ol 191
14.1.9 Sour ces of Hydr ogen and Modes of Entr y 191
14.1.10 Mechani sm of Corrosi on of H
2
S CO
2
192
14.2 Mechani sm of Carbon Di oxi de Corrosi on 193
References 194
Part B : Stability of Metals
14.3 Thermodynami cs and the Stabi l i ty of Metal s 195
14.4 Potenti al pH (or Pourbai x) Di aphragms: Uses and Abuses 198
14.5 El ectronati on Reacti on i n Corrosi on 200
14.6 The Corrosi on Current and Corrosi on Potenti al s 201
14.7 The Basi c El ectrodi cs of Corrosi on i n the Absence of Ozi de Fi l ms 203
14.8 Factors Affecti ng the Rate of Corrosi on and Evans Di agrams 204
14.9 Some Common Exampl es of Corrosi on 208
14.10 Control of Corrosi on Current i n the Corrosi on Process 209
14.11 Vari ous Factors i n Determi ni ng Corrosi on 209
Part C : Passivation
14.12 Passi vati on : Transformati on from a Corrodi ng and Unstabl e Surface
to a Passi ve and Stabl e Surface 212
14.13 The Mechani sm of Passi vati on 213
14.14 The Thermodynami cs of Passi vati on 213
14.15 Rol e of Hydrogen i n Corrosi on 214
15. CONVERSION AND STORAGE OF ELECTROCHEMICAL ENERGY 216
Section A
15.1 Present Status of Energy Consumpti on 216
15.2 Status of Energy Consumpti on 217
15.3 Di rect Energy Conversi on by El ectrochemi cal Means 218
15.4 Di rect Energy Conversi on by El ectrochemi cal Means 218
15.5 The Maxi mum I ntri nsi c Effi ci ency of an El ectrochemi cal Converter 219
15.6 The Actual Effi ci ency of an El ectrochemi cal Energy Converter 220
15.7 Physi cal I nterpretati on of the Absence of the Carnot Effi ci ency
Factor i n El ectrochemi cal l y Energy Converters 220
15.8 The Power Output of an El ectrochemi cal Energy Converters 222
Section B
El ectrochemi cal Generators (Fuel Cel l s) 222
Cel l s Usi ng Fuel s other than Hydrogen 223
The Hydr ogen-Oxygen Cel l 224
Hydrogen Ai r Cel l s 225
(xvi i )
16. ELECTROCHEMICAL ENERGY STORAGE : THE IMPORTANT
QUANTITIES IN ELECTRICITY STORAGE 226
16.1 El ectri ci ty Storage Densi ty 226
16.2 Energy Densi ty 226
Power 229
El ectri ci ty Storage 230
Cl assi cal Batteri es 233
Zi nc Manganese Di oxi de 234
Rel ati vel y New El ectri ci ty Stores Si l ver Zi nc Cel l 235
Storers wi th Zi nc i n Combi nati on wi th an Ai r El ectrode 236
Future El ectri ci ty Storers 237
Storage by Usi ng Al kal i Metal s 238
Storers i nvol vi ng Non-aqueous Sol uti ons 239
17. KINETICS OF ELECTRODE PROCESS 241
I ntroducti on 241
17.1 Essenti al s of El ectrode reacti on 243
17.2 Butl er Vol mer Model of El ectrode Ki neti cs R 244
Effects of Potenti al on Energy Barri ers 244
One Step, One-El ectron Process 246
17.3 I mpl i cati ons of the Butl er-Vol mer
Model for the One Step, One El ectron Process 248
17.4 The Current Overpotenti al Equati on 249
17.5 The Standard Rate Constant 249
17.6 The Transfer Coeffi ci ent 250
17.7 Approxi mate Forms of the i - n Equati on 252
(a) No Mass-Transfer effects 252
(b) Li near Characteri sti c at Smal l 252
(c) Tafel Behavi our at Lar ge 253
(d) Tafel Pl ots 254
Exchange Current pl ots (Tafel Pl ots) 254
17.8 Effects of Mass Transfer 255
References 256
18. BIOELECTRODICS 257
I ntroducti on 257
Useful Prel i mi nari es 257
Membrane Potenti al s 259
Si mpl i sti c Theory 261
Modern Approaches to the Theory of Membrane Potenti al s 262
El ectri cal Conducti on i n Bi ol ogi cal Organi sms 264
El ectri cal Conducti on i n Bi ol ogi cal Organi sms Protoni c 265
(xvi i i )
The El ectrochemi cal Mechani sms of the Nervous System
an Unfi ni shed Secti on 266
Enzymes as El ectrodes 267
Enzymes 267
El ectrodes Carryi ng Enzymes 267
The el ectrochemi cal Enzyme-Catal yzed Oxi dati on of Styrene 269
APPENDIX 270
Questi ons 279
PART-I
POLAROGRAPHY
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CHAPTER 1
POLAROGRAPHY
1.1 INTRODUCTION AND BASIC PRINCIPLES
Pol arography i s the branch of vol tammetry i n whi ch a droppi ng mercury el ectrode i s
used as the i ndi cator el ectrode. I t i s the el ectroanal yti cal techni que that deal s wi th the
effect of the potenti al of an el ectrode i n an el ectrol ysi s cel l on the current that fl ows
through i t. The el ectrode whose potenti al i s vari ed i s cal l ed the i ndi cator el ectrode
vol tammetri c i ndi cator el ectrodes may be made from qui te a l arge number of materi al s
say for i nstance mer cur y, pl ati num, gol d and gr aphi te, havi ng var yi ng shapes and
constructi on. They may be stati onary or i s moti on and the sol uti ons i n whi ch these are
used may be stati onary or qui et.
Pol arography was the fi rst of the vol tammetri c techni ques to gai n promi nence.
Certai nl y the most popul ar constant potenti al method i s d.c. pol arography at a droppi ng
mercury el ectrode (DME). The reason bei ng that there are several advantages pecul i ar
to the DME, these are descri bed further.
The essenti al features of current potenti al curves obtai ned wi th DME are shown i n
Fi g. 1.1. Cur ve b i s the pol arogram of a di l ute sol uti on of hydrochl ori c aci d and the curve
a bei ng obtai ned under exactl y the same condi ti ons after addi ti on of a smal l concentrati on
of cadmi um i on. Here, each osci l l ati on represents the l i fe cycl e of one drop. I t i s the
di fference between the currents on the two curves whi ch i s of i nterest. No detectabl e
change of current resul ts at potenti al s l ess negati ve than about 0.5 V from the addi ti on
of cadmi um i on. The reason bei ng that these potenti al s are i nsuffi ci entl y negati ve to
bri ng about the reducti on of any appreci abl e fracti on of the cadmi um i on at the surface
of the drop. At potenti al s more negati ve than thi s, however, a wave appears, i.e., the
reducti on of cadmi um i on proceeds more and more rapi dl y as the potenti al becomes
more negati ve unti l eventual l y, at potenti al s more negati ve than about 0.7 V i s attai ned.
I t i s so fast that cadmi um i ons are reduced as rapi dl y as they get di ffused from the bul k
of the sol uti on upto the surface of the el ectrode. The rate of thi s di ffusi on depends on
a number of factors. Out of these the concentrati on of cadmi um i on i n the bul k of the
sol uti on i s of speci al i mportance. More concentrated the sol uti on, the greater the rate
at whi ch cadmi um i ons reach, the el ectrode surface, and the greater the di ffusi on current
that resul ts from thei r reducti on. The proporti onal i ty between the di ffusi on current and
the concentrati on of the substance responsi bl e for the wave i s the basi s for nearl y al l
quanti tati ve pol arographi c anal ysi s. The ease of reducti on or oxi dati on di ffers for di fferent
substances, and i s refl ected by the posi ti on of the wave wi th respect to the potenti al
4 I ntroduction to Polarography and Allied Techniques
axi s. Thi s i s termed by a parameter cal l ed the hal f wave potenti al ( E ). Thi s i s
defi ned as the potenti al at whi ch the current due to the reducti on or oxi dati on of the
substance responsi bl e for the wave, i s hal f as l arge as on the pl ateau. The hal f wave
potenti al of cadmi um i on can be seen i n Fi g. 1.1 (a). Under a set of defi ned experi mental
condi ti on, each i on has i ts own characteri sti c hal f wave potenti al whi ch i s the basi s of
qual i tati ve pol arographi c anal ysi s. I n cases, the el ectrode reacti on may be so rapi d that
equi l i bri um i s cl osel y approached at every potenti al i n a ti me much shorter than the
drop l i fe. Thi s i ndi cates the wave to be reversi bl e. Studyi ng the effects of potenti al and
sol uti on composi ti on on the cur r ents al ong the r i si ng par t of the wave pr ovi des
i nformati on on the thermodynami cs of the hal f reacti on.
20
15
10
5
0
0 0. 3 0. 6 0. 9 1. 2
C
u
r
r
e
n
t
i
n
m
i
c
r
o
a
m
p
e
r
e
s
E Vol ts i n S. C. E.
d.c
( a)
Diffusion
Current
E
( b)
(a) 1 F hydrochl ori c aci d wi th 0.5 mM (b) 1 F hydrochl ori c aci d al one
Cadmi um i on
Fi g. 1.1 : Pol ar ogr am
I n some cases the el ectrode reacti on may i nvol ve a step havi ng a l arge acti vati on
over potenti al than the vari ati on of the current potenti al and sol uti on composi ti on are
due to ki neti c rather than thermodynami c effects. I n such cases i nformati on on the
mechani sm of the rate determi ni ng step can be secured.
Pol arographi c anal ysi s can be used di rectl y for the determi nati on of any substance
sol i d, l i qui d or gaseous, organi c compounds contai ni ng conjugated doubl e or tri pl e bonds
i ncl udi ng pol ynucl ear aromati c ri ng systems, as wel l as compounds l i ke oxi mes, i mi nes,
ketones, al dehydes ni tro di azo compounds and hal o substi tuted compounds.
One of the most i mportant advantage of pol arography and other vol tammetri c
techni ques i s that two or even more substances can be determi ned by a si ngl e current
potenti al curve.
Another i mportant anal yti cal techni que cl osel y rel ated to pol arography i s that of
amperometri c ti trati on.
Pol arography i s getti ng more wi del y used i n fi el ds as bi ochemi stry and pharmaceuti cal
chemi stry. Even i t has been used to study such di verse topi cs l i ke hydrol ysi s, sol ubi l i ty,
compl ex formati on, absorpti on, ki neti cs of chemi cal reacti on and mechani sm of el ectrode
reacti ons.
1.2 POLAROGRAPHS AND THEIR APPLICATIONS
There are two ki nds of pol arographs: manual and recordi ng. Wi th a manual i nstrument,
the potenti al appl i ed to the cel l i s adjusted to some desi red val ue and the current i s
measured. A si ngl e poi nt on the pol arogram i s thus obtai ned. I f the whol e curve i s
wanted, the procedure must be repeated many ti mes. Thi s i s tedi ous, speci al l y when
several waves or a compl ex pol arogram i s to be observed as such, the manual pol arograph
i s not very conveni ent. For such observati ons a recordi ng i nstrument i s most sui tabl e.
The manual pol ar ogr aphs ar e not a di sadvantage ei ther . The di ffusi on-cur r ent
measurements can be made more preci sel y and more qui ckl y wi th manual than wi th
recordi ng pol arograph.
I n a recordi ng pol arograph, the potenti al appl i ed to the cel l i s obtai ned from a
motor-dri ven vol tage di vi der. Two procedures have been most frequentl y empl oyed for
r ecor di ng the cur r ent. I n one, the cur r ent i s passed thr ough a gal vanometer , and the
defl ecti ons of the gal vanometer are recorded photographi cal l y or a pi ece of photographi c
paper movi ng at a known rate past a sl i t. I n the other, whi ch i s now by for the more
common, the current i s passed through a standard resi stor i n seri es wi th the cel l , and
the resul ti ng iR drop i s presented to a stri p-chart recordi ng potenti ometer, whi ch pl ots
the iR drop agai nst ti me. Correl ati ng the rates of moti on of the chart and the vol tage
di vi der makes i t possi bl e to i nterpret the curve as a pl ot of current agai nst appl i ed
potenti al . Usual l y, a recordi ng pol arograph empl oys a rate of change of potenti al of
about 0.2 vol t per mi nute and furni shes a compl ete pol arogram i n about 10 mi nutes.
1.3 THE POLAROGRAPHIC CELLS AND THE EXPERIMENTAL SET UP
The cel l i s that porti on of the apparatus that contai ns the sol uti on whi ch bei ng studi ed.
I t al so i ncl udes a non-pol ari zabl e el ectrode to whi ch the potenti al of the droppi ng el ectrode
i s referred.
The most i mportant part of a cel l i s i ts reference el ectrode. Two ki nds of reference
el ectrodes, i nternal and external are i n general use. An i nternal el ectrode i s i n di rect
contact wi th the sol uti on bei ng studi ed, whi l e an external el ectrode i s separated from
i t by a sal t bri dge or a porous membrane. I nternal el ectrodes are chi efl y val uabl e i n
routi ne anal yses i n whi ch a l i mi ted constancy of potenti al i s uni mportant. They are al so
often used i n work (when very hi gh negati ve potenti al s) where contami nati on by al kal i
metal i ons or other consti tuents of a sal t bri dge woul d be harmful ; i n cel l s contai ni ng
Polarography 5
onl y one or two drops of sol uti on are used. Here the di ffi cul ty ari ses by bri ngi ng an
external el ectrode i nto contact wi th so smal l a vol ume of the sampl e. I n conti nuous
pol arographi c anal ysi s, where the sl ow contami nati on of an external el ectrode woul d
eventual l y render i ts potenti al as uncertai n as that of an i nternal one.
I nternal reference el ectrode i s made by coi l i ng about 1520 cm of 14 gauge si l ver
wi re i nto a hel i x. I t i s often
conveni ent to coi l i t around
the droppi ng el ectrode. I n a
sol uti on contai ni ng an i on
X
that for ms an i nsol ubl e

si l ver sal t, the potenti al of
thi s el ectrode depends onl y
on the acti vi ty of X
i n the
sol uti on, provi ded of course,
th at th e s ol u ti on i n
saturated wi th Ag X. I f i ts
sol ubi l i ty i s ver y smal l ,
enough Ag X to sati sfy thi s
requi rement wi l l be formed
by r eacti on wi th di ssol ved
oxygen, an ai r satur ated
sol uti on i s pl aced i n contact
wi th the el ectr ode befor e
deaerati on. I f the sol uti on i s
neutr al and unbuffer ed, i t
may i n v ol v e par ti al
hydr ol yti c pr eci pi tati on of
heavy metal i ons. The el ectrode shoul d not be used unl ess a preci pi tate resul ts when
a drop of sol uti on contai ni ng 0.01 M si l ver i on i s added to 10 ml of the sampl e sol uti on.
Otherwi se the concentrati on of di ssol ved si l ver i on, and hence the potenti al of the
si l ver el ectrode, may change consi derabl y duri ng the recordi ng of the pol arogram. I n
addi ti on the concentr ati on of si l ver i on may become hi gh enough to gi ve r i se to
substanti al current at the droppi ng el ectrode.
The si l ver el ectrode i s not workabl e i n sol uti ons contai ni ng ammoni a, cyani de,
thi osul phates and hi gh concentrati ons of hal i des as wel l as i n sol uti ons contai ni ng onl y
ni trate, acetate perchl orate and other i ons whose si l ver sal ts are appreci abl y sol ubl e.
The coati ng of i nsol ubl e sal ts that terms on the el ectrode when i t i s used as the
anode cel l shoul d be removed by treatment wi th ammoni a, thi osul phate, or cyani de,
fol l owed by ri nsi ng wi th di sti l l ed water.
1.4 THE HALF-WAVE POTENTIAL AND ITS SIGNIFICANCE
The most i mportant constant i n pol arography i s the hal f-wave potenti al . Chemi cal ,
thermodynami c and structural i nformati on may be obtai ned from the measurements of
the hal f-wave potenti al s of reversi bl e and i rreversi bl e waves under varyi ng experi mental
condi ti ons.
Fi g. 1.2 : Experimental set up in Polarographic Experiment
Galvanometer
G
Mercury reservoir
oxygen free
nitrogen
solution of unknown subs.
with excess inert salt
+
+
The manner i n whi ch the current i s affected by el ectrode potenti al on the ri si ng
part of the wave i s to be noted. On the pl ateau, el ectron transfer i s so fast that the i ons
or mol ecul es of the el ectroacti ve substances are reduced or oxi di zed as rapi dl y as they
arri ve or are formed at the el ectrode surface. As the potenti al moves from the pl ateau
of the wave towards i ts foot, the rate of the el ectron-transfer process decreases and the
reducti on or oxi dati on becomes l ess and l ess compl ete.
I t i s conveni ent to di vi de el ectrode reacti ons i nto two extreme cl asses : (i) Reversi bl e
reacti ons, and (ii) i rreversi bl e reacti ons. (i) The reversi bl e reacti ons are so rapi d that
thermodynami c equi l i bri um i s very nearl y attai ned at every i nstant duri ng the l i fe of
a drop at any potenti al . For such reacti ons the vari ati on of current wi th potenti al
refl ects the changi ng posi ti on of the equi l i bri um and i s descri bed by Nernst equati on.
The other extreme i s that of total l y i rreversi bl e reacti ons, whi ch are so sl ow that they
proceed onl y by a fracti on of the way towards equi l i bri um duri ng the l i fe of each drop.
For these reacti ons i t i s the rate of the el ectron-transfer process and the manner i n
whi ch thi s i s i nfl uenced by the el ectrode potenti al that governs the rel ati onshi p between
current and potenti al . The pol arographi c data serve to el uci date the ki neti cs of the rate
determi ni ng step i n total l y i rreversi bl e processes.
1.4.1 Significance of Half-wave Potentials
I t fol l ows from the equati on deri ved on current potenti al curves that the hal f-wave
potenti al s gi ven by the term, RT/ nF. I n D /v, equal s the standard oxi dati on-reducti on
potenti al found wi th other i ndi cator el ectrodes such as pl ati num el ectrodes. Thi s property
hol ds onl y for an oxi dati on-reducti on system, whose oxi di zed and reduced terms are
both present i n the sol uti on, e.g., Fe
2+
/Fe
3+
. Thi s was confi rmed by many previ ous workers.
I f one of the two terms (may be the reduced one) reacts wi th the materi al of the
el ectrode (metal s wi th i nformati on of an amal gam), then the hal f-wave potenti al di ffers
from the standard oxi dati on-reducti on potenti al for the metal /i on system. I t can be
readi l y shown that the di fference between the hal f-wave and the standard potenti al i s
gi ven by the fr ee ener gy of amal gamati on.
1.4.2 Influence of Ionic Strength on Half-wave Potentials
Very accurate measurements poi nt to the fact that the hal f-wave potenti al s of cati ons
depend on the i oni c strength. Get shi fted to more negati ve potenti al s wi th i ncreasi ng
i oni c strength. Thi s i s caused by the dependence of E on the acti vi ty coeffi ci ents of
both the oxi di zed form f and the reduced form f . Thi s i s when the acti vi ti es are
consi dered i nstead of concentrati on. The potenti al of an oxi dati on-reducti on system i s
gi ven by the for mul a:
E = E
0
( )
( )
0
Red
ln
RT
nF ox
...(1)
wher e ( ) denote the acti vi ti es.
On expressi ng the above equati on i n terms of concentrati ons the fol l owi ng equati on
resul ts:
Polarography 7
E = E
0
| |
0
0
[Red]
ln
RT RT f
nF f nF OX
...(2)
The hal f-wave potenti al i s defi ned by the rel ati onshi p
| |
| |
0
0
Red
D
ox D
=
...(3)
On obtai ni ng thi s condi ti on, we obtai n
E = E
0
l n l n
RT f RT D
nF f nF D
...(4)
For the hal f-wave potenti al .
I n thi s equati on the l ast two terms depend on the i oni c strength. I f cati ons are
deposi ted a very di l ute amal gam i s formed and f i s vi rtual l y one. The acti vi ty coeffi ci ent
f of the cati on i n the supporti ng el ectrol yte i s, however, l ess than one and si nce f
decreases wi th i ncreasi ng i oni c strength, E i s shi fted to more negati ve potenti al s.
Li ngane studi ed i t fi rst [2].
Vl cek [1] mode more accurate thermodynami c cal cul ati ons and recommended that
E be extrapol ated to = 0 :
(E )
= 0
= E
0
0
0
l n
RT D
nF D
...(5)
[D
0
and D
0
are the correspondi ng di ffusi on coeffi ci ent for = 0].
The hal f-wave potenti al s cal cul ated from the thermodynami c standard potenti al s
for = 0 agreed wi th the extrapol ated hal f-wave potenti al s as was shown by Vl cek [1]
i n cases of Tl
+
, Pb
2+
and al kal i metal s.
1.4.3 Factors which Affect the Half-wave Potentials
1. The temperature coeffi ci ent of the hal f-wave potenti al i s mostl y between 2
and +2 mv/degree. For a reversi bl e wave i t may be ei ther posi ti ve or negati ve.
For an i rreversi bl e wave i t i s usual l y posi ti ve and may exceed several mi l l i vol ts
per degr ee.
2. The hal f wave potenti al i s al most al ways i ndependent of the concentrati on of
the el ectroacti ve speci es (i.e., of the di ffusi on current) after proper correcti on i s
appl i ed for the iR drop. However, the hal f-wave potenti al of a reversi bl e wave
does not vary wi th concentrati on i f a sol i d product i s termed, or more general l y,
whenever the number of the i ons or mol ecul es of the product of vari abl e acti vi ty
di ffer from the number of i ons or mol ecul es of reactant of vari abl e acti vi ty i n
the equati on for the hal f-r eacti on. Such var i ati ons can be descr i bed onl y by
thermodynami c equati ons. The hal f-wave potenti al of an i rreversi bl e wave may
al so vary wi th concentrati on of the reacti on mechani sm i nvol vi ng some rate
governi ng step that i s not the fi rst- or pseudo-fi rst order. When i t does vary, i t
most often becomes more negati ve as the concentrati on i ncreases.
3. The hal f-wave potenti al of a r ever si bl e wave i s near l y i ndependent of the
capi l l ary characteri sti cs, i.e., m and t. When the di ffusi on cur r ent obeys the
Koutocky equati on and when the di ffusi on coeffi ci ent of the oxi di zed and reduced
speci es di ffer a smal l dependence of the hal f-wave potenti al on t
1/6
and m
1/3
can
be predi cted.
Changes i n m, t and the concentrati on of the el ectroacti ve speci es may, however,
produce apparent vari ati ons of the hal f-wave potenti al unl ess both are corrected.
The iR drop al ways produces an apparent shi ft of the hal f-wave potenti al toward
more negati ve val ues for the cathodi c waves and toward more posi ti ve val ues
for anodi c waves and the shi ft i s proporti onal to the l i mi ti ng current.
4. The hal f-wave potenti al of a total l y i r r ever si bl e wave, however , var i es
si gni fi cantl y wi th t, becomi ng more posi ti ve for a cathodi c wave as t i ncreases.
The magni tude of the var i ati on depends on n
a
and may be used for i ts
eval uati on. Typi cal l y, i f n
a
= 0.5, the hal f-wave potenti al becomes about 20 mV
more posi ti ve i f t i s doubl ed.
5. Changes i n the nature and concentrati on of supporti ng el ectrol yte may effect
the hal f-wave potenti al i n many ways. For reversi bl e waves the effect i s due to
compl ex formati on. Qui te some i nformati on about the i denti ti es and di ssoci ati on
constants of r ever si bl y r educed metal compl exes can be obtai ned fr om
pol arographi c measurements. I n the reversi bl e reducti on or oxi dati on of an
or gani c compound i t i s the pH of the suppor ti ng el ectr ol yte that i s most
i mportant. For such processes i t i s possi bl e to obtai n i nformati on concerni ng
the occurrence and equi l i bri um constants of aci d-base reacti ons i nvol vi ng the
oxi di zed and reduced forms of the coupl e.
6. When a compl ex metal i on i s reversi bl y reduced to a metal sol ubl e i n mercury,
i ts hal f-wave potenti al i s al ways more negati ve than that for the reversi bl e
reducti on of the correspondi ng si mpl e or aquo-compl ex i on. The di fference bei ng
rel ated to the free energy of di ssoci ati on of the compl ex. When compl ex formati on
takes pl ace the hal f-wave potenti al i s usual l y more negati ve when a metal i on
i s reduced to a l ower oxi dati on state and when the product remai ns di ssol ved
i n the sol uti on phase. The opposi te effect i s onl y occasi onal and when i t takes
pl ace i t si gni fi es that the reduced compl ex i s more stabl e than the oxi di zed one.
Hydrogen i on i s nearl y al ways consumed i n the reversi bl e reducti on of an
organi c compound, and as such the hal f-wave potenti al for such a process
al ways becomes more negati ve as the pH i s i ncreased. I t may remai n constant
over a certai n range of pH val ues because of the i nfl uence of pri or or subsequent
proton transfer reacti ons.
7. Compl ex for mati on may cause the hal f-wave potenti al i n the i r r ever si bl e
reducti on of a metal i on to become ei ther more negati ve or more posi ti ve. Thi s
depends on the nature of the l i gand used. Exampl e coul d be of ni ckel i on. The
hal f-wave potenti al i s 1.01 V vs. SCE i n 0.1 F sodi um per chl orate but no wave
i n ethyl ene di ami ne tetra acetate sol uti ons. Where as i n medi a contai ni ng
thi ocyanate or hi gh concentrati on of hal i de, the hal f-wave potenti al s of ni ckel
(I I ) are consi derabl y more posi ti ve than 1.0 V. The reason bei ng that these
Polarography 9
l i gands faci l i tate el ectron transfer and decrease acti vati on energy i nvol ved i n
the reducti on. The hal f-wave potenti al s for the i rreversi bl e reducti on of an
or gani c compound may al so get affected by a chemi cal r eacti on wi th the
supporti ng el ectrol yte. The exampl e coul d be of carbonyl compounds. The hal f-
wave potenti al s are al tered by addi ti on of ammoni a or hydroxyl ami ne, whi ch
converts them i nto i mi nes or oxi mes. I n the absence of any reacti on wi th the
supporti ng el ectrol yte the doubl e l ayer effects and the l i qui d-juncti on potenti al
can al so produce changes i n the hal f-wave potenti al s.
8. When there a change made i n the supporti ng el ectrol yte concentrati on, the
hal f-wave potenti al may be affected i n i rreversi bl e waves. Where upon the rate
of el ectron-transfer steps on equi l i bri um posi ti on of some fast chemi cal reacti on
that precedes i t, coul d be the reason and al so the potenti al di fference between
the el ectrode and that surface and thus the rate of el ectron transfer. The di recti on
and magni tudes of these doubl e-l ayer effects depend on the potenti al at whi ch
the wave occurs, on the nature of i oni c medi um, on the charge on the speci es
actual l y reduced and on the mechani sm by whi ch the reducti on occurs. I n some
cases the hal f-wave potenti al become more negati ve on i ncreasi ng the sal t
concentrati on whi l e i n others i t becomes more posi ti ve. Large shi fts have been
observed. I t i s therefore desi rabl e to keep the nature and concentrati on of the
suppor ti ng el ectr ol yte near l y constant speci al l y whi l e studyi ng i r r ever si bl e
processes. I n studyi ng the behavi our of an organi c compound, the resul ts can
be obtai ned consi stent by usi ng buffers of i denti cal i oni c strengths [3].
9. I n reversi bl e waves, the effects of sal t concentrati on on the hal f-wave potenti al s
ar e due to mass-acti on effects on compl ex equi l i br i a, changes of acti vi ty
coeffi ci ents of the speci es i nvol ved i n the hal f reacti on and vari ati ons of l i qui d-
juncti on potenti al [4]. Al l these can be referred to the data (5) on the hal f-wave
potenti al of cadmi um i on i n ni trate sol uti ons at i oni c strengths up to 12 M.
10. I n non-aqueous sol uti ons havi ng l ow di el ectri c constants, el ectroacti ve i ons wi l l
be l argel y converted wi th i on pai rs or hi gher i oni c aggregates. I n thi s, i t may
be poi nted out that one consequence of the Stern doubl e-l ayer theory i s that the
di el ectri c constant decreases rapi dl y as the el ectrode surface i s approached,
becomi ng as smal l as 2 or 3 or the el ectrode-sol uti on i nterface even i n an
aqueous sol uti on. The tr ansi ent for mati on of an i on-aggr egate under these
condi ti on has no effect on the hal f-wave potenti al of a reversi bl e wave, but
because i t may al ter the charge borne by the el ectroacti ve speci es i t may affect
that of an i rreversi bl e one.
References
1. Vl cek A.A., Chem. Li st Y. 48, 1474 (1954); Col l ecti on Czechosl ov, Chem. Communs. 19,
862 (1954).
2. Li ngane J.J.: J. Am. Chem. Soc. 61, 2099 (1939).
3. Mei tes L.J. El ectroanal . Chem. 5, 270, (1963).
4. Moros, S.A. and Mei tes, L.J. El ectrochem. 5, 103, (1963).
5. Li ngane J.J., El ectroanal yti cal Chemi stry, I ns., N.Y., 2nd ed. 1958, pp. 351415.
CHAPTER 2
THE ELECTRODES
2.1 MERCURY ELECTRODES
Mercury i s wi del y used i n the practi ce of el ectroanal yti cal chemi stry both for worki ng
el ectrodes and for reference el ectrodes, i n the l atter case usual l y as an el ectrode of the
second ki nd.
The use of mercury i s nearl y an i deal choi ce for the constructi on of worki ng el ectrodes
for several reasons. Mercury has a l arge l i qui d range (38.9 to 356.9C at normal
pressure) and therefore el ectrodes of vari ous shapes can easi l y be prepared. The surface
of such el ectrodes i s hi ghl y uni form and reproduci bl e, i f the mercury i s cl ean.
The preparati on of pure mercury i s not very di ffi cul t. Al l metal s wi th a standard
potenti al more negati ve than that of mercury may be oxi di zed easi l y (excepti on bei ng
Ni ckel , whi ch forms an i nter metal l i c compound) by di spersi ng mercury i nto a sol uti on
of i ts sal ts aci di fi ed wi th ni tri c aci d and saturated wi th oxygen. The el i mi nati on from
mercury of metal s more nobl e than i tsel f to accompani ed by repeated di sti l l ati on under
reduced pressure.
One of the most i mportant reasons for the appl i cati on of mercury to the constructi on
of worki ng el ectrode i s the very hi gh over vol tage for hydrogen evol uti on on such
el ectrodes. Rel ati ve to a pl ati num el ectrode, the over vol tage of hydrogen evol uti on
under comparabl e condi ti ons on mercury wi l l be 0.8 to 1.0 V.
I t i s, therefore, possi bl e i n neutral or (better) al kal i ne aqueous sol uti ons to reduce
al kal i metal cati ons at mercury el ectrodes gi vi ng rel ati vel y wel l -defi ned pol arographi c
waves at potenti al s more negati ve than 2.0 V vs SCE.
Usi ng supporti ng el ectrol ytes such as tetra al kyl -ammoni um sal ts, potenti al s as
hi gh as 2.6 V vs SCE i n aqueous sol uti ons, whi l e i n some non-aqueous systems even
3.0 V vs SCE (aqueous) i s possi bl e. Mercury el ectrodes do have seri ous l i mi tati ons i n
appl i cati ons at posi ti ve potenti al s. Sol i d metal and carbon el ectrodes are useful i n such
cases. Oxi dati on of mercury occurs at approxi matel y +0.4 V vs SCE i n sol uti ons of
perchl orates or ni trates si nce these ani ons do not form i nsol ubl e sal ts or stabl e compl exes
wi th mercury cati ons. I n al l sol uti ons contai ni ng ani ons whi ch form such compounds,
oxi dati on of the mercury proceeds at potenti al s l ess than +0.4 V vs SCE. For exampl e,
i n 0.1 M KCl thi s occurs at +0.1 V, i n 1.0 M KI at 0.3 V, and so on.
A number of mercury el ectrodes have been wi del y used for vol tammetry. Of these,
the droppi ng mercury el ectrode (DME) has been extensi vel y used both for anal yti cal
and fundamental studi es. Others are hangi ng mercury drop el ectrode (HDME), streami ng
mercury el ectrode (SME), and mercury fi l m el ectrode (MFE) so al so the stati c mercury
drop el ectrode (I MDE) whi ch i s recentl y devel oped.
2.1.1 Dropping Mercury Electrode
The DME i s the essenti al component of al l pol arographi c experi ments. I t was i ntroduced
by Kucera i n 1903 [1]. Later i n 1921, Heyrovsky appl i ed thi s el ectrode i n the ori gi nal
pol arographi c apparatus [2]. Usual l y, the DME i s formed of gl ass capi l l ary tubi ng
connected to a stand pi pe of pl asti c or gl ass attached to a mercury reservoi r. When the
l evel of the mercury i n the standpi pe i s suffi ci entl y hi gh wi th respect to the ti p of the
capi l l ary, mercury fl ows from the capi l l ary at a steady rate and smal l drops from at the
end and fal l at a regul ar i nterval . These drops have nearl y spheri cal shape i f thei r
mass i s not greater than about 15 mg and the radi us of the capi l l ary i s of the order
of 0.05 mm. El ectrol ysi s i s carri ed out on the surface of the mercury drops. One of the
most i mportant advantages of (DME), as gi ven further, i s the conti nuous renewal of the
el ectrode surface. The peri odi ci ty of thi s renewal i s governed by the l i fe of an i ndi vi dual
dr op.
The basi c concept i nvol ved i n the formati on of mercury drops are used to defi ne the
capi l l ary characteri sti cs requi red for sati sfactory el ectrodes. Thi s i s parti al l y di scussed
by Kol thoff and Li ngane [3].
2.1.2 Flow of Mercury from Capillaries
The rate of fl ow of a l i qui d through a capi l l ary can be defi ned by the Poi seui l l e equati on.
The vol ume V of l i qui d that fl ows i n ti me t i s gi ven by
4
8
c
n
r Pt
V
l
=
...(i)
where r
c
and l are the i nternal radi us of a capi l l ary and i ts l ength, n i s the vi scosi ty
of the fl owi ng l i qui d, and P i s the effecti ve hydrostati c pressure (i.e., P i s not exactl y
equal to the pressure created by the di fference between the l evel of l i qui d i n the
reservoi r and the l ower end of the capi l l ary).
The above equati on can be r ear r anged to fr om
4
8
c
n
r Pd Vd
m
t l
= =
...(ii)
where d i s the densi ty of the l i qui d.
The effecti ve pressure that acts on the mercury i s not exactl y equal to the total
pressure, P
t
, whi ch i s gi ven by the equati on
P
t
= h
t
gd ...(iii)
where h
t
i s the verti cal di stance between the end of the capi l l ary and the l evel of the
mercury i n the reservoi r and g i s gravi tati onal constant.
Mercury fl ows from the capi l l ary i n smal l drops. The si ze of these drops i s determi ned
by the i nterfaci al tensi on at the mercury sol uti on i nterface. The i nternal pressure i n
the drop acti ng agai nst P
t
i s, accordi ng to Kucer a [1], gi ven by the r el ati on
P
b
=
2r
r
...(iv)
Thi s i nternal pressure P
b
, often cal l ed back pressure i s proporti onal to the i nterfaci al
tensi on r at the mercury sol uti on i nterface and i s i nversel y proporti onal to the radi us
of the dr op.
Equati on (iv) shows that the back pressure i n a gi ven sol uti on changes wi th the
growth of a drop and reaches the smal l est val ue at the moment of detachment of a drop
from the capi l l ary. Taki ng an exampl e, a capi l l ary wi th an i nternal di ameter of 0.06
mm pl aced i nto 3 M KCl at a potenti al 0.6 V, the back pressure changes from 10.44
to 0.97 cm of mercury duri ng the l i fe of the drop. I f the mercury col umn i s l ower than
the fi rst val ue, obvi ousl y the outfl ow of mercury wi l l not be observed.
For constructi on of the el ectrode (DME) capi l l ari es are commerci al l y avai l abl e. I n
case i t i s to be prepared from capi l l ary tubi ng
manual l y, the uni formi ty i s the pri me consi de-
rati on. The l ength of the capi l l ary used depends
on i ts i nternal di ameter and on the experi mental
objecti ves. Usual l y, the l argest drop ti mes shoul d
not exceed 78 sec. I n gener al , the capi l l ar y
shoul d be such as to gi ve a drop ti me of the
or der of 34 wi th h
t
equal to ca. 40 cm when
the capi l l ary i s di pped i nto sol uti on. I f drop ti mes
are too l ong, i t shoul d be cut because a l i near
dependence exi sts between l ength of the capi l l ary
and t
d
.
The mercury reservoi r usual l y has a vol ume
var yi ng between 100 and 200 cm
3
. The pl ati num
wi re used to make contact to the DME may be
di pped i n mercury reservoi r or seal ed i n the
stand tube. The common assembl y used i s shown
i n Fi g. 2.1. The connecti on to the mer cur y
reservoi r i n normal l y made usi ng a soft pl asti c
tubi ng such as Tygon. The i nsi de di ameter of
thi s tubi ng shoul d be of the order of 57 mm
and the connecti on to the capi l l ary shoul d be
rei nforced wi th wi re.
Once the capi l l ary has been connected, the
mer cur y r eser voi r shoul d be fi l l ed wi th pur e
mercury (tri pl y di sti l l ed mercury). Whi l e fi l l i ng
entrappi ng of ai r bubbl es shoul d be mi ni mi sed.
The DME requi res a stand that faci l i tates
changi ng posi ti on of the mercury reservoi r. The
mercury reservoi r shoul d al ways be el evated and
the fl ow of mercury observed, before the capi l l ary
Mercury
Reservoir
Drop knocking
device
Capillary
Fig. 2.1 : Mer cur y r eser voi r assembl y
for use i n droppi ng mercury el ectrodes
The Electrodes 13
i s pl aced i n an experi mental sol uti on. When the experi ment i s over, the capi l l ary be
pl aced i n di sti l l ed water, washed wel l wi th i t (i f requi red non-aqueous sol vent). Mercury
shoul d drop there before washi ng.
For parameters characteri zi ng the DME coul d be determi ned i n the fol l owi ng way.
The capi l l ary i s pl aced i n a sol uti on of the supporti ng el ectrol yte. The mercury reservoi r
i s adjusted to a gi ven h
t
and a potenti al i s appl i ed, ei ther a val ue rel ated to experi mental
measurements or i n the range 0.5 to 0.6 V vs S.C.E. A stop watch i s used to measure
the ti me for 1020 drops to form and the drop ti me, t
d
, i s obtai ned by di vi di ng the
el apsed ti me by the number of drops col l ected. Mass fl ow rate of mercury, m, can be
measured by col l ecti ng drops for a measured ti me and then wei ghi ng the washed and
dri ed mercury. Usual uni ts are mi l l i grams per second.
2.1.3 Advantages of DME
The droppi ng mercury el ectrode has several advantages over sol i d el ectrodes, these are
summari zed as fol l ows :
1. The drops are very easi l y reproduced and thus gi ve reproduci bl e resul ts. The
regul ar droppi ng of pure mercury ensures that the el ectrochemi cal process
al ways occur s at a fr esh sur face, vi r tual l y i ndependent of the pr ecedi ng
pol ari zati on. As al ready i ndi cated the resul ts obtai ned i n thi s manner are
reproduci bl e regardl ess of the i rregul ar droppi ng i n case preci pi tates are formed.
The regul ar renewal of the surface ensures that the current i s i ndependent of
the ti me of el ectrol ysi s and that the current vol tage curve i s the same whether
recorded wi th i ncreasi ng or decreasi ng vol tages or even rapi dl y or sl owl y.
2. Owi ng to the very hi gh over vol tage of hydrogen towards mercury, the DME can
be used over a consi derabl e cathodi c range of potenti al s wi thout i nterference
from hydrogen evol uti on. Pol arographi c curves for al kal i metal i ons may be
r ecor ded befor e hydr ogen evol uti on takes pl ace. I nstead of mer cur y di l ute
amal gams may drop from the droppi ng el ectrode and anodi c processes i n the
di ssol uti on of the l ess nobl e metal s may be studi ed. Wi th commonl y used
supporti ng el ectrol ytes, such as potassi um chl ori de and potassi um ni trate, the
r ange extends to about 1.8 V (vs SCE).
3. I n vi ew of the behavi our of mer cur y as a nobl e metal , r el ati vel y posi ti ve
potenti al s, but not of course exceedi ng that for the di ssol uti on of mercury (about
+0.4 V vs NCE) may be appl i ed to the DME and the el ectrode may serve as an
i ndi fferent redox el ectrode for the study of oxi dati on reducti on systems. Moreover,
i t i s not subject to passi vati on or poi soni ng owi ng to constant renewal of mercury
surface. Thi s i s i n contrast to other el ectrodes.
4. Onl y smal l quanti ti es of substances are deposi ted i n the vi ci ni ty of the droppi ng
el ectr ode dur i ng el ectr ol ysi s. For the r eason ther e i s no depl eti on of the
depol ari zer i n the sol uti on provi ded the vol ume of the el ectrol yzed sol uti on i s
not too smal l . The curves obtai ned are i denti cal even after several runs.
5. Ther e i s al so an i mpor tant factor for the appl i cati on of pol ar ogaphy i s
mi croanal ysi s because wi th a thi n drawnout capi l l ary the el ectrol ysi s of very
smal l vol umes (0.01 0.005 ml ) may be studi ed.
6. Processes may be studi ed that take pl ace i n aqueous sol uti on i n the potenti al
r ange +0.4 to 2.6 V; and i n non-aqueous sol uti on upto 3.0 V (mi x of di oxan
and water) agai nst the (NCE) normal cal omel el ectrode. At potenti al s more
posi ti ve than +0.4 V anodi c di ssol uti on of mercury and at potenti al s more
negati ve than 2.6 V (or 3.0 V) decomposi ti on of water or of the gi ven sol vent
takes pl ace. Besi des, the advantages the use of DME i s somewhat restri cted. At
posi ti ve potenti al s mercury undergoes oxi dati on and therefore other type of
el ectrodes (standi ng mercury el ectrode or sol i d el ectrodes) must therefore be
used.
The vol ati l i ty of mer cur y pr events the use of the DME i n mel ts at hi gher
temperatures. Good resul ts are obtai ned at temperatures upto 100C.
2.1.4 Hanging Mercury Drop Electrode
(a) HMDE Suspended on a Metallic Contact : A si mpl e HMDE was devel oped by
Geri scher [4]. Usi ng thi s approach 1 or 2 mercury drops fal l i ng from the cl assi cal
DME are col l ected on a mi ni ature spoon and transferred to a smal l metal
contact scal ed i s gl ass or pl asti c materi al (Fi g.
2.2). The l ength of the exposed contact wi re i s
usual l y on the order 0.10.5 mm and i ts di ameter
i s about 0.5 mm.
El ectr odes of thi s sor t have many di ffer ent
chemi cal properti es from pure mercury el ectrodes,
because of the formati on of a gol d or pl ati num
amal gam [5]. Normal l y, a drop i s suspended just
pr i or to an exper i ment and thi s pr obl em wi l l ,
ther efor e, be of no consequence. Never thel ess,
si nce the sol ubi l i ty of these nobl e metal s i n
mercury i s of the order of 0.05 M, the concent-
rati on of gol d or pl ati num i n mercury may be
qui te si gni fi cant on a l onger ti me scal e. I n such
cases gol d or pl ati num may form i ntermetal l i c
compou n ds wi th s ev er al metal s wh i ch ar e
el ectrodeposi ted i nto the mercury [5].
(b) Capillary HMDE : Thi s type of the HMDE consi sts
of a smal l mercury drop wi th radi us usual l y not
exceedi ng 1 mm whi ch hangs on a thi n mer cur y
thread i n a gl ass capi l l ary. The i nner di ameter of
thi s capi l l ary i s about 0.150.21 mm, consi derabl y
l arger than for the DME. An el ectrode of thi s
type was used for the fi rst ti me by Antwei l er [6].
Preparati on of reproduci bl e HMDE as per thi s
ori gi nal model was very di ffi cul t. Kemul a and Kubl i k [7] poi nted out that
suspended HMDE i s mor e r epr oduci bl e i n compar i son to the ear l y desi gn
capi l l ary HMDEs.
Threaded plunger
Plastic collar
Reservoir and
Capillary (glass)
Fig. 2.2 : Assembl ed uni t,
Hangi ng Mercury Drop
El ectrode
The Electrodes 15
I n the most successful desi gns, the mercury i s pushed out mechani cal l y. Randl es
and Whi te [8] used thi s type of el ectrode, where mercury was pushed from the capi l l ary
by turni ng mi crometer screw. The most popul ar el ectrode used these days was devel oped
by Kemul a and Kubl i k [7].
A detai l ed assembl y of thi s el ectrode i s shown i n Fi g. 2.2. I t i s composed of a thi ck
wal l ed gl ass tubi ng wi th an i nternal di ameter of 4 mm, approxi matel y 5 cm l ong. Thi s
forms a mercury reservoi r whi ch i s seal ed to a thi ck wal l capi l l ary. The i nternal di ameter
of thi s capi l l ary i s commonl y 0.18 mm, but may vary somewhat around thi s val ue.
The l ength of the capi l l ary wi l l depend on the si ze of the el ectrol yti c cel l . A ground-
gl ass joi nt on the mercury reservoi r can provi de a conveni ent means of supporti ng
el ectrode i n a cel l . A Tefl on thermometer adapter al so works wel l . The top of the
reservoi r resembl es a gl ass ri ng whi ch i s fl at and very smoothl y pol i shed. Thi s part of
the el ectrode i s connected to the pl asti c head, whi ch i s composed of two parts. These
parts are shown i n Fi g. 2.2. After the capi l l ary i s i nserted through part b, part c is
screwed rather ti ghtl y i nto part b. The end of the mercury reservoi r shoul d then be
ti ghtl y seal ed by the bottom part c.
To provi de a ti ght seal a smal l pl asti c cyl i nder i s extended from part c, bei ng bi t
thi cker than the i nternal di ameter of the gl ass tubi ng. Thi s smal l cyl i nder, schemati cal l y
shown i n Fi g. 2.2, shoul d enter i nto the reservoi r tubi ng wi th a pressed fi t when al l
parts of the HMDE are put together.
A threaded steel pi ston of 2 mm i n di ameter moves i n part c. By turni ng thi s screw
by a fi xed angl e, for i nstance 90 or 180 mercury wi l l be pushed out from the capi l l ary
and wi l l hand as a drop from i ts end. I t i s i mportant that the pi ston screw be set ti ght
i n the pol yethyl ene par t as shown i n Fi g. 2.2.
I n Fi g. 2.2 the HMDE i s shown ready for use. To ensure that the el ectrode works
properl y, speci al care shoul d be taken to coat the i nternal part of the capi l l ary wi th a
hydrophol i c si l i cone fi l m. The capi l l ary shoul d be thoroughl y cl eaned before a new
coati ng i s appl i ed. Sodi um hydroxi de (2 M) shoul d be used to remove any resi dual
si l i cone. The capi l l ary shoul d them be washed wi th 3 M ni tri c aci d, ri nsed wi th di sti l l ed
water, and dri ed thoroughl y. Then a 5% sol uti on of di chl orodi methyl si l ane i n CCl
4
is
pul l ed through the capi l l ary, fol l owed by ai r. After several hours at room temperature
or about 15 mi n. at 110C, the capi l l ary i s ready for use. The si l i cone coati ng shoul d
be renewed from ti me to ti me. Speci al l y when rangi ng drop tends to fal l duri ng an
experi ment. Thi s happens when the si l i cone coati ng and the capi l l ary wal l i s partl y
destroyed and sol uti on enters between the gl ass and the mercury thread.
The mercury reservoi r and the capi l l ary shoul d be compl etel y fi l l ed wi th mercury.
There must be no entrapped ai r. The vessel shoul d be fi l l ed wi th mercury such that the
end of the capi l l ary i s covered when the vessel i s pl aced i n a hori zontal posi ti on. Wi th
al l of the mercury i n part b, the vessel i n connected to a vacuum pump, wi th a three
way stop cock to decrease the pressure i n the vessel and i n the el ectrode down to 0.01
mm.
After evacuati on, the vessel i s ti l ted i nto the hori zontal posi ti on as shown i n the
Fi g. 2.3 and the stop cock i s turned to di sconnect the pump and then turned further
to admi t ai r i nto the vessel . The pressure of ai r acti ng on the mercury i n the vessel
3 mm spectroscopic
graphite
7 mm O.D. Pyrex
tubing
Teflon insert machined
for press fit
10 mm
Polished flat
Fig. 2.3 : Conventi onal Carbon Paste El ectrode
pushes i t i nto the reservoi r and the capi l l ary of the HMDE. I f the pressure had been
decreased to 0.01 mm, mercury fi l l s i n the reservoi r and capi l l ary compl etel y. The
HMDE i s now r eady for use. By tur ni ng the scr ew to a fi xed angl e, a known amount
of mercury i s pushed out, formi ng a drop.
Such an el ectrode can be prepared i n the l aboratory. These el ectrodes are equi pped
wi th a mi crometer type of screw of pressi ng out a wel l -defi ned amount of mercury.
2.2 CARBON ELECTRODES
Many i nteresti ng reacti ons can be studi ed whi ch are not accessi bl e at a mercury surface.
A wi de range of materi al s have been empl oyed as sol i d el ectrodes, but the nobl e metal s
parti cul arl y pl ati num and gol d, and carbon have emerged as the most popul ar ones.
The i deal properti es of a materi al for use as sol i d el ectrode are that: (i) i t shoul d
be easy to i ncorporate i nto an el ectrode, (ii) i t shoul d have a l ar ge potenti al r ange, a
l ow el ectri cal resi stance, and (iii) an easi l y reproduci bl e surface. These cri teri a are met
onl y to some degree by many materi al s. The properti es of vari ous types of carbon make
i t the materi al of choi ce for many appl i cati ons.
2.2.1 Carbon Paste Electrodes
The carbon paste el ectrodes (CPE) was i ntroduced by Adams [8] and general l y consi sts
of a Tefl on wel l i nto whi ch i s i nserted a
pl ati num, copper , steel or gr aphi te
contact. The Tefl on wel l may be mounted
i n the end of a sui tabl e gl ass tube or
consi sts si mpl y of a pi ece of Tefl on tube
as i l l ustrated i n the Fi g. 2.3.
The wel l i s fi l l ed wi th a paste, made
by mi xi ng powder ed gr aphi te wi th a
sui tabl e mul l i ng l i qui d. Practi cal consi d-
erati on requi re that the mul l i ng l i qui d
shoul d have a l ow vol ati l i ty, puri ty wi th
respect to el ectroacti ve i mpuri ti es, and
very l ow sol ubi l i ty i n the medi um to be
empl oyed. These consi derati on general l y
l i mi t the choi ce of mul l i ng l i qui d to
br omofor m, br omon aph th al en e, or
mi neral oi l (Nujol ).
Preparation : A typi cal paste for
CPE may be prepared by mi xi ng Nujol
and gr aphi te powder thor oughl y (coul d
be UCP 1 M fr om u l tr a car bon
cor por ati on ) u n ti l th e mi x tu r e i s
uni forml y wetted. The resul tant paste
shoul d have a consi stency si mi l ar to that
The Electrodes 17
of peanut butter. The best woul d be to take 3 gm of carbon to 2 ml of oi l . Carbon rough
surface shoul d not be used si nce they gi ve poorer peak current reproduci bi l i ty. Pastes
that appear sati sfactory for conventi onal experi ments at mi l l i mol ar concentrati on may
gi ve ri se to many di sconcerti ng background peaks when pul se vol tammetry at the
mi cromol ar l evel i s tri ed. Hi gh puri ty graphi te i s i mportant and the graphi te (and
paste) shoul d not be unnecessari l y exposed to the l aboratory atmosphere. I t i s advi sabl e
to di vi de freshl y prepared paste i nto l ots of about 1 gm and to store these i n smal l wi de
mouth vi al s.
I n practi ce a smal l amount of paste i s pl aced on a cl ean card (coul d be an unused
I BM computer card); the el ectrode i s gentl y pressed i nto thi s pi l e and then rubbed on
the card to remove excess paste and to attai n a fl at surface. The wel l i s fi l l ed compl etel y,
l eavi ng no hol es or channel s. Any paste remai ni ng on the mantl e i s careful l y wi ped
away wi th a paper ti ssue. El ectrodes may be assembl ed and packed i n quanti ty and
stored i n covered box. El ectrodes may be renewed by removi ng a smal l amount of paste
from the surface wi th a paper ti ssue and repacki ng wi th fresh paste.
I t i s i mportant to note that when packi ng the wel l , avoi d appl yi ng too much pressure.
Thi s may resul t i s separati on of the carbon and oi l . Thi s woul d resul t i n hi gh resi stance
contact between the paste and the metal .
Other methods of pastes and el ectrode preparati on are bei ng descri bed by many
wor ker s.
The formul ati ons and methods of preparati on of the CPE as descri bed above are
qui te sati sfactory for use i n aqueous sol uti ons contai ni ng perhaps as much as 25%
al cohol or other sol vents. However, when carbon paste el ectrodes of thi s type are used
i n non-aqueous medi a (e.g., acetoni tri l e, ni tromethane, propyl ene carbonate), the pool
of carbon paste tends to di si ntegrate. The cause of thi s di si ntegrati on appears to be
di ssol uti on of the mul l i ng l i qui d or the preferenti al wetti ng of the graphi te by the
sol vent. Thi s di ffi cul ty can be overcome by addi ti on of a surface acti ve agent, such as
sodi um l auryl sul phate, to the paste [15]. The advantage i s that the l atter compound
causes the graphi te to be wetted equal l y wel l by both, mul l i ng l i qui d and the non-
aqueous sol vent.
I t i s a normal practi ce to prepare a new el ectrode surface before runni ng each
vol tammogram. Thi s i s done by removi ng the surface l ayer of paste and refi l l i ng the
Tefl on hol der. Thi s i s qui ckl y reproduci bl e manual l y as recommended by many workers.
The preparati on of a CPE wi th an i ncreased posi ti ve potenti al range (+ 1.7 V vs
SCE i s 0.1 M H
2
SO
4
) has al so been descr i bed [17].
I t has been reported by several authors that adsorpti on of el ectroacti ve speci es at
the el ectrode surface takes pl ace whi l e usi ng CPE. Thi s may be due pri mari l y to the
di ssol uti on of the el ectroacti ve speci es i n the organi c phase of the CPE, al though the
effect i s not of a major i mportance.
Al l carbon paste el ectrodes descri bed i n the l i terature have been desi gned for
vol tammetri c studi es. The range of potenti al s over whi ch the CPE can be used i n qui te
l arge (l arge l i terature val ues are avai l abl e).
2.2.2 Glassy Carbon Electrode
Gl assy carbon was fi rst used as an el ectrode materi al
by Zi ttel and Mi l l er [34], al though i t i s commerci al l y
avai l abl e.
For thi s el ectrode a l ength of 3 mm di ameter gl assy
carbon rod i s scal ed i nto a l ength of 5-mm tubi ng
wi th epoxy cement. A few mi l l i meters of carbon are
then exposed then fr om the end of the gl ass tube
usi ng a gl ass cutti ng wheel . The end of gl ass tube-
car bon r od assembl y i s then pol i shed wi th emer y
paper, fol l owed by pol i shi ng al umi na unti l a mi rror
fi ni sh i s obtai ned. Before each vol tammogram i s run
the el ectrode i s buffed for about 5 sec. wi th 1 m
al umi na, ri nsed and pl aced i n the el ectrochemi cal cel l .
Some authors al so used the el ectrode for stri ppi ng
anal ysi s and others have used i t i n mol ten sal ts as
wel l .
Typi cal data on posi ti ve and negati ve potenti al
l i mi ts at GCE are gi ven i n the l i terature.
Methods to modi fy the el ectrode are al ready i n
pr ogr ess.
2.3 POLAROGRAPHIC CELLS AND
SATURATED CALOMEL ELECTRODE
I t i s a l ong-standi ng custom of referri ng al l pol arographi c potenti al s to the saturated
cal omel el ectrode. Thi s i s done to permi t compari son of hal f-wave potenti al s measured
i n di fferent medi a. Si nce the potenti al of an i nternal reference el ectrode vari es from
one medi um to another such compari sons can be made onl y i f the potenti al of the
i nternal el ectrode i s measured agai nst an external saturated cal omel el ectrode.
The cel l i s that porti on of the apparatus whi ch contai ns the sol uti on bei ng studi ed.
I t al so i ncl udes a non-pol ari zabl e el ectrode to whi ch the potenti al of the droppi ng
el ectrode i s referred. Oxygen must usual l y be removed by bubbl i ng an i nert gas through
the sol uti on before measurement, because oxygen i s reduci bl e at the droppi ng el ectrode
over most of the range of potenti al s whi ch are i mportant i n pol arography. I t may al so
have other undesi rabl e effects.
The most i mportant part of a cel l i s i ts reference el ectrode. The pol arograph appl i es
a vol tage across the cel l ; even negl ecti ng for the moment the iR drop. Any vari ati on or
error i n the potenti al of the reference el ectrode l eads to a correspondi ng uncertai nty i n
the potenti al of the droppi ng el ectrode. I t i s al so i mportant that the potenti al of the
reference el ectrode be not onl y known but al so essenti al l y i ndependent of the current
fl owi ng through i t. Two ki nds of reference el ectrodes are i n general use. These are
i nternal and external el ectrodes, whi ch are general l y used. An i nternal el ectrode i s
i n di rect contact wi th the sol uti on bei ng studi ed, whi l e the external el ectrode i s separated
5 mm O. D. Pyrex t ubi ng
Mercury
3 mm Gl assy Carbon
sealed with epoxy resin
The Electrodes 19
Fig. 2.4 : Typi cal Gl assy
Car bon el ectr ode for
Vol tammetri c Studi es
from i t by a sal t bri dge or a porous membrane. I nternal reference el ectrodes cannot be
used i n sol uti ons contai ni ng oxi di zi ng agents whi ch have power ful ener gy to oxi di ze the
el ectrode metal , or reduci ng agents are powerful enough to reduce the poi si ng sal t
(Ag X, Hz
2
X
2
). Not are they as useful when the droppi ng el ectrode i s the anode or when
i t i s the cathode. I n the former case the sol uti on i s usual l y capabl e of reduci ng the
poi soni ng sal t chemi cal l y, and even of thi s reacti on were sl ow the poi soni ng sal t woul d
be reduced at the reference el ectrode as the pol arogram was recorded.
External reference el ectrodes, on the other hand have potenti al s that are ei ther
accuratel y known or can be measured once and for al l (usual l y the SCE i s used) and
that are i ndependent of the composi ti on of the sampl e sol uti on. Wi th thi s onl y very
fr equent checki ng i s needed to ensur e that no contami nati on has occur r ed. When
car eful l y used they r ar el y need r enewi ng. They may be used wi th sol uti on contai ni ng
strong oxi di zi ng or reduci ng agents. They al so render the presence of a depol ari zi ng
ani on i n the sampl e unnecessary, thereby permi tti ng the range of the droppi ng el ectrode
to be extended to somewhat more posi ti ve potenti al s.
The most wi del y used cel l wi th an
external reference i s the H-cel l .
A sampl e i s shown i n Fi g. 2.5. I t consi sts
of two compar tments. One contai ni ng the
s ol u ti on bei n g s tu di ed an d th e oth er
contai ni ng the reference el ectrode. To avoi d
pol ari zati on of the reference el ectrode, the
compartment contai ni ng i t shoul d be made
fr om tubi ng of at l east 20 mm i .d. The
di mensi on of the sol uti on compartment can
be vari ed wi del y to accommodate any desi red
vol ume of sol uti on. As per the Li ngane-
Lai ti nen cel l as shown i n the Fi g. 2.5, these
compar tments ar e separ ated by a cr oss-
member fi l l ed wi th a 4% agar -satur ated
potassi um chl ori de gel , whi ch i s hel d i n pl ace
by a medi um-parosi ty si ntered-Pyrex di sc.
I n or der to faci l i tate r api d and compl ete
deaerati on of the sol uti on, the di sc shoul d
be pl aced as n ear to th e s ol u ti on
compartment as possi bl e. At the same ti me
the si de tube through whi ch the i nert gas i s
passed through the sol uti on shoul d be as
near to the bottom of the cel l as possi bl e.
The agar gel i s prepared by warmi ng 4
gm of agar and 90 ml of water i n a smal l
fl ask whi ch i s put i n l arge beaker fi l l ed wi th
boi l i ng water or on a steam bath unti l
sol uti on i s compl ete. After thi s 30 gm of
Fig. 2.5 : H-cel l and stand tube accordi ng to
Li ngane and Lai ti nen
10 cm.
Reference
Cell
Sintered
Glass Disc
Solution
of Sample
Agar
Plug
Nitrogen
Inlet
Tubes
Annular
Space for
Escape of
Nitrogen
For Contact
To Reference
Electrode
Capillary Tube
75 cm
Constant-
Head
Mercury
Reservoir
For Contact to
Mercury Column
potassi um chl ori de are added and the whol e thi ng i s sti rred thoroughl y. After thi s the
gel i s al l owed to sol i di fy whi ch must be whi te to avoi d contami nati on of the sol uti on
comi ng i n contact wi th i t. When the sal t i s di ssol ved, the cl ean dry cel l i s cl amped wi th
the cross-member verti cal and the sol uti on compartment down. The gel i s pi petted i nto
the cross-member unti l i t i s al most compl etel y fi l l ed. The cel l i s then al l owed to stand
undi sturbed unti l the gel i s sol i di fi ed. The unused gel may be stored i n a l i ghtl y
stoppered fl ask whi ch coul d be used agai n after rel i qui ng i t.
After the gel i s sol i di fi ed, the cel l i s turned upri ght the enough pure mercury i s
added to the reference-el ectrode compartment to gi ve a l ayer 1 to 2 cm deep. Thi s i s
then covered wi th an equal l y thi ck l ayer of a paste made by sti rri ng equal wei ghts of
mercurous and potassi um chl ori des wi th a l i ttl e saturated potassi um chl ori de. The
compartment i s then fi l l ed wi th saturated potassi um chl ori de sol uti on contai ni ng a
l arge excess of sol i d sal t. El ectri cal connecti on to the mercury i s made by means of a
gl ass tube through whi ch a smal l pl ati num wi re i s seal ed so as to project i nto the
mercury for a few mi l l i meters. Thi s tube i s fi l l ed wi th mercury and i nserted i nto a
rubber stopper whi ch serves to seal the reference-el ectrode compartment l i ghtl y. The
wi re l eadi ng to the reference-el ectrode termi nal of the pol arograph i s si mpl y di pped
i nto the mercury i n thi s tube.
The sol uti on compartment of the cel l shoul d fi nal l y be fi l l ed wi th saturated potassi um
chl ori de sol uti on and a day or two shoul d be al l owed for the SCE to attai n equi l i bri um.
Whi l e i n use, the sol uti on compartment i s empti ed, washed wi th water and ei ther
dri ed or ri nsed wi th several porti on of the sampl e. Then enough sol uti on i s added to
cover the enti re fri tted di sc.
Di ssol ved ai r i s removed by passi ng ni trogen i nto the si de tube so that i t bubbl es
through the sol uti on. Measurements shoul d not be attempted whi l e the gas i s bubbl i ng
through the sol uti on. Sti rri ng may cause hi gh errati c currents. Fi nal l y the droppi ng
el ectrode i s i nserted through another hol e i n the stopper and the measurements be
carri ed out. I t i s advi sabl e to keep two cel l s avai l abl e i n routi ne work so that the
sol uti on can be deaerated i n one whi l e the other sol uti on i s bei ng exami ned i n the
other cel l .
I nserti on of droppi ng el ectrode shoul d be deferred to avoi d prol onged contact between
mercury and the sol uti on. I f i t i s i nserted before deaerati on i s compl ete, mercurous or
mercuri c i on may be formed accordi ng to the reacti on:
4 Hg + O
2
+ 4H
+
= 2Hg
2
++
+ 2H
2
O
I n case, the sol uti on i n aci di c and contai ns no i on yi el di ng i n sol ubl e mercury sal t,
or an appreci abl e fracti on of a heavy metal i on may be l ost by a reacti on l i ke
Pb
++
+ 2Hg + 2Cl
+
1
2
O
2
+ H
2
O = Hg
2
Cl
2
+ Pb(OH)
2
i f the sol uti on i s neutral and unbuffered.
The sol uti on compartment of an H-cel l shoul d never be al l owed to stand empty for
more than a few mi nutes at a ti me. The agar bri dge wi l l dry out and shri nk, al l owi ng
bul k fl ow of the l i qui d between the two compartments of the cel l . I t shoul d al ways be
The Electrodes 21
kept fi l l ed wi th ei ther water or, for overni ght or l onger peri od wi th saturated potassi um
chl ori de. Mercury must al so be removed before the cel l i s al l owed to stand even overni ght
to avoi d ai r oxi dati on of mercurous sal ts.
Contami nati on of H-cel l must be avoi ded usi ng vari ous sampl es.
2.4 MERCURY POOL ELECTRODE
Mer cur y pool r efer ence el ectr ode has been wi del y used si nce the begi nni ng of
pol arography. I t i s si mpl y a pool of pure mercury on the bottom of the cel l , connected
to the pol arograph vi a a pl ati num wi re seal ed through the wal l of the cel l . The area
of the mercury pool el ectrode shoul d not be too smal l but need not exceed several
square centi meters. Mi cro cel l s of vari ous si zes can al so be used whi ch may contai n
smal l vol umes of sol uti on.
Mercury pool el ectrodes shoul d be used onl y i n sol uti ons that contai n i ons gi vi ng
i nsol ubl e mercurous or mercuri c i ons.
References
1. Kucera, B. Ann. Phys. 11:529 (1903).
2. Heyrovspy, J., Chem. Li sty 16:256 (1992) Phi l os. Mag. J. Sci . 45:303 (1923).
3. Kol thoff, I .M., and Li ngane J.J., Pol arography, Vol . I , I nter Sci ence, N.Y. 1952.
4. Geri scher, M., Z. Phys. Chem. 202:302 (1953).
5. Kemul a M. and Coworbers, Bul l . Acad., Pol . Sci . Cl . 111 7:73 (1959).
6. Ant Wei l er, H.J., Z. El ectrochem. 44:831 (1938).
7. Kemul a W., and Kubl i k Z., Advances i n anal yti cal Chemi stry and I nstrumentati on,
Vol . 2, Wi l ey I nt. N.Y. (1963) p. 123.
8. Randl es, J.E.B. and Whi te. W., Z. El ectrochem. 59:666 (1955).
9. Adams R.N., Anal . Chem. 30:1576 (1958).
10. Marcoux, L.S. and Coworbers, Abel . Chem. 37:1446 (1965).
11. Li nd qui st, J. Anal . Chem. 45:1006 (1973).
12. Zi ttel , H.E. and Mi l l er, F.J., Anal . Chem. 37:200 (1965).
CHAPTER 3
THE TECHNIQUE
3.1 POLAROGRAPHIC CIRCUIT
Pol arography consti tutes a uni que type of el ectrol ysi s i n that i t i nvol ves the study of
current vol tage rel ati onshi ps at a droppi ng mercury el ectrode under certai n control l ed
condi ti ons.
A current-vol tage (or current-potenti al ) curve can be obtai ned by gradual l y i ncreasi ng
the appl i ed vol tage and measuri ng the correspondi ng mean currents; pl otti ng the
currents agai nst vol tage. I n order to avoi d ti me consumi ng measurements and curve-
pl otti ng, automati c recordi ng pol arographs are avai l abl e. These i nstruments serve for
recordi ng based on el ectrochemi cal pol ari zati on.
Any el ectrol ysi s i nvol ves two mai n types of processes, e.g., transference of matter
through a sol uti on towards and away from el ectrodes and el ectrochemi cal processes
i nvol vi ng as an essenti al part the exchange of el ectrons at the el ectrode surfaces.
Duri ng an el ectrol ysi s, three mass transfer processes are of i mportance, namel y,
mi grati on, di ffusi on and convecti on. The fi rst of these i s an el ectri cal effect dependi ng
upon the charge carri ed by an el ectroacti ve speci es and upon i ts transference number.
Thus, the effect i s encountered onl y wi th charged speci es. Si nce processes of di ffusi on
are non el ectri cal i n ori gi n, these are for al l speci es i n sol uti on whether they are
charged or not. Convecti on effects i ncl ude moti on of smal l parti cl es under the i nfl uence
of sti rri ng, mechani cal agi tati on, and temperature gradi ents.
3.2 THE SIGNIFICANCE OF DIFFUSION IN CLASSICAL POLAROGRAPHY
Whi l e studyi ng the pol arographi c work, the mi grati on effect i s usual l y el i mi nated and
i t i s usual to study the oxi dati on or reducti on of el ectroacti ve speci es i n sol uti on under
condi ti ons such that the l atter arri ves at the i ndi cator el ectrode by natural di ffusi on
onl y. Suppressi on of mi grati on effect i s achi eved by mi xi ng together wi th the speci es
under study, an excess of supporti ng el ectrol yte or i ndi fferent el ectrol yte normal l y
50100 fol d i s excess of the el ectroacti ve component of the sol uti on. Thi s added el ectrol yte
i s so chosen that no el ectrode reacti ons characteri sti c of i t i nterferes wi th those of the
speci es under i nvesti gati on. Supporti ng el ectrol ytes serve as current carri ers and, by
vi rtue of bei ng i n excess effecti vel y reduce thei r transference numbers to zero.
Convecti on effects are el i mi nated by carryi ng out the el ectrol ysi s i n adequatel y
control l ed thermostats so as to protect the apparatus from al l forms of shocks and
vi br ati ons.
Basi cal l y, pol ar ogr aphy consi sts of
el ectrol ysi ng a sol uti on contai ni ng several
cati ons between a dr oppi ng mer cur y
el ectrode and some reference el ectrode. The
droppi ng mercury el ectrode (DME) usual l y
functi oni ng as cathode. A potenti al i s
appl i ed between these el ectr odes and
i ncreased i n a step-wi se manner. Duri ng
thi s process, correspondi ng current changes
bei ng observed at each appl i ed potenti al .
Essenti al s of the el ectri cal ci rcui t requi red
ar e shown i n the Fi g. 3.1. The appl i ed
potenti al i s vari ed by means of a potenti al
di vi der ci rcui t whi l e the current fl owi ng i s
i ndi cated on a sensi ti ve gal vanometer .
Di ffusi on-control l ed currents observed i n
pol ar ogr aphy ar e usual l y of the or der of a
few mi cro-amperes si nce the el ectroacti ve materi al used i s of the order of 10
3
mol ar.
As al ready gi ven i n Chapter 2, a droppi ng mercury el ectrode consi sts of a seri es of
smal l mercury dropl ets whi ch emerge, at a constant rate, from the ti p of a capi l l ary
attached to a constant head devi ce. The l i fe-durati on of each drop normal l y l i es between
37s.
Consi deri ng the reference el ectrode and anode a l arge area mercury pool on the
bottom of the el ectrol ysi s cel l i s shown to be used. Thi s i s just for the sake of si mpl i ci ty.
Due to i ts l arge area and the smal l magni tude of the currents normal l y encountered,
the potenti al of such a el ectrode remai ns fai rl y constant wi th varyi ng appl i ed potenti al .
For most practi cal measurements, i t i s normal to repl ace thi s by a saturated cal omel
el ectrode (SCE) [see Chapter 2] or
s ome oth er r el i abl e r efer en ce
el ectr ode wh os e poten ti al i s
i n depen den t of th e i mpos ed
potenti al .
To exami ne the natur e of the
cu r r en t v ol tage r el ati on s h i ps
observed on reducti on of a metal
i on i n sol uti on, i t i s necessary to
fl ush the wor ki ng sol uti on wi th
some i nert gas, such as ni trogen
or hydr ogen, so as to r emove
di ssol ved oxygen whi ch may cause
i nter fer ence by i tsel f under goi ng
reducti on, i n two stages, wi thi n the
nor mal potenti al wor ki ng r ange.
When thi s i nterference i s removed
ve
+ve
Fig. 3.1 : Essenti al Pol arographi c Ci rcui t
C
u
r
r
e
n
t
i
Diffusion current id
Residual current
Half wave
potential E
applied e.m.f.
Fig. 3.2 : Essential features of a polarographic currents
vol tage curve/pol arogram or pol arographi c wave
the current-vol tage curve for the reducti on of the metal i on wi l l have the appearance
of that shown i n Fi g. 3.2.
At fi rst, as the potenti al i s i ncreased cathodi cal l y from zero, onl y a very smal l
currents fl ows. Thi s i s cal l ed the resi dual current. Thi s i s essenti al l y a chargi ng current
ar i si ng fr om the char gi ng of the doubl e l ayer at each dr op and i s non-far adai c. The
resi dual current may al so contai n smal l (faradai c) components due to the presence of
r educi bl e i mpur i ti es i n the sol uti on. These may be i ntr oduced thr ough the hi gh
concentrati on of the supporti ng el ectrol ytes used. Onl y the resi dual current fl ows unti l
the decomposi ti on potenti al of the reduci bl e i oni c speci es i s reached. At thi s poi nt the
i ons, desi gnated m
n+
, begi n to be di scharged owi ng to thei r reducti on by the process:
M
n+
+ ne M (Hg) ...[1]
(Product of el ectrode reacti on)

Very often the metal atoms produced are absorbed i nto the mercury drop i n the
form of amal gam. A steep ri se i n current i s now observed and, wi th a further smal l
i ncrease i n appl i ed, potenti al , the ri se
wi l l conti nue. However , the M
n+
i ons
arri ve at the DME by the rel ati vel y
sl ow process of natural di ffusi on. Si nce
the rate of reducti on i ncreases wi th
the appl i ed potenti al , a poi nt i s
eventual l y r eached at whi ch the i ons
ar e r educed as fast as they di ffuse
across the concentrati on gradi ent set
up at the el ectrode surface. The Fi g.
3.3, r epr esents the concentr ati on
gradi ent i n the i mmedi ate vi ci ni ty of
pl anar secti on of the el ectrode surface.
When the concentrati on of i ons at the
el ectrode surface approaches zero, the
cur r ent no fur ther i ncr eases i n the
overal l el ectrode reacti on rate whi ch
i s now the decomposi ti on potenti al of
some other reduci bl e speci es present i n sol uti on i s reached. Thi s coul d be regarded as
the di schar ge of suppor ti ng el ectr ol yte cati on, though not hydr ogen due to the
excepti onal l y l ar ge hydr ogen over vol tage on mer cur y.
Parti cl es reduced at the mercury surface subsequentl y di ffuse away from the surface
and thi s may occur i n one of the two ways:
(i) I f an amal gam i s formed, e.g., wi th thal l i um, l ead, cadmi um, zi nc and al kal i
metal s. I n thi s case, the reduced parti cl es di ffuse from the drop surface i nto the
bul k of mercury formi ng the drop whi ch subsequentl y detaches from the capi l l ary
ti p;
Depolarizer
Concentration
C = Bulk concentration
0
Electrode
Surface
Distance from electrode surface
C = Surface concentration solution
S = Diffusion layer thickness
Fig. 3.3 : Concentrati on gradi ent at copl anar
secti on of el ectr ode sur face i nduced by the
occurrence of an el ectrode process.
The Technique 25
(ii) I f amal gam for mati on does not occur , e.g., for the r educti on pr ocesses
Fe
3+
Fe
2+
and Sn
4+
Sn
2+
. The reduced speci es si mpl y di ffuse back
i nto the bul k of the sol uti on.
The i mpor tance of pol ar ogr aphy for quanti tati ve anal ysi s l i es i n the di r ect
proporti onal i ty whi ch exi sts between the l i mi ti ng di ffusi on current and the concentrati on
of the reduci bl e speci es or depol ari ze. I t i s to be noted that at the foot of the current-
vol tage curve, or pol arographi c wave, and at the l i mi ti ng current pl ateau, the droppi ng
el ectrode behaves i s accordance wi th the defi ni ti on of a pol ari zed el ectrode. That i s
to say, the potenti al appl i ed to i t may be al tered at wi l l wi thi n these regi ons wi thout
si fni fi cantl y al teri ng the current fl ow.
On the ri si ng part of the wave, the current changes consi derabl y for onl y a smal l
vari ati on i n appl i ed potenti al and the DME i s sai d to be depol ari zed. I n the regi on
of the pl ateau current, id, the droppi ng el ectrode i s compl etel y concentrati on pol ari zed,
si nce the el ectrode reacti on rate i s control l ed by the di ffusi on rate and hence by the
concentrati on gradi ent at the el ectrode surface.
The potenti al correspondi ng to the mi d-poi nt of the wave, where the current i s
exactl y one-hal f of the maxi mum val ue id/2, i s known as the hal f-wave potenti al , E
. Thi s i s depol ar i zed under fi xed sol uti on condi ti on. Measur ement of hal f-wave
potenti al s therefore serves as a means of i denti fi cati on of di fferent reduci bl e speci es.
(ii) Experimental Technique : For experi mental purpose l et us consi der the
el ectrol ysi s of a sol uti on contai ni ng a cati on or a sol uti on contai ni ng several
di ffer ent cati ons, e.g., Cu
+2
, Tl
+
, Zn
+2
, etc. There i s a certai n reversi bl e potenti al
at whi ch each i on i s di scharged at the cathode. The potenti al depends on the
standard E
0
of the el ectrode M/ M
+2
and on the concentr ati on of M
+2
i n the
sol uti on. At 25C,
E = E
0
+
| |
2
00592
l og
M
.
a
z
+
...[2]
Thus a tenfol d change i n the i oni c acti vi ty changes the di scharge potenti al of the
i ons by 0.0592/(z) vol ts. A factor of 10
2
i n acti vi ty corresponds to 0.1184/(z) vol ts.
On gradual l y i ncreasi ng the potenti al appl i ed to the cel l , the cati on wi th the hi ghest
val ue of E deposi ts fi rst. On conti nui ng to i ncrease the appl i ed potenti al , the current
densi ty al so i ncrease. As the current densi ty ri ses, the concentrati on of the i on bei ng
di scharged becomes more and more depl eted i n the nei ghbourhood of the cathode,
parti cul arl y i f the sol uti on i s not sti rred. Thi s i s the phenomenon of concentrati on
pol ari zati on. Eventual l y the l i mi ti ng val ue of
d
I
i s reached for the care of stati onary

el ectrodes. The I
d
vs vol tage curve becomes fl at and the potenti al ri ses to a val ue
determi ned by the reversi bl e di scharge potenti al of the cati on wi th next hi gher E.
When thi s happens the second i on begi ns to be di scharged, even though there may sti l l
be an appreci abl e concentrati on of the fi rst i on i n the bul k of the sol uti on. Wi th i ncreasi ng
E, thi s process may be repeated wi th a thi rd ki nd of i on, and so on.
I f concentr ati on pol ar i zati on i s used to di ffer enti ate r educi bl e substances i n a
sol uti on, i t i s necessary to have a cathode of ti ny area, si nce otherwi se the current
through the cel l woul d become very hi gh. Transference must al so be el i mi nated on the
part of the el ectroacti ve i on so that the current i s not strongl y dependent upon the
mobi l i ty of the ani on present. Al so the cathode surface shoul d be cl ean, reproduci bl e
and, r eadi l y r enewabl e. These condi ti ons ar e met by the DME, whi ch pr ovi des a
conti nuous fl ow of dropl ets of mercury, about 0.5 mm i n di ameter. The anode shoul d
be practi cal l y non-pol ari zabl e. A pool of mercury l ocated at the bottom of the cel l can
serve as a reference el ectrode and anode. I t i s negl i gi bl y pol ari zed because of i ts l arge
area. Al ternati vel y, standard reference el ectrodes of l arge area can be used as reference
anodes. These speci fi cati ons are al ready gi ven i n previ ous chapters.
A typi cal current densi ty vs vol tage curve i n shown i n Fi g. 3.4.
0
2
1
1.2 1.2 1.2 1.6
a b
c
C
u
r
r
e
n
t
,
m
i
c
r
o
a
m
p
e
r
e
s
E , volts vs. S.C.E
d.e.
Fig. 3.4 : Pol arograms of 0.5 mM zi nc (I I ) i n 2F sodi um hydroxi de. The drop ti me
at 1.6 V. vs. S.C.E. was (a) 12, (b) 4, and (c) 1.4 sec.
The hi gh over vol tage for hydr ogen di schar ge on mer cur y i s a gr eat advantage i n
the pol arographi c study si nce, i t al l ows many i ons to be studi ed whi ch have reversi bl e
el ectrode potenti al s bel ow H
2
/ H
+
. Even Na
+
and K
+
may be di schar ged befor e H
+
at
the droppi ng mercury el ectrode.
Duri ng the process of experi ment, the current osci l l ates between a maxi mum and
a mi ni mum as each mercury drop grows and fal l s. The overal l ri se from one fl at porti on
The Technique 27
of the curve to the next i s cal l ed the pol arographi c wave (as al ready descri bed). The
hal f-wave potenti al (al ready shown i n fi gures) serves to i denti fy the reduci bl e i on. The
val ue of the di ffusi on l i mi ted current for each i on i s proporti onal to the concentrati on
of the i on.
The theoreti cal cal cul ati on of di ffusi on current i s a sol uti on of the di ffusi on equati on
gi ven by I l kovi c, [2]
I = 0.732F | z| D
1/2
cm
2
t
1/6
...[3]
where mi s the mass of mercury fl owi ng per second, D i s the di ffusi on coeffi ci ent of the
i on, t the drop ti me and c the mol ar concentrati on.
Thi s proporti onal i ty i s the basi s of quanti tati ve appl i cati on of pol arography. I t i s to
be noted that the current i s proporti onal to the concentrati on for a gi ven capi l l ary and
for a gi ven i on. The I l kovi c equati on can al so be used to esti mate [z] or D under the
condi ti ons of the experi ment.
Stati onary mi cro el ectrodes are sel dom used i n practi cal pol arography because the
di ffusi on current decreases markedl y wi th ti me as the thi ckness of the di ffusi on l ayer,
, i ncreases. I n such experi ments rotati ng pl ati num el ectrodes are used.
From the equati on [3] i t i s predi cted that the pl ot of E
d.m.e.
vs l og [I / I I ] shoul d
be l i near for a reacti on that behaves reversi bl y under di ffusi on control l ed condi ti ons
and the sl ope of thi s l i near pl ot shoul d be RT/2.303/z/F and that the i ntercept denotes
the E .
Pol arography i s useful i n research because i t i s a conveni ent method for measuri ng
el ectrode potenti al s and for studyi ng el ectrode reacti on.
3.3 SOLVENTS AND SUPPORTING ELECTROLYTES
Al l el ectrochemi cal phenomena occur i n a medi um, whi ch general l y consi sts of a sol vent
contai ni ng a supporti ng el ectrol yte. The sol vent system i s a term to descri be the
medi um consi sti ng of both the sol vent and the supporti ng el ectrol yte.
As a matter of fact there i s no uni versal sol vent, and general l y a system i s used
whose meri ts outwei ghs i ts di sadvantages for a parti cul ar appl i cati on. I t may happen
that a good sol vent system for one type of experi ment or compound may be total l y
unacceptabl e for other appl i cati on. I t i s therefore ones choi ce as to how the chemi cal
and el ectrochemi cal properti es of the el ectrode reacti on i n whi ch one i s i nterested may
be affected by a parti cul ar sol vent system.
For al l practi cal purposes, the sol vent system shoul d not undergo any el ectrochemi cal
reacti on over a range of potenti al s on whi ch the reacti on i s to be carri ed out. A sol uti on
of tetr abutyl ammoni um hexafl uor ophosphate i n acetoni mi l e exhi bi ts posi ti ve and
negati ve decomposi ti on potenti al s of +3.4 and 2.9 V (SCE) respecti vel y. I n practi ce
one rarel y needs both posi ti ve and negati ve ranges i n a si ngl e set of experi ments.
Sol vents ar e often used whi ch exhi bi t ei ther a ver y negati ve or ver y posi ti ve
decomposi ti on potenti al , but not both. For exampl e both ni trobenzene [3] and methyl ene
chl ori de [3] have been used for studi es of oxi dati on processes because they are oxi di zed
wi th di ffi cul ty, not wi thstandi ng wi th the fact that they are actual l y qui te easi l y reduced.
On the contrary, l i qui d ammoni a and methl ami ne are good sol vents for el ectrochemi cal
reducti on, al though poor for oxi dati on.
As a matter of fact the potenti al l i mi t i n a gi ven sol vent system i s set not by the
sol vent i tsel f but by the el ectrochemi cal behavi our of the supporti ng el ectrol yte. I t has
been known for years that the reducti on of al kal i metal i ons to the correspondi ng
metal s (2 V vs SCE) i s general l y the potenti al l i mi ti ng process i n aproti c sol vents and
that by use of tetra al kyl ammoni um sal ts one can reach consi derabl y more negati ve
potenti al s. The decomposi ti on potenti al s of tetra al kys ammoni um i ons of mercury
become more negati ve as the al kyl groups become l arger, e.g., Me
4
N
+
: 2.65 V; Bu
4
N
+
:
2.88 V.
I n order to support passage of an el ectri cal current, the sol vent system shoul d have
l ow el ectri cal resi stance and a moderatel y hi gh di el ectri c constant ( 10). A number of
most commonl y used sol vents used i n or gani c el ectr o chemi str y have sati sfactor y
di el ectri c constants, e.g., di methyl formani de (3.6), acetoni tri l e (37.5) and di methyl
sul phoxi de (46.7). So al so thei r el ectrol yti c sol uti ons have acceptabl y hi gh conductances.
Consi deri ng the sol vent power, an el ectrochemi cal sol vent must be abl e to di ssol ve
a wi de range of substances at acceptabl e concentrati ons. Thi s general l y means that
el ectrol ytes must be sol ubl e at l east to the extent of 0.1 M, whi l e the el ectroacti ve
materi al must form approxi matel y mi l l i mol ar sol uti on for appl i cati on of the vari ous
el ectr oanal yti cal techni ques or gr eater for pr epar ati ve el ectr ol yses. Tetr a al kyl
ammoni um perchl orates, hexafl uoro phosphates and tetra fl uoroborates general l y exhi bi t
the most sati sfactory sol ubi l i ty as el ectrol ytes i n organi c sol vents.
As a matter of fact chemi cal i nertness of the sol vent i s an i mportant aspect to be
consi dered. The sol vent, as such shoul d not react wi th the el ectroacti ve materi al , nor
wi th i ntermedi ates or products of the el ectrode reacti on under i nvesti gati on. No one
sol vent coul d reasonabl y be expected to be unreacti ve toward al l of the many ki nds of
reacti ve speci es whi ch can be generated el ectrochemi cal l y. I t i s known that many
anodi c organi c reacti ons generate cati oni c speci es [1] and hence to use a nucl eophi l i c
sol vent i s not desi rabl e. Acetoni tri l e i s commonl y used i n anodi c studi es but i t i s
moderatel y nucl eophi l i c. Therefore attempts to characteri ze el ectrochemi cal l y generated
cati ons may requi re a l ess reacti ve sol vent, e.g., methyl ene chl ori de or one of the super
aci d sol vents. On the other hand, reducti ons of organi c speci es general l y form ani ons,
and use of pr oti c sol vents to avoi d aci d-base r eacti ons between the sol vent and
cathodi cal l y generated i ntermedi ates. On the whol e sol vent shoul d reasonabl y be stabl e
so that puri fi cati on, preparati on, and storage of standard sol uti on does not create
major probl ems.
Al so the sol vent shoul d have a conveni ent l i qui d range. No doubt thi s depends on
the experi ment i nvol ved. Much depends whether the experi ment i s to be carri ed out at
r oom temper atur e or other wi se. Mor eover the sol vents and el ectr ol ytes shoul d be
i nexpensi ve, nontoxi c, and non-fl ammmabl e. The l atter two characteri sti cs are not wel l
sati sfi ed by most organi c sol vents. They can be used wi th i n acetoni tri l e and are stabl e
to very posi ti ve and negati ve potenti al s sal ts l i ke hexa fl uorophosphate are rather
i nsol ubl e i n water, whi ch means that they are non-hydroscopi c and can often be separated
fr om r eacti on pr oducts by evapor ati on of the acetoni tr i l e fol l owed by appr opr i ate
treatment (e.g., extracti on wi th a non-pol ar sol vent). I norgani c el ectrol ytes l i ke NaBF
4
or NaCl O
4
may be useful i n such cases. Methyl ene chl ori de i s useful i n organometal l i c
The Technique 29
el ectrochemi stry i n si tuati ons where acetoni tri l e i s found to di spl ace l i gands coordi nated
to a metal center.
Di methyl formami de, acetoni tri l e, and di methyl sul phoxi de are al l excel l ent sol vents
for reducti ve el ectrochemi stry of organi c compounds. Water and al cohol s are useful for
i norgani c el ectrochemi stry. Di methyl sul foxi de i s parti cul arl y useful sol vent for cathodi c
el ectrochemi stry, al though wi th i nconveni ent l i qui d range (18189C). TBAHFP and
TBATFB are good el ectrol ytes for use i n organi c sol vents. Di methyl sul phoxi de i s an
excel l ent sol vent for both organi c and i norgani c compounds. Water whi ch i s al ways
present i n di pol ar aproti c sol vents i s a poor proton donor i n DMSO. TBAHFP and
TBATFB are two of many el ectrol ytes for use i n DMSO.
I rregul ar drop ti me behavi our i s observed i n pol arography i n DMSO, possi bl y due
to strong proper venti l ati on and safety precauti ons. Neverthel ess, the property, vi scosi ty
may be of i mportance. When ti me i nterval i s wi shed to be extended, i.e., the ti me
i nterval over whi ch mass transfer i s occurri ng sol el y by di ffusi on (e.g., potenti al -step
experi ments) but woul d be a di sadvantage where effi ci ent mass transfer i s requi red, as
i n preparati ve-scal e el ectrol yses.
3.3.1 Recommended Solvents and Electrolytes
Much i norgani c oxi dati ve and reducti ve el ectrochemi stry has been carri ed out i n water
wi th l i ttl e di ffi cul ty. Organi c and organometal l i c compounds general l y ei ther are not
very sol ubl e i n water or are reacti ve towards i t. Thi s has created i nterest i n the use
of non-aqueous sol vents i n el ectrochemi stry. Ethanol and methanol are good organi c
sol vents, i nexpensi ve, readi l y avai l abl e i n hi gh puri ty and di ssol ve sal ts readi l y. Al cohol s,
l i ke water are rather easi l y oxi di zed and are hi ghl y nucl eophi l i c. Hence i t has been
more common to use aproti c organi c sol vents for el ectrochemi cal oxi dati ons. At the
pr esent ti me acetoni tr i l e i s the most commonl y used or gani c sol vent for anodi c
el ectrochemi stry. I t i s preferred sol vent for most purposes havi ng a conveni ent l i qui d
r ange (45.7 81.6C). Tetr abutyl ammoni um hexafl uor ophosphate or tetr afl uor obor ate
sal ts are hi ghl y sol ubl e adsorpti on of DMSO or di methyl sul phi de on the mercury
sur face.
Most wi del y used organi c sol vent for cathodi c chemi stry has been DMF. I t has a
number of desi r abl e pr oper ti es at the same ti me i t i s qui te toxi c and under goes
undesi rabl e reacti ons on storage.
I t i s fel t that acetoni tri l e and di methyl sul phoxi de are preferabl e to DMF as sol vents
for most appl i cati ons.
Hexamethyl phosphor ami de (HMPA), ammoni a and methyl ami ne ar e excel l ent
sol vents for el ectr ochemi cal gener ati on of sol vated el ectr ons. Li thi um chl or i de i s
recommended as the supporti ng el ectrol yte for thi s appl i cati on. The properti es of HMPA
are otherwi se general l y si mi l ar to those of DMF and DMSO.
Tetrahydrofuran (THF) and other ether sol vents are useful aproti c sol vents for
cathodi c el ectrochemi stry i nspi te of thei r l ow di el ectri c constants, because they can be
dri ed more effi ci entl y than the other pol ar sol vents.
Note : More detai l s are gi ven i n the chapter descri bi ng non-aqueous sol vents.
3.4 POLAROGRAPHIC MAXIMA
I t i s often observed on pol arographi c curves that an i ncrease of current above the
l i mi ti ng val ue takes pl ace i n the form of vari ous shapes. I n some cases the ori gi n of the
current maxi mum i s connected wi th the mechani sm of the el ectrode process, as happens
dur i ng the catal yti c di schar ge of hydr ogen i ons. Mor e fr equentl y, the pol ar ogr aphi c
maxi ma are caused by i ncreased transport of the depol ari zer towards the el ectrode by
a streami ng moti on of the sol uti on. Such maxi ma are reproduci bl e and are cal l ed
streami ng maxi ma. These are di vi ded i nto maxi ma of the fi rst and of the second ki nd.
Maxi ma of the fi rst ki nd appears on the ri si ng porti on of the pol arographi c curve and
usual l y occur i n di l ute sol uti ons. The maxi ma of the second ki nd are observed i n more
concentrated sol uti ons and at hi gh mercury fl ow rates. They appear onl y over the
range of the l i mi ti ng current. These are usual l y rounded and do not fal l di sconti nuousl y
to the l i mi ti ng current l i ke the maxi ma of the fi rst ki nd.
3.4.1 Maxima of the First Kind
Kucera [3] put forth that streami ng maxi ma of the fi rst ki nd are connected wi th the
anomal i es obser ved on el ectr ocapi l l ar y cur ves. Maxi ma of thi s ki nd appear s on
pol arographi c curves for currents governed by di ffusi on, usual l y i n di l ute sol uti on of
the supporti ng el ectrol yte used (bel ow 1 N), the rati o of the concentrati on of depol ari zer
to that of the supporti ng el ectrol yte bei ng from 1 : 1 to 1 : 100. Maxi ma have been
observed duri ng the pol arographi c reducti on and oxi dati on [4] of cati ons, ani ons and
neutral mol ecul es and wi th anodi c waves for the di ssol uti on of amal gam [5], i n both
aqueous and non-aqueous [6] sol uti ons and i n mel ts [7].
Thei r shape i s characteri sti c. The i ncrease i n current starts on the ri si ng porti on
of the pol arographi c wave. The current ri ses rapi dl y wi th i ncreasi ng vol tage unti l i t i s
several ti mes greater than the l i mi ti ng current. The maxi mum for the reducti on of
mercurous i ons can be as much as 40-ti mes hi gher than the l i mi ti ng current [8] and
then fal l s di sconti nuousl y to the normal current. Thus, a more or l ess sharp current
peak whi ch i s typi cal of thi s ki nd of maxi ma i s formed on the curve.
The hei ght of the maxi mum vari es wi th di fferent depol ari zers. Wi th the same
substance i t depends on the supporti ng el ectrol yte, on i ts concentrati on and on the
pr esence of other substances pr esent i n the sol uti on. At constant depol ar i zer
concentr ati on, the maxi mum i ncr eases wi th i ncr easi ng concentr ati on of suppor ti ng
el ectrol yte upto a certai n l i mi t and then decreases agai n.
The dependence of the maxi mum on temperature, drop-ti me and mercury fl ow-rate
cannot be expressed by si mpl e a rel ati onshi p [9]. The hei ght of the maxi mum i s vi rtual l y
i ndependent of the hei ght of the mer cur y head.
I n addi ti on to other factors (depol ari zer concentrati on, conducti vi ty of the sol uti on
and drop-ti me), the vol tage at whi ch the decrease i n maxi mum current starts depends
on the di recti on i n whi ch the appl i ed el ectromoti ve force i s vari ed. The peak of the
maxi mum on a reducti on wave i s upto 100 mV more negati ve wi th an i ncreasi ng
appl i ed el ectr omoti ve for ce than wi th a decr easi ng one. Thi s phenomenon, cal l ed
hysteresi s of the maxi mum [10] i s speci al l y evi dent wi th l onger drop-ti mes and sol uti ons
of l ow conducti vi ty.
The Technique 31
Streami ng mercury el ectrodes do not gi ve maxi ma. Parti cul arl y hi gh maxi ma are
ter med dur i ng r educti on of si l ver , mer cur y, copper , i ndi um and al kal i metal s,
persul phates and mol ecul ar oxygen. The cati ons of al kal i metal s, on the other hand,
gi ve smal l maxi ma. Cadmi um whi ch i s reduced at the same potenti al as i ndi um forms
no maxi ma. As a r ul e, no maxi ma ar e obser ved wi th al dehydes and most ni tr o
compounds.
Maxi ma on the anodi c waves for di ssol uti on of amal gams exhi bi t the same features
as those on the pol arographi c curves for depol ari zers present i n sol uti on. The hi ghest
maxi ma about twi ce as hi gh as the l i mi ti ng current are gi ven by amal gam of thal l i um,
cadmi um, and zi nc. Smal l er maxi ma were observed wi th ti n and l ead [11].
3.4.2 Suppression of Maxima of the First Kind
The hei ght of a maxi mum of the fi rst ki nd i s very sensi ti ve to the presence of surface
acti ve substances i n sol uti on.
Due to maxi ma i t i s i mpossi bl e to eval uate preci sel y the pol arographi c curves.
Hence, i t i s necessary to remove maxi ma by addi ng surface acti ve agents. I n practi ce,
gel ati n i s usual l y empl oyed but al so, si mi l ar effect i s found wi th other hi gher-mol ecul ar
organi c substances such as vari ous aci ds and al cohol s, dyes, terpenes and neutral
detergents l i ke Tri ton X and some others.
These substances suppress maxi ma over potenti al range wi thi n whi ch they are
adsorbed on the mercury surface, hence the i nfl uence of the same surface agent on the
maxi ma of di fferent depol ari zers i s di fferent. I n cases where i ndi vi dual substances do
not suppress maxi ma suffi ci entl y, thei r mi xtures are often used [6].
I t i s i mportant not to add more surface acti ve agent than i s necessary. Even a sl i ght
excess may affect the el ectrode process whi ch woul d not al l ow correct eval uati on of the
pol arographi c curve. Substances wi th a hi gher mol ecul ar wei ght or a l ow sol ubi l i ty
suppress the maxi ma more effi ci entl y than l ow mol ecul ar and easi l y sol ubl e substances.
3.4.3 Polarity of Maxima of the First Kind
I n cases where the mercury surface bears a posi ti ve charge, the maxi mum i s descri bed
as a posi ti ve maxi mum. Thi s takes pl ace i f the hal f-wave potenti al of the depol ari zer,
the maxi mum for whi ch i s bei ng i nvesti gated, l i es on the posi ti ve si de of the
el ectrocapi l l ary curve. I f on the other hand, duri ng the formati on of the maxi mum, the
el ectrode i s negati vel y charged wi th respect to the sol uti on, i t i s reported as negati ve
maxi mum [Fi g. 3.5].
No maxi ma of the fi rst ki nd are formed at the potenti al of el ectrocapi l l ary zero. The
reducti on of cadmi um i ons [12] can be taken as an exampl e. At about 0.60 V (vs NCE)
i s the hal f-wave potenti al of free cadmi um i ons and no maxi mum i s formed on the
wave. On addi ng a trace of i odi de the maxi mum on the el ectrocapi l l ary parabol a shi fts
to a more negati ve potenti al and a posi ti ve maxi mum appears on the cadmi um wave.
I n the presence of ammoni a or cyani des, both of whi ch form stabl e compl exes wi th
cadmi um i ons, the reducti on potenti al of cadmi um shi fts to negati ve potenti al s and a
negati ve maxi mum occur s on the r educti on wave.
The pol ar character of maxi ma
becomes evi dent from the way i n
whi ch they are suppressed [Fi g.
3.6]. The negati ve maxi ma ar e
suppressed by pol yval ent cati ons
at suffi ci entl y l ower concentrati on
by di - or monoval ent cati ons. The
suppr essi on occur s i n thi s case
r egar dl ess of the ani on of the
added sal t. On the other hand the
posi ti ve maxi ma are not sensi ti ve
to the val ency of the cati ons. They
ar e mor e easi l y suppr essed by
el ectr ol ytes wi th di val ent than
wi th monoval ent ani ons. Other
pr oper ti es of i ons ar e effecti ve
besi des the char ge. Thus heavy
cati ons suppr ess maxi ma mor e
r eadi l y than those of the l i ght
el ements.
The pol ari ty of posi ti ve and negati ve maxi ma al so appears when dyes and col l oi ds
are added. Posi ti ve maxi ma are suppressed by ani oni c dyes, but negati ve maxi ma by
cati oni c dyes or al kal oi ds. Si mi l arl y posi ti ve col l oi ds easi l y suppress negati ve maxi ma
and negati ve col l oi ds ar e mor e
power ful i n suppr essi ng posi ti ve
maxi ma.
Apar t fr om th e di ffer en t
beh av i ou r of s u ppr es s i on , th e
posi ti ve and negati ve maxi ma
di ffer somewhat i n thei r shapes.
The posi ti ve maxi ma exhi bi ts a
r el ati vel y br oad r i si ng por ti on,
rounded peaks too and fal l di rectl y
to th e l i mi ti n g cu r r en t. Th e
negati ve maxi ma on the other hand
are on the l ower si de, more acute
an d often decr eas e bel ow th e
l i mi ti ng current.
Tl
0. 3V
1. 0V
Ni
+
Mn
1. 6V
S = 3: 1000
Fig. 3.5 : Posi ti ve maxi mum on the reducti on wave for
thal l us i ons and negati ve maxi ma for ni ckel (I I ) and
manganese (I I ) i ons
1
2
3
4
5
Fig. 3.6 : I nfl uence of Ba
2+
on posi ti ve and negati ve
maxi ma. To 25 ml of 5.10
3
N Tl Cl and Ni Cl
2
the
fol l owi ng vol umes were added: 1 0; 2 0.05 ml ; 3 0.1 ml ;
4 0.2 ml ; 5 0.4 ml of 1 N BaCl
2
.
The Technique 33
3.4.4 Streaming of Electrolyte and Maxima of the First Kind
Bruns and hi s co-workers [13] observed a streami ng accompanyi ng the maxi ma at a
mercury cathode of 5 m di ameter duri ng the reducti on of mercurous ni trate (i n ni tri c
aci d wi th 70% ethanol ) at l ow temper atur es. The str eami ng occur s both at r oom
temperature and at 37C. At 38C, when mercury sol i di fi es, the streami ng and the
maxi mum di sappears.
Exampl es of streami ng and maxi ma do not appear wi th sol i d el ectrodes except
duri ng the reducti on of mercurous i ons at a pl ati num el ectrode when a fi l m of metal l i c
mercury [14] forms on the pl ati num surface.
Popova and Kryukova [15] demonstrated that the sti rri ng at the surface of a droppi ng
mercury el ectrode and the correspondi ng pol arographi c maxi mum can be evoked by
pl aci ng the droppi ng el ectrode i n an el ectri c fi el d between two pl ati num el ectrodes.
I n cases where, the surface acti ve agents are added to the sol uti on they are adsorbed
on the el ectr ode sur face and ar e car r i ed away by the moti on of the mer cur y and of the
el ectrol yte to the pl ace of greatest surface tensi on. They accumul ate there and decrease
the surface tensi on and thus a force agai nst the streami ng ari ses.
The iR drop i ncrease wi th the growth of the mercury drop provi ded the resi stance
of the ci rcui t i s suffi ci entl y l arge and the potenti al of the drop becomes more posi ti ve.
Thus streami ng may start suddenl y on a drop through whi ch a di ffusi on current passed
at the begi nni ng and on the current-ti me curve a jump up to the maxi mum current
appears. Thi s mechani sm may expl ai n the current-ti me curves observed by Bri di cka
[16] and the hysteresi s of the pol arographi c maxi ma. I f a pol arographi c cathodi c curve
i s recorded wi th decreasi ng vol tage then the iR drop i n the di ffusi on current i s smal l er
than that at the maxi mum and the zero potenti al i s reached, i.e., the maxi mum appears
at the l ower appl i ed vol tage than wi th pol ari zati on i n the reverse di recti on.
Maxi ma of the second ki nd may be suppressed by reduci ng the fl ow rate, e.g., by
l ower i ng the hei ght of the mer cur y head.
I n accordance wi th thi s dependence on the fl ow rate, no maxi mum of thi s ki nd has
been observed wi th stati onary mercury or other el ectrodes. I t occurs wi th a rotati ng
mercury el ectrode, but not wi th a streami ng mercury el ectrode because of i ts speci fi c
hydrodynami c properti es.
At constant fl ow-r ate and constant dr op-ti me, a maxi mum of the second ki nd
i ncr eases as a l i near functi on of the depol ar i zer concentr ati on. Wi th i ncr easi ng
concentrati on of the supporti ng el ectrol yte, the decrease i n current i n the di recti on
from the potenti al of el ectrocapi l l ary zero becomes l ess steep.
An external resi stance i n the pol ari zi ng ci rcui t does not affect the hei ght of a
maxi mum of the second ki nd. No hysteresi s has been observed wi th maxi ma of thi s
ki nd. The temperature coeffi ci ent i s greater than wi th di ffusi on currents.
3.4.5 Maxima of the Second Kind
Maxi ma of the second ki nd occurs on both cathodi c and anodi c pol arographi c di ffusi on
currents [17]. These occur usual l y i n concentrated sol uti ons of supporti ng el ectrol yte,
above 0.1 N. They appear on the l i mi ti ng cur r ent and may, depend on the pur i ty of the
sol uti on, exceed i t fi ve ti mes. I n contrast to the maxi ma of the fi rst ki nd, the current
for these maxi ma does not fal l back abruptl y to the l i mi ti ng current. I t onl y decrease
sl owl y and the greater the di stance from the el ectrocapi l l ary zero the sl ower the decrease.
Excepti onal l y, a maxi mum of the second ki nd may occur wi th an extremel y pure sol uti on
of 0.01 N 0.1 N supporti ng el ectrol yte at the potenti al of the el ectrocapi l l ary zero. I ts
form then resembl e a maxi mum of the fi rst ki nd [Fi g. 3.7]. The fl ow rate of the mercury
i s a deci si ve factor for the occurrence of maxi ma of the second ki nd. They appear as
curves as soon as the l i near speed of fl ow exceeds 2 cm /sec, thi s corresponds to m =
2.14 mg sec for a capi l l ar y wi th a di ameter of 0.1 mm. The maxi mum gr ows
approxi matel y l i nearl y wi th i ncreasi ng fl ow-rate. Above the rate 8 cm/sec further growth
of the maxi mum i s retarded.
3.4.6 Suppression of Maxima of the Second Kind
Maxi ma of the second ki nd are al so sensi ti ve to the presence of surface acti ve agents
l i ke those of the fi rst ki nd. They refl ect better the adsorpti on of substance of wi del y
di ffer i ng char acter , si nce they ar e dr awn out over a br oader r ange of potenti al s than
those of the fi rst ki nd. A decrease i n the
maxi mum on a pol arographi c curve occurs
i n the pr esence of a sur face acti ve
substance at the potenti al , at whi ch the
substance i s adsorbed. At the adsorpti on
potenti al , the current attai ns the ori gi nal
val ue associ ated wi th the absence of
adsorpti on. The sensi ti vi ty of a maxi mum
of the second ki nd to adsorpti on i s some
one hundr ed ti mes gr eater than the
sensi ti vi ty of the shape of el ectrocapi l l ary
cur ves to adsor pti on, wi th i ncr easi ng
concentrati on of adsorpti ve substance, the
decr ease on the cur ve becomes mor e
pronounced unti l the current fal l s fi nal l y
to the nor mal l i mi ti ng val ues and the
maxi mum of the second ki nd r emai ns
suppressed unti l the desorpti on potenti al
i s r eached. The pl ot of the maxi mum
cur r ent agai nst the l ogar i thm of the
concentrati on of the surface acti ve substance i s S-shaped curve, i.e., the maxi mum i s
most sensi ti ve to the addi ti on of a surface-acti ve substance when the maxi mum has
been suppressed to one-hal f of i ts ori gi nal hei ght.
The maxi mum to the suppressi ve acti on of surface-acti ve substance ri ses wi th
i ncreasi ng drop-ti me.
The adsor pti on of a number of nor mal al i phati c al cohol s wer e i nvesti gated by
Kr yukova and Fr umki n [18] who suppr essed the maxi ma on the Hg
2
Cl
2
wave i n 3 N
id
0.5 1.0 1.5 V 0
10
20
30
40
A
Fig. 3.7 : A maxi ma of the second ki nd
The Technique 35
KCl . The adsorpti on of the al cohol on the el ectrode ri ses wi th i ncreasi ng chai n l ength.
Wi th easi l y sol ubl e al cohol s l i ke ethanol , propanol or butanol , they observed i ncreasi ng
suppressi ve acti vi ty upto a certai n concentrati on. On further addi ti on, the maxi mum
i ncr eased agai n.
Whi l e prepari ng sol uti on for studyi ng adsorpti on by means of a maxi ma of the
second ki nd, the utmost puri ty must be secured.
Mi cka [19] recommended the puri fi cati on of sol uti ons by means of acti ve carbon.
The shape of a pol arographi c wave wi th a maxi mum of the second ki nd depends on
the puri ty of the sol uti on as regards surface-acti ve agents.
3.4.7 Streaming of Electrolyte with Maxima of the
Second Kind
The i ncrease of current above the l i mi ti ng val ue due to a
maxi mum of second ki nd i s accompani ed by streami ng of the
sol uti on around the droppi ng el ectrode [20]. The di recti on of
thi s str eami ng i s al ways the same fr om the bul k of the
sol uti on to the bottom of the drop, over the mercury surface
to the neck of the drop and there hori zontal l y al ong the ti p
of capi l l ary i nto the sol uti on (Fi g. 3.8). The i ntensi ty of thi s
moti on attai ns i ts maxi mum at the potenti al of the
el ectrocapi l l ary zero and sl owl y decreases wi th the di stance
from thi s potenti al . The vel oci ty of thi s streami ng exceeds
for that for maxi ma of the fi rst ki nd by about one order.
There i s a l i near dependence between the fl ow rate of the
mercury and the speed of moti on of the sol uti on.
3.4.8 Interpretation of Maxima of the Second Kind
As maxi ma of the second ki nd have a purel y hydrodynami c ori gi n, as compared wi th
the maxi ma of the fi rst ki nd, and are not caused by any process at the el ectrode.
As wi th the maxi ma of the fi rst ki nd, the rel ati ve moti on of the mercury and of the
sol uti on or maxi ma of the second ki nd i s anal ogous to the fal l of a mercury drop i n the
sol uti on.
The fal l i n the maxi mum wi th potenti al on ei ther si de of the el ectrocapi l l ary zero
i s caused by i ncreasi ng i nhi bi ti on of the moti on of the surface due to el ectri c charge of
the doubl e l ayer, whi ch because of streami ng accumul ates at the neck of the drop.
Thus, an el ectri c fi el d i s formed whi ch decreases the surface tensi on and counteracts
the moti on of the mercury.
I f a surface-acti ve substance i s present i n sol uti on i t i s adsorbed at the el ectrode
surface and the moti on of mercury carri es i t to the neck of the drop where i t accumul ates.
The mechani sm of suppressi on i s the same as that for maxi ma of the fi rst ki nd, because
of i ncreased adsorpti on the surface tensi on at the neck decreases as compared wi th
that at the bottom. The di fference i n surface tensi on gi ves ri se to force opposi ng the
di recti on of the moti on. When the drop-ti me i s l owered, there i s not enough ti me for
Fig. 3.8 : Di r ecti on of
sti r r i ng acti on i n mer cur y
and i n a sol uti on wi th a
maxi mum of the second
kind
the accumul ati on of a suffi ci ent amount of suppressi ng agent. At thi s stage, the fal se
waves di sappear and pure maxi ma occur. A suffi ci ent decrease i n the fl ow-rate removes
the fal se waves by stoppi ng the moti on of the mercury surface.
I t often happens i n practi cal pol arography that the experi mental condi ti ons favour
the formati on of maxi ma of both the fi rst and second ki nd as a si ngl e curve. The
fundamental requi rement i s a suffi ci entl y hi gh fl ow rate of mercury. Al so curves wi th
di fferent shapes are encountered that at fi rst si ght coul d be ascri bed to maxi ma of
ei ther the fi rst or the second ki nd, but are due to catal yti c ori gi n onl y.
3.4.9 Practical Applications of Polarographic Maxima
Si nce the maxi ma are sensi ti ve to the presence of surface-acti ve agents, maxi ma that
i nterfere wi th the accurate evol uti on of pol arographi c curves i n normal pol arographi c
measurements someti mes permi t the detecti on and the determi nati on of substances
that are nei ther oxi di zabl e nor reduci bl e, but are onl y absorbed on the el ectrode surface.
Thus, the so cal l ed pol arographi c adsorpti on anal ysi s i s not speci fi c, but i t proved to
be useful i n determi ni ng the puri ty of vari ous substances whi ch contai n i mpuri ti es of
col l oi dal character mostl y of organi c. The methods maki ng use of a maxi mum of the
fi r st ki nd ar e on an aver age sensi ti ve to 0.0001% of i mpur i ti es. Those based on
suppressi on of a maxi mum of the second ki nd are more exacti ng as regards the puri ty
of the sol uti ons and chemi cal s used, but they are by about two orders more sensi ti ve.
Pol arographi c adsorpti on anal ysi s i s used extensi vel y: (i) I n the control water puri ty,
(ii) I n sugar i ndustr y for r efi ni ng sugar s, (iii) The chemi stry of pol ymers, oi l s and
photographi c gel ati ns, (iv) I n food anal ysi s, anal ysi s of i ndustri al products, (v) Soi l
anal ysi s and pl ant physi ol ogy.
3.5 POLAROGRAPHY IN NON-AQUEOUS SOLVENTS
The pol arographi c i nvesti gati ons of chemi cal substances to measurements i n aqueous
sol uti ons onl y. The search for sui tabl e sol vents was i ni ti ated to i nvesti gate great number
of water-i nsol ubl e organi c compounds. Not onl y the pure sol vents but al so the mi xture
of sol vents was found to be sui tabl e for quanti tati ve anal ysi s.
The magni tude of di ffusi on current and, someti mes, the shape of the wave so al so
the hal f-wave potenti al ar e i nfl uenced by usi ng non-aqueous sol vents. These effects ar e
chi efl y due to change i n sol vati on and i n the di ffusi on coeffi ci ents.
Wel l defi ned waves can be obtai ned i n non-aqueous sol vents for substances that
gi ve curves wi th i l l -defi ned l i mi ti ng currents i n water. We can take for exampl e, Ca
2+
and Mg
2+
gi ve easi l y measurabl e waves i n acetoni tri l e i n contrast to thei r behavi our i n
water .
The theoreti cal i nvesti gati on of substances i n non-aqueous/sol vents e.g., i n the
determi nati on of di ffusi on coeffi ci ents and standard potenti al s, to the reversi bi l i ty of
the el ectrode process and compl ex equi l i bri a has been drawn i n the pol arographi c
studi es.
Thus for sol vents wi th a l ow di el ectri c constant, Schaap [21] deri ved an equati on
for the reversi bl e wave of a cati on, the reduced form of whi ch yi el ds an amal gam wi th
The Technique 37
mercury. The formati on of i oni c pai rs i s operati ve i n thi s case and the deri vati on i s
si mi l ar to that for consecuti ve compl ex formati on.
3.5.1 Solvents that are Frequently Used
(i) Acetic Acid : The possi bi l i ty of pol arographi c anal ysi s i n aceti c aci d was fi rst
menti oned by MacGi l l avry [22]. More detai l ed i nvesti gati on si nce then were
gi ven by many wor ker s.
The di ffusi on currents for cati ons, e.g., Cd
2+
, Pb
2+
and Zn
2+
are about two-thi rds
of those i s water. Thi s i s due to the greater vi scosi ty of gl aci al aceti c aci d. I ons,
such as Cu
2+
, whi ch are reduced at very posi ti ve potenti al form acute maxi ma.
Thi s coul d be suppressed by Puchsi n as shown by previ ous workers. Not onl y
thi s there were several other substances found sui tabl e for suppressi ng maxi ma
i n gl aci al aceti c aci d.
(ii) Acetonitrile : Among other sol vent acetoni tri l e proved very conveni ent and
useful . Pr evi ous wor ker s, e.g., Kol thoff and Coetzee [23] and many other s have
gi ven qui te useful i nformati on on such i nvesti gati ons. The energi es of sol vati on
of the cati ons and the ani ons are smal l er than i n water and most cati ons are
reduced at more posi ti ve potenti al s than i n water. I n addi ti on to thi s, more
negati ve potenti al s can be attai ned than i n water, and wel l -defi ned waves for
i ons l i ke cal ci um and magnesi um can be obtai ned usi ng tetraethyl ammoni um
perchl orate or tetra butyl -ammoni um i odi de as supporti ng el ectrol yte. Normal l y
an aqueous saturated cal omel el ectrode i s empl oyed as reference el ectrode wi th
an Ag/Ag
+
or Ag/AgCl el ectrode as al ready poi nted out by previ ous workers. The
potenti al s, referred to an aqueous SSE for the Ag/Ag
+
coupl e i n acetoni tri l e i n
the presence of di fferent supporti ng el ectrol ytes have al so been compared.
I nor gani c i ons have been di vi ded i nto two gr oups by Kol thoff and Coetzee [24].
The fi rst group i ncl udes cati ons wi th si mi l ar behavi our i n acetoni tri l e and i n
water. The hal f-wave potenti al s become more posi ti ve i n sequence Li
+
, Rb
+
, K
+
,
Na
+
, NH
4
+
, Ca
+
, Sr
2+
, Ba
2+
, Zn
2+
, Cd
2+
, whereas i n water the fol l owi ng sequence
hol ds: Li
+
, Ca
2+
, K
+
, Na
+
, Sr
2+
, Rb
+
, Ba
2+
, Zn
2+
, Cd
2+
. The reducti on of nNa
+
, K
+
,
Rb
+
and Zn
2+
proceeds reversi bl y, and that of other i ons i rreversi bl y.
The i nfl uence of ani ons on the el ectrode process i s pecul i ar. Zi nc ni trate i n
tetraethyl ammoni um perchl orate gi ves a reversi bl e wave at 0.70 V vs. NCE,
whi l e zi nc chl ori de i n tetraammoni um bromi de gi ves an i rreversi bl e wave at
al most 2.0 V. The hori zontal porti on of the di ffusi on current cannot be obtai ned
i n the presence of tetraethyl ammoni um i odi de.
Accordi ng to Kol thoff and Coetzee [24] the second group i nvol ves cati ons whose
pol arographi c behavi our i n acetoni tri l e di ffers consi derabl y from that i n water.
I n contrast to thei r behavi our i n water, these cati ons are mostl y reversi bl y
reduced or at l east approach a reversi bl e behavi our i n acetoni tri l e. The fol l owi ng
reducti ons take pl ace reversi bl y : Ag
I
/Ag
0
, Cu
I
/Cu
0
, MN
I I
/Mn
0
...wel l defi ned waves,
al though not ful l y reversi bl e, are obtai ned wi th Fe
I I
, Cr
I I
, Be
I I
...Eu
0
and Yb
I I
Yb
0
.
When smal l amounts of water i s added to acetoni tri l e formati on of hydrated
cati ons take pl ace. The waves whi ch i n acetoni tri l e were reversi bl e and appeared
at posi ti ve potenti al , become i rreversi bl e and are shi fted to more negati ve
potenti al s. Changes i n di ffusi on coeffi ci ents of Ag
+
, Tl
+
and Cu
2+
were i nvesti gated
by Tachi and Takahashi [25] i n mi xtures of acetoni tri l e and water.
The hydrogen overvol tage i n anhydrous acetoni tri l e i s consi derabl y l owered.
Vl cek [26] found E = 0.60 V (vs NCE) for the hal f-wave potenti al of hydrogen
r educed fr om per chl or i c aci d i n Acetoni tr i l e satur ated wi th tetr a methyl
ammoni um i odi de and the over vol tage
1/2
= 0.56 V as compared wi th
1/2
=
1.34 V i n water. Coetzee and Kol thoff i nvesti gated a l arge number of aci ds i n
acetoni tri l e and found a far greates di spersi on of hal f-wave potenti al s than i n
water. But due to the i rreversi bi l i ty of the process, the strength of aci ds i n
acetoni tri l e cannot be compared on the basi s of thei r hal f-wave potenti al s.
(iii) Alcohols : Al cohol s, e.g., ethanol , methanol and thei r mi xtures wi th water are
most frequentl y used as sol vents. The di ffusi on currents are usual l y smal l er
than those i n water. Accordi ng to Vl cek[27] anodi c waves for al kal i metal s are
obtai ned i n absol ute ethanol . Al so, the amal gam of al kal i metal s are rel ati vel y
stabl e so that oxi dati on reducti on waves for the system i on amal gam of the
al kal i metal s can be obtai ned. As such these waves provi de a proof of the
reversi bi l i ty of al kal i metal s at the DME.
Properti es of compl exes al so change consi derabl y i n al cohol i c sol uti on as shown
by previ ous workers. Al so the formati on of cadmi um compl exes wi th chl ori des,
bromi des and thi ocyanates take pl ace at much l ower concentrati on than i n
water.
Most organi c substance are readi l y sol ubl e i n mi xtures of ethanol or methanol
wi th benzene i n water permi ti ng pol arographi c esti mati ons.
The reversi bl e organi c substances whi ch consume protons duri ng the el ectrode
process, the addi ti on of organi c sol vents onl y produces a change i n hal f-wave
potenti al . Thi s was descri bed as a change i n the acti vi ty of the hydrogeni ous,
Schwabe [28] al so deter mi ned pH val ue fr om change i n hal f-wave potenti al
whi l e wi th i r r ever si bl e pr ocesses the i nfl uence of sol vent on E i s mor e
compl i cated.
I t was al so evi dent that the rate constant for the el ectrode process measured
at constant potenti al decreases exponenti al l y wi th i ncreasi ng concentrati on of
ethanol .
(iv) Ethylenediamine : Ethyl enedi ami ne i s al so sui tabl e for pol arographi c anal ysi s
si nce a number of sal ts di ssol ve i n i t. I n reversi bl e el ectrode process, an esti mate
of the magni tude of stabi l i ty constant [29] for the correspondi ng ethyl enedi ami ne
compl ex i n water can be determi ned from the di fference between the hal f-wave
potenti al s of the cati ons i n water and i n ethyl enedi ami ne.
The potenti al of the anode coul d be determi ned from the acti vi ty of mercuri c
i ons i n l i qui d ammoni a whi l e worki ng wi th a mercury pool anode.
(v) Sulphuric Acid : For studyi ng the property l i ke dehydrati on of the depol ari zer,
the aci d i s useful . Concentrati on up to a 92 vol . % or 17 M has been used whi ch
The Technique 39
di spl ays mi ni mum vi scosi ty and maxi mum conducti vi ty whi ch i s qui te
comparabl e to that of 1 N KCl .
I n sul phuri c aci d Tl
+
[30] form a compl ex whi ch i s reduced reversi bl y and has
a hal f wave potenti al 0.5 V. Thi s i s more negati ve than that i n water (1.01 V
vs NCE). The behavi our of Tl
+
i s worth menti oni ng because i t rarel y forms
compl exes i n aqueous sol uti on (e.g., wi th EDTA) and has a hal f-wave potenti al
that i s taken as reference i n aqueous sol uti ons.
(vi) Formic Acid : I n formi c aci d sol uti on [31] the hal f-wave potenti al s of cati ons
are more posi ti ve than those i n water. The maxi ma of the fi rst ki nd are al so
suppressed to a l arge extent by the surface-acti ve mol ecul es of formi c aci d.
(vii) Liquid Ammonia : Al kal i metal s are reduced reversi bl y gi vi ng val uabl e resul ts.
The l i mi ti ng currents fol l ow I l kovi c equati on. The temperature was kept constant
at 36C 0.2C. The di ffusi on currents for al kal i metal s i n the sol vent at thi s
temperature are 23 ti mes hi gher than those i n water at 25C. The mi grati on,
i s not ful l y suppressed, because tetrabutyl ammoni um i odi de, used as supporti ng
el ectrol yte, i s onl y sol ubl e up to 5.7, 10
3
M. The sequence of i ons of the al kal i ne
earths i s the same as i n water.
Thal l i um [32] i s reduced al most reversi bl y. Cu
2+
gi ve two waves of equal hei ght.
The fi rst one i s reversi bl e. The di ffusi on coeffi ci ents for thal l i um and copper
agree wi th those determi ned from the conducti vi ty data obtai ned at i nfi ni te
di l uti on. Al umi ni um al so gi ves a measurabl e wave i n l i qui d ammoni a.
Mercurous i ons,
2
2
Hg
+
are unstabl e i n l i qui d ammoni a. Mercuri c i on, Hg
2+
, are
reversi bl y reduced to Hg. As a consequence, the Hg
2+
/Hg el ectrode functi ons
r ever si bl y. The potenti al of a mer cur y pool anode does not depend on the
concentrati on of ni trate, chl ori de, i odi de or ammoni um i ons, but onl y on the
concentrati on of mercuri c i ons. The hal f-wave potenti al of Thal l i um was taken
as reference for determi ni ng the hal f-wave potenti al s.
Pol ari zati on i s repeated two or three ti mes i n usual practi ce. Thi s resul ts i n
anodi c di ssol uti on of smal l quanti ty of mercuri c i ons, whi ch control the el ectrode
potenti al .
(viii) Other Solvents : The pol arographi c behavi our of several cati ons and al so
oxygen i n anhydrous ethyl ene gl ycol has al so been studi ed [33]. Wel l defi ned
waves wi th hal f-wave potenti al s al most the same as those i n water wer e
obtai ned.
Other sol vents l i ke acetone [34], aceti c anhydri de [35], ani l i ne [36], benzoyl chl ori de
[37], butanol , di methyl for mami de [38], di methyl sul phoxi de [39], and di oxan [40][50]
al so the mi xtures wi th water have al so been used. Research i n thi s area al so conti nues.
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39. Schober G.; Gutmann W.: Advances i n Pol arography I .S. Longmai r, Ed. p. 940. Pergmon
Press, London 1960.
40. Stackel berg M.V., Stracke W. : Z. El ektrochem. 53, 118 (1949).
The Technique 41
CHAPTER 4
THEORY OF CURRENT
POTENTIAL CURVES
4.1 THE ILKOVIC EQUATION
The di r ect pr opor ti onal i ty between the l i mi ti ng di ffusi on cur r ent and depol ar i zer
concentrati on i s expressed i n an equati on deri ved by I l kovi c. Due to the growth of each
drop of mercury, the observed di ffusi on current vari es wi th the vari ati on of the surface
area of each drop. Thus, at a parti cul ar appl i ed potenti al the current wi l l be observed
to osci l l ate between wel l -defi ned upper and l ower l i mi ts. For an i nstantaneous current
at any ti me duri ng the drop-l i fe, the I l kovi c equati on may be expressed i n the form:
i
d
= 706
n
D
1/2
m
2/3 1 6
1
t C ...(1)
Here, n i s the number of el ectrons transferred i n the reducti on process [the i ons
desi gnated as Mn
+
whi ch begi n to be di scharged owi ng to thei r reducti on by the process:
M
n+
+ ne M (Hg)
(1)
and the i ons M
n+
arri ve at DME by the rel ati vel y sl ow process
of natural di ffusi on m i s the rate of mercury fl ow expressed i n mgs
1
, D i s the di ffusi on
coeffi ci ent of the depol ari zer i n cm
2.51
, t
1
i s the drop-ti me expressed i n seconds and C
i s the depol ari zer concentrati on gi ven i n m mol es per l i ter. Wi th these uni ts and the
numeri cal constant 706, the observed current i s gi ven i n mi croamperes. I t i s more
usual to consi der mean currents. I t i s observed that the i nstantaneous current at the
end of the drop-l i fe, i
max
, i s rel ated to the mean current duri ng the drop-l i fe, i, by the
rel ati on, =
6
7
i
max
. Thus, the form of the I l kovi c equati on for the mean di ffusi on
current i s expressed as:
i
d
= 607
n
D
1/2
m
2/3
t
1/6
C ...(2)
The I l kovi c equati on i s al ternati vel y used i n the fol l owi ng form, for the mean
di ffusi on current
i
d
= 0.627
n
D
1/2
m
2/3 1 6
1
t C ...(3)
whi ch, for D i n cm
2s1
, m i n g
s1
, t
1
i n seconds and C i n mol e cm
3
, gi ves the current i n
amperes. For most work the I l kovi c equati on i n the above for ms has pr oved to be
sati sfactory, the l i near rel ati on between i
d
and C bei ng mai ntai ned to wi thi n 1%.
However, the di ffusi on current constant I , defi ned by
I = 0.627
n
FD
1/2
=
1 6 2 3
1
d
i
cm t
...(4)
onl y mai ntai ns constancy wi thi n 5%. A typi cal cal i brati on curve i s shown i n Fi g. 4.1.
5
4
3
2
1
0
0.3 0.4 0.5 0.6 0.7 0.8
(
A
)
Fig. 4.1 : Pol arogram showi ng current osci l l ati ons. Worki ng composi ti on :
5 10
4
M Cd
4
, 0.1 M KNO
3
, 0.001% gel ati n
Many corrected forms of the equati on have been deri ved by several workers. The
fi nal forms of whi ch essenti al l y i denti fy wi th the equati on and di ffer onl y i n the val ue
gi ven to numeri cal constant, A.
Equati on (2) may be wri tten i n the form
i
d
= 0.627
n
FD
1/2
C : m
2
/3
1 6
1
t ...(5)
15.0
10.0
5.0
0.0
0.5 1.0 .5
i
A
d
C(mM/L)
Fig. 4.2 : Mean di ffusi on current versus mi l l i mol ar concentrati on for Cd
2+
i n the range 0.163 mM
to 1.22 mM, 0.1 M KNO
3
as supporti ng el ectrol yte wi th 0.001% gel ati n
Theory of Current Potential Curves 43
Sol uti on factors : el ectrode factors
I f the sol uti on factors are mai ntai ned constant, then
i
d
= const. m
2/3 1 6
1
t ...(6)
By Poi seui l l es equati on the rate of fl ow of l i qui d through a capi l l ary under a head
of the l i qui d i s di rectl y proporti oned to the hei ght of the col umn, h. Thus the rate of
fl ow, v i s the proporti onal to m whi ch i s porporti onal to h. Al so v i s proporti onal to
1/t
1
.
Ther efor e, i
d
= const. h
2/3
. h
1/6
= const. h
1/2
...(7)
The proporti onal i ty whi ch i s bei ng observed between i
d
and h
1/2
i s an acceptabl e
cri teri on of a di ffusi on control l ed process. See for exampl e the Fi g. 4.2.
4.1.1 Consequences of Ilkovic Equation
The fol l owi ng consequences can be drawn from the I l kovi c equati on.
1. The di ffusi on current i s di rectl y proporti onal to the anal yti cal concentrati on of
depol ari zer i n the sol uti on, e.g.,
i
d
=

kc ...(8)
Thi s i s fol l owed from the I l kovi c equati on and the condi ti ons bei ng that for a
gi ven val ue of m and t
1
, i.e., when the same capi l l ary i s used wi th a constant
hei ght, where k i s the I l kovi c constant, e.g.,
k = 0.627
n
FD
1/2
m
2/3
t
1/6
...(9)
Thi s equati on forms the basi s of quanti tati ve determi nati on i n pol arographi c
anal ysi s. I f the l i mi ti ng di ffusi on current val ues or wave hei ghts i s mm are
pl otted agai nst the concentrati on of a gi ven compound, a strai ght l i ne passi ng
through the ori gi n i s obtai ned. See Fi g. 4.3. Thi s may be used as a cal i brati on
curve for determi ni ng the concentrati on of the compound i n unknown sampl es.
1 2 3 4 5 6 7 8 9 0
10
20
30
40
h(cm)
i
d
(
a
r
b
.
)
Zn
2+
Cd
2+
Fig. 4.3 : i
d
ver sus
h
pl ots for a sol uti on contai ni ng 5 10
4
M Cd
2+
and
9.8 10
4
M Zn
2+
; 0.1 M KNO
3
as supporti ng el ectrol yte wi th 0.001% gel ati n.
The l i near dependence of di ffusi on current on cencentrati on does not bol d exactl y
wi th short drop-ti mes as was fi rst shown by Mass [2] and other workers too. As
a resul t the drop-ti me shoul d not be l ess than two sec. The reason bei ng that
under these condi ti ons whi rl i ng occurs and destroys the di ffusi on l ayer and the
currents gets i ncreased. The most sui tabl e drop-ti me i s from 3 to 5 sec.
I t further fol l ows from equati on (8) that equi val ent concentrati ons of substances
wi th equal di ffusi on coeffi ci ents gi ve equal currents, si nce a l arge number of
cati ons have si mi l ar di ffusi on coeffi ci ents and si nce smal l di fferences have onl y
a smal l effect. The reason bei ng that square root of D i s used i n the cal cul ati on,
di ffusi on currents for the same equi val ent concentrati ons are roughl y equal
(Tabl e 4.1).
TABLE 4.1
Comparison of percentage differences between observed and
calculated mean diffusion currents
I on i
d
I lkovic equation i
d
correct equation
% %
Tl
+
0.8 13.7
Pb
2+
+1.0 8.7
Cd
2+
+7.8 0
Zn
2+
+4.9 3.7
Cu
2+
1.3 10.7
I O
3
+0.4 9.3
( )
3
Fe CN
6
+8.1 16.9
2
CrO
4
3.6 15.2
I f the di ffusi on coeffi ci ent i s known the number of el ectrons n parti ci pati ng i n
the el ectrode process may be cal cul ated from the I l kovi c equati on. Actual l y
compari son can be made under the same condi ti on the di ffusi on current of
substances to be i nvesti gated wi th the di ffusi on current of a substance taki ng
up a known number of el ectr ons, i.e., wi th the same capi l l ary, concentrati on,
hei ght of mercury head and temperature. From the rati o of the di ffusi on currents,
the val ue of n can be determi ned.
2. Dependence on the Height of Mercury Head, Capillary Characteristics
and Potential : I f the hei ght of the mer cur y head i s changed at constant
concentr ati on of the substance, the fl ow-r ate m and dr op-ti me t char ge
si mul taneousl y. Accordi ng to the fol l owi ng equati ons:
m= k' h = k' (h
a
h
b
) ...(10)
t
1
= k
n
1
h
...(11)
m i s di rectl y proporti onal and t
1
i nversel y proporti onal to the corrected hei ght
of h of the mer cur y head:
m = k' h; t
1
= k"
1
h
...(12)
Substi tuti ng i n the I l kovi c equati on i t takes the form:
i
d
= Km
2/3 1 6
1
t = K (k' h)
2/3
1 6
k"
h
| |
|
\ .
...(13)
and on combi ni ng al l constants
i
d
= k h ...(14)
i.e., the di ffusi on cur r ent i s di r ectl y pr opor ti onal to the squar e-r oot of the
corrected hei ght of the mercury head (reservoi r). Thi s l i near dependence provi des
an easi l y accessi bl e experi mental test for di ffusi on control l ed currents.
The corrected hei ght of the mercury head may be cal cul ated from the above
equati on (10). I n qui te some i nvesti gati ons i nto the character of l i mi ti ng currents
i t i s suffi ci ent to pl ot the l i mi ti ng current agai nst the square-root of the actual
hei ght of the mercury head. I n case of di ffusi on control l ed current the pl ot gi ves
a strai ght l i ne, but thi s l i ne does not pass through the ori gi n, i t onl y cuts a
smal l i ntercept on the current axi s.
4.2 REVERSIBLE AND IRREVERSIBLE ELECTRODE PROCESSES
I t i s qui te possi bl e to control the rates of most el ectrode processes wi th some preci si on,
whi ch i s qui te unl i ke the case for normal chemi cal reacti ons. Control of the appl i ed
potenti al control s the current fl ow by control l i ng the hei ght of the acti vati on energy
barri er for the process.
A si mpl e el ectrochemi cal reducti on process i s consi dered here, e.g.,
A + ne B ...(15)
whi ch i s occurri ng at an i nert el ectrode and al so that both oxi dant and reductant are
sol ubl e i n the sol vent medi um used. A si mpl e vi ew of the effect of an appl i ed potenti al ,
E, assumes i t to cause a decrease i n the reacti on energy barri er i n one di recti on and
an i ncrease i n the reverse di recti on. An i ncrease of negati ve potenti al i ncreases the
forward rate of reacti on Eq. (15), the energy barri er to i ts progress bei ng reduced by
an amount (E E
0
) nF. The energy barri er of the reverse reacti on i s correspondi ngl y
i ncr eased by an amount (E E
0
) nF. Here the expressi ons E and E
0
are the appl i ed
and standard potenti al s respecti vel y, whi l e and are termed the transfer coeffi ci ents
rel ated through the expressi on + = 1. A transfer coeffi ci ent may thus be regarded
as the fracti on of the appl i ed potenti al whi ch ei ther assi sts or hi nders the process
under consi derati on. Observi ng the di agram bel ow, the si gni fi cance of and can be
seen i n Fi g. 4.4.
(EE
0
)nF
(EE
0
)nF
Backward ( oxi dati on) process
Forward (reducti on) process
Fig. 4.4 : Diagram showing effect on forward and backward reaction activation
energy barri ers of an appl i ed potenti al i n excess of E
0
.
I n ter ms of cur r ent densi ti es, the r ates of for war d (r educti on) and backwar d
(oxi dati on) processes for the reacti on* (15) may be expressed as fol l ows:
r
1
=
cath
I
nF
= k
cath
[A]
e
...(16)
and r
2
=
an
I
nF
= k
an
[B]
e
...(17)
I n these equati ons r
1
and r
2
represent the two rates, I
cath
and I
an
, i.e., the cathodi c
and anodi c current densi ti es respecti vel y. The terms k
cath
and k
an
and the appropri ate
rate constants. [A]
e
and [B]
e
refer to concentrati ons of oxi di zed and reduced forms of the
depol ari zer at the el ectrode surface.
I f the appl i ed potenti al i s E
0
, wi th for war d and backwar d r ates bei ng equal , the
every barri er to ei ther process i s the acti vati on energy, Q. That i s to say, Q i s the
acti vati on energy of the el ectron transfer from el ectrode to depol ari zer parti cl e A, at
the surface, at zero appl i ed potenti al between the el ectrode and the sol uti on. At an
appl i ed potenti al di fference, E, thi s ener gy i s r educed by an amount
ne
E, e bei ng the
uni t el ectroni c charge. Thus, for the rate of el ectro-reducti on we have
r
1
= k [A]
e
exp
ne
Q E
kT
+ (
(

...(18)
= k [A]
e
exp
n
FE
RT
(
(

where k and k are constants for the parti cul ar process and k i s the Bol tzmann
constant. k i ncl udes the term e
Q
. A anal ogous expr essi on may be had for the r ate of
el ectr o-oxi dati on.
Cathodi c and anodi c rate constants may be expressed as:
k
cath
= k
0
exp ( )
0 n
F
E E
RT
(

(

...(19)
and k
an
= k
0
exp
( )
( )
0
1
n
F
E E
RT
(
(
(

...(20)
I n the above equati ons, k
0
represents the heterogeneous rate constant of the el ectrode
process at the standard potenti al , E
0
, and i ncl udes the term e
Q
. These expressi ons may
be i nser ted i n the equati ons (15) and (17) to gi ve:
I
cath
= nFk
0
[A]
e
exp ( )
0 n
F
E E
RT
(

(

...(21)
and I
an
= nF k
0
[B]
e
exp ( )
0 n
F
E E
RT
(
(

...(22)
I n these l atter two equati ons, the conventi on that has been adopted as regard to a
cathodi c current as posi ti ve and an anodi c current as negati ve.
The al gebrai c sum of the cathodi c and anodi c contri buti on, as observed by the
current densi ty I , are represented as:
I = nF k
0
| | ( ) | | ( )
0 0
exp exp
n n
e e
F F
A E E B E E
RT RT
( (

`
( (
)
...(23)
or I =
| | ( ) | | ( )
0 0
0
exp exp
n n
e e
F F
I A E E B E E
RT RT
( (

`
( (
)
...(24)
where I
0
= nF k
0
and i s termed the exchange current densi ty i.e., the condi ti on when
E = E
0
at whi ch no net current i s observed, the cathodi c and anodi c components bei ng
of equal magni tude but fl owi ng i n opposi te di recti ons. For smal l val ues of Q, k
0
i s very
l arge; such a condi ti on i s found i n reversi bl e systems where the el ectrochemi cal
processes are consi dered to be very rapi d. For consi deri ng the essenti al di fferences
between reversi bl e and i rreversi bl e el ectrode processes, the form taken i n the above
equati on I and E under such condi ti ons that k
0
i s very l arge or very smal l .
4.3 REVERSIBLE POLAROGRAPHIC WAVE
A system consi sti ng of a perfectl y pol ari zabl e droppi ng mercury el ectrode and a non-
pol ari zabl e stati onary el ectrode. I f an external vol tage i s appl i ed to such a system, the
enti re potenti al drop i s concentrated at the i nterface between the droppi ng el ectrode
and the sol uti on under i nvesti gati on. Due to thi s reason the pol arographi c curves are
determi ned sol el y by the processes occurri ng at the DME. The dependence of the current
on the potenti al of the mercury el ectrode, the pol arographi c curve gi ves a parti cul ar
shape. Thi s concl udes the character of the el ectrode process ari si ng out of the current
vol tage curves.
The parti cl es of depol ari zer subject to el ectrochemi cal change i.e., r educti on or
oxi dati on at the el ectrode reach the el ectrode by di ffusi on onl y. The equati on deri ved
for thi s ki nd of current, the di ffusi on current, requi res a constant concentrati on of
depol ari zer at the surface of the el ectrode for a gi ven potenti al . I f the shape of the
current potenti al curve i s to be deri ved, the rel ati onshi p between the concentrati on at
the el ectrode surface and the potenti al must be taken i nto account. For reversi bl e
processes, thi s rel ati onshi p i s obtai ned from the Nernst equati on. By a reversi bl e process
i s meant one i n whi ch the rati o of the concentrati ons of oxi di zed reduced form at the
el ectrode surface i s gi ven by the Nernst equati on:
E = E
0
| |
| |
0
0
Red
ln
RT
nF OX
...(25)
I n thi s equati on [Red]
0
and [OX]
0
denote the concentrati ons of the reduced and
oxi di zed form of the depol ari zer at the el ectrode surface respecti vel y. E
0
, the standard
oxi dati on reducti on potenti al of the system and E the potenti al of the droppi ng mercury
el ectrode as determi ned by the appl i ed e.m.f. I t i s conveni ent to refer both potenti al s
to the potenti al of the non-pol ari zabl e el ectrode rather than to the standard hydrogen
el ectrode, E i s then numeri cal l y equal to the appl i ed e.m.f.
Emphasi s i s l ai d on the fact that Ner nst equati on whi ch hol ds for r ever si bl e
thermodynami c equi l i bri a, i.e., under condi ti ons when no current i s fl owi ng. The use
of the Nernst equati on i s justi fi ed i f the equi l i bri um rate of el ectron exchange between
el ectrode and reactants i s so great that i t can easi l y accommodate the smal l net current
fl ow wi thout a si gni fi cant departure from the equi l i bri um concentrati on.
4.3.1 Cathodic Wave
On consi deri ng a cathodi c reducti on the oxi di zed form of the depol ari zer (e.g., Tl
+
, Cd
2+
or reduci bl e mol ecul es) al one i s present i n the sol uti on. I t accepts el ectrons from the
droppi ng el ectrode and so el ectrons fl ow from the non-pol ari zabl e el ectrode i.e., anode
to the DME vi a the exter nal ci r cui t. Thi s i s the so cal l ed cathodi c cur r ent. The
pol arograph i s conventi onal l y connected i n such a way that on pol arograms thi s current
appears above the gal vanometer zero-l i ne.
Accordi ng to the I l kovi c equati on, the mean cur r ent suppl i ed by di ffusi on of a
depol ari zer to the el ectrode surface i s gi ven by:
i = k [OX] [OX]
0
...(26)
i n whi ch k = 0.627nF D
1/2
m
2/3 1 6
1
t ...(27)
i s the I l kovi c constant. The parti cl es reduced at the surface thereupon di ffuse away. I n
cases where amal gam formati on takes pl ace, e.g., i n metal s l i ke Tl , Pb, Cd, Zn and
al kal i metal s, these are transported by di ffusi on i nto the mercury drop. I f no amal gam
i s formed, e.g., i n reducti ons of Fe
3+
Fe
2+
, Sn
4+
Sn
2+
and i n some organi c systems
l i ke qui none qui nol , the reduced parti cl es di ffuse back i nto the bul k of the sol uti on.
The equati on governi ng thi s di ffusi on away from the surface i n ei ther di recti on i s:
i = k' [Red]
0
[Red] ...(27a)
i n whi ch k' = 0.627nF D
1/2
m
2/3 1 6
1
t di ffers form k onl y i n the val ue of di ffusi on coeffi ci ent
for the reduced parti cl e D.
As al ready stated above, i t i s assumed that onl y the oxi di zed form i s present i n the
bul k of the sol uti on, i.e., [Red] = 0, and so the precedi ng equati on now takes the form:
i = k' [Red]
0
...(27b)
I f the concentrati ons of the reduced and oxi di zed forms at the surface of the el ectrode
are el i mi nated from equati ons (27, 27a, 27b). The fol l owi ng equati on i s obtai ned:
E =E
0
| |
ln
' '
RT i k
nF k OX i k
...(28)
Heyr ovsky and I l kovi c fi rst deri ved thi s equati on for a cathodi c wave [4].
Fig. 4.5 : Reversi bl e cathodi c wave. 5. 10
3
M Tl
2
SO
4
, 1 M Li
2
SO
4
, 0.04%
gel ati n; sens. 1 : 150, 208 mV/scal e uni t
Si nce | | ,
d
k OX i = ...(29)
where i
d
i s the mean l i mi ti ng cathodi c di ffusi on cur r ent, equati on (28) i s r eadi l y
transformed i nto the Tomes form [5]
0
ln
d
RT i D
E E ;
nT i i D
=

...(30)
the rati o of the I l kovi c constant k/k' is D D Si nce for many depol ari sers the di ffusi on
coeffi ci ent of the oxi di zed and the reduced forms are nearl y equal and, i n thei r square
root form, the expressi on D D may be set equal to uni ty. The for goi ng equati on then
fi nal l y takes the form:
0
ln
d
RT i
E E
nF i i
=
...(31)
Thi s equati on i s the si mpl est mathemati cal expressi on for the shape of a reversi bl e
cathodi c wave.
Experi mental reversi bl e cathodi c waves accord perfectl y wi th the deri ved equati ons.
The poi nt on the pol arographi c curve correspondi ng to one-hal f of the l i mi ti ng
di ffusi on current represent the i nfl exi on poi nt of the curve. I t i s termed the hal f-wave
poi nt or correspondi ngl y the hal f-wave potenti al , E . The expr essi on for the hal f-wave
potenti al may r eadi l y be der i ved fr om the equati on for the pol ar ogr aphi c wave
i ntr oduci ng i = i
d
/2. Thus i s obtai ned:
E = E
0
ln
RT D
nF D
...(32)
fr om the equati on (22) or
E = E
0
fr om equati on (23)
The hal f-wave potenti al i s a constant that i s i ndependent of the concentrati on of
the depol ari zer, of the capi l l ary characteri sti cs and of the gal vanometer sensi ti vi ty and
has a val ue characteri sti c of the gi ven depol ari zer. I f the reducti on product does not
form an amal gam wi th mercury, the hal f-wave potenti al i s vi rtual l y i denti cal wi th the
standard oxi dati on-reducti on potenti al (Eq. 23). I f an amal gam i s formed, the hal f-
wave potenti al corresponds to the standard potenti al of the amal gam el ectrode (see
hal f-wave potenti al and i ts si gni fi cance). When the depol ari zer concentrati on i s vari ed,
the hei ght and the tar get-potenti al of the wave change, the hal f-wave potenti al for a
reversi bl e wave remai ns constant. Not onl y thi s but the rel ati ve hei ght i/i
d
of the wave
at a gi ven potenti al i s i ndependent of depol ari zer concentrati on.
An i mportant property of a reversi bl e pol arographi c curves i s i ts symmetry wi th
respect to E . Thus the di stance between E and E i s the same as that between
E and E .
I f an amal gam i s formed the hal f-wave potenti al corresponds to the standard potenti al
of the amal gam el ectrode as gi ven i n Chapter 1. When the depol ari zer concentrati on
i s var i ed, the hei ght and the tangent potenti al of the wave change, but the hal f-wave
potenti al for a reversi bl e wave remai ns constant (see Fi g. 4.6). Furthermore, the rel ati ve
hei ght i/i
d
, of the wave at a gi ven potenti al i s i ndependent of depol ari zer concentrati on.
From the equati ons deri ved for the pol arographi c wave, the fi nal equati on i s:
E = E
ln
d
RT i
nF i i
...(33)
4.3.2 Anodic Wave
Anodi c oxi dati ons are of two ki nds:
(i) The reduced form i s i n mercury drop so that i nstead of pure mercury an amal gam
fl ows out of the capi l l ary [3
6]. Thi s reduced form i n whi ch
the metal i s oxi di zed at the
sur face of the DME and the
cati on s th u s for med ar e
transported by di ffusi on i nto
the bul k of the sol uti on, and
(ii) Th e r edu ced for m of th e
depol ari zer i s present i n the
sol uti on and i s transported by
di ffusi on to the DME, where
i t i s ox i di zed an d th en
r etur ned to the bul k of the
sol uti on. Here the exampl e of
Fe
2+
and qui nol i s workabl e.
I n both oxi dati ons, the di recti on
of di ffu s i on of th e ox i di zed an d
reduced forms i s the reverse of that
i n a cathodi c reducti on. The el ectrons
fl ow fr om th e DME th r ou gh th e
external ci rcui t to the non-pol ari zabl e
el ectrode. The resul ti ng anodi c current
(negati ve si gn) i s recorded beneath the
gal vanometer zone-l i ne (excepti ons are
of mi xed currents).
Consi der i ng the di ffusi on of the
r edu ced for m th e fol l owi n g
rel ati onshi p must hol d:
i = k ([Red] [Red]
0
) ...(1)
The oxi di zed form di ffuses from the surface of the el ectrode back i nto the bul k of the
sol uti on, where i ts concentrati on i s zero. The current can, therefore, be rewri tten as
i = k [OX] ...(2)
On substi tuti ng these di ffusi on rel ati onshi ps (foregoi ng equati ons) i n the equati on:
E = E
0
| |
| |
0
0
Red
ln
RT
nF OX
...(3)
E
+
Fig. 4.6 : I ndependence of hal f-wave potenti al
fr om concentr ati on. The concentr ati on of Cd
2+
i ncreases up to 10
3
N
the equati on of the current-potenti al curve for anodi c oxi dati ons at DME i s obtai ned
as fol l ows:
E = E
0
ln
RT k'Red k
i
nF i k'
+
...(4)
The anodi c di ffusi on cur r ent [Red]
0
= 0, i s attai ned when [Red]
0
= 0, hence on
substi tuti ng thi s rel ati onshi p i n the foregoi ng equati on we obtai n:
E = E
0
ln
d
i i RT D
nF i D
...(5)
The whol e anodi c curve appears beneath the gal vanometer zero l i ne as i s shown i n
the Fi g. 4.7.
I f, as i n the cathodi c reducti on, i i s made equal to i
d
/2, and expressi on i denti cal
wi th equati on i s obtai ned e.g.,
E = E
0
0
ln
RT D
E
nF D
=
...(6)
when i can be negl ected compared wi th i
d
= k [Red] i n equati on (7) we obtai n the
exponenti al form of the anodi c curve wi thout
con cen tr ati on pol ar i zati on i .e., the
concentr ati on of the depol ar i zer at the
el ectrode surface was the same as that i n the
body of the sol uti on, even wi th a cur r ent
passi ng through the system:
E = E
0
Red
ln
RT k' i k
nF i k'
+
...(7)
4.3.3 Cathodic-Anodic Waves
Whi l e consi der i ng an oxi dati on-r educti on
system, where both forms are avai l abl e for
el ectrol ysi s, i t i s observed that two di ffusi on
cur r ents ar e r esul ti ng. Wi th i ncr easi ng negati ve potenti al s, the dr oppi ng mer cur y
el ectrode becomes depl eted of the oxi di zed form and the cathodi c di ffusi on current i
d
appears. And an depl eti on of the reduced form wi th i ncreasi ng posi ti ve potenti al s the
anodi c di ffusi on current (see Fi g. 4.8) appears.
Two si tuati ons are observed:
(a) The oxi di zed form i s i n sol uti on (e.g., cati ons of metal s such as Tl
+
and Cd
2+
)
and the reduced form i n the mercury (i.e., the metal s that form amal gam).
(b) Both the oxi di zed and reduced form are i n the sol uti on Fe
2+
and Fe
3+
i n oxal ate.
I n both the si tuati ons the current i s gi ven by the equati ons:
i =

k [OX] [OX
0
] ...(8)
i.e., di ffusi on of the oxi di zed form to the el ectrode surface.
Fig. 4.7 : A Typi cal Anodi c wave
+E
+i
i
E
i
d
CHAPTER 5
TYPES OF CURRENTS
5.1 MASS TRANSFER AND ELECTROCHEMICAL PROCESSES
Two mai n types of processes are i nvol ved i n any el ectrol ysi s. These are : transference
of matter through a sol uti on towards and away from the el ectrodes, and the other i s
i n whi ch the el ectrochemi cal process i nvol ves the exchange of el ectrons at the el ectrode
surface as an essenti al part.
Dur i ng an el ectr ol ysi s thr ee mass tr ansfer pr ocesses ar e of i mpor tance, e.g.,
mi grati on, di ffusi on and convecti on. The fi rst of these i.e., mi grati on i s an essenti al
effect dependi ng upon the charge carri ed by an el ectroacti ve speci es and upon i ts
transference number. Thus, the effect i s encountered onl y wi th charged speci es. Si nce
the processes of natural di ffusi on are non-el ectri cal i n ori gi n, these are observed for al l
speci es i n sol uti on whether they are charged or not. Convecti on effects i ncl ude the
moti on of smal l parti cl es under the i nfl uence of sti rri ng, mechani cal agi tati on, and
temperature gradi ents.
I n pol arographi c work the mi grati on effect i s usual l y el i mi nated. The convecti on
effects are el i mi nated by carryi ng out any el ectrol ysi s i n an control l ed thermostat and
al so by protecti ng the apparatus from al l forms of vi brati ons and shocks.
5.2 DIFFUSION CURRENT
The most i mportant component of the wave hei ght i s the di ffusi on current, whi ch
refl ects the rate at whi ch the i ons or mol ecul es of the substance responsi bl e for the
wave reach the el ectrode surface under the sol e i nfl uence of a di ffusi ve force. On the
pl ateau of the wave these i ons or mol ecul es get reduced of oxi di zed as rapi dl y as they
reach the el ectrode surface, and thei r concentrati on i n the l ayer of sol uti on i mmedi atel y
adjacent to the el ectr ode sur face i n ther efor e vi r tual l y zer o. Hence ther e i s a
concentrati on gradi ent between the bul k of the sol uti on and the l ayer at the el ectrode
surface, and i t i s thi s concentrati on gradi ent whi ch i s responsi bl e for the exi stence of
the di ffusi ve force.
The di ffusi on current i s very i mportant i n pol arographi c anal ysi s because most
practi cal methods are based on i ts measurements.
The rate at whi ch the el ectroacti ve materi al can reach the el ectrode surface may
however be affected by many other phenomena. The or i gi nal speci es or another
el ectroacti ve one, may be regenerated by a reacti on between the product of the el ectrode
reacti on and some other consti tuent of the sol uti on, and i n such a case, the current due to
the reducti on of the regenerated substance wi l l then al so be i ncl uded i n the wave hei ght.
I f the sol uti on contai ns a speci es that i s not el ectroacti ve i s i n sl ow equi l i bri um
wi th one that i s, the wave hei ght wi l l i ncl ude not onl y the di ffusi on current of the
el ectroacti ve speci es but al so a current due to the reducti on of addi ti onal el ectroacti ve
materi al s formed from the non-el ectroacti ve speci es as equi l i bri um between them i s
di spl aced at the drop surface. I n some cases excess of the el ectroacti ve substance to the
el ectrode surface may be barred by a fi l m of adsorbed materi al , or the el ectroacti ve
substance or i ts reducti on (or oxi dati on) product may undergo adsorpti on on the drop
surface and the current may then be l i mi ted by the number of i ons or mol ecul es whi ch
can be adsor bed on each dr op.
As al ready descri bed a current whose magni tude i s control l ed by the rate of di ffusi on
i s cal l ed a di ffusi on current. I n pol arographi c measurements an excess of supporti ng
el ectrol yte i s used for several reasons. I t not onl y el i mi nates the effects of mi grati on,
i nstead i t al so greatl y di mi ni shes the potenti al drop iR, thus transformi ng the current
vol tage curves at DME i nto current potenti al curves. The supporti ng el ectrol yte al so
si gni fi es great practi cal i nfl uence i n anal yti cal pol arography.
A general rel ati onshi p may be wri tten for the el ectrol yti c current at DME, accordi ng
to Faradays l aw:
i = nF
dN
dt
...(1)
where dN/ dt denote the number of mol e of the depol ari zer that reaches the el ectrode
i n uni t ti me and i s subject to el ectrochemi cal change. [F i s the Far aday (96500 cont.)
and n i s the number of el ectrons taken up or deri ved by a si ngl e mol ecul e of depol ari zer
duri ng the el ectrode process]. I f the depol ari zer i s transported to the el ectrode by
di ffusi on al one, the val ue dN/ dt can be cal cul ated from Fi cks Second Law. I n thi s way,
the equati on for the di ffusi on cur r ent can be der i ved.
5.2.1 Diffusion to Stationary Electrodes
Linear Diffusion : Di ffusi on may be descri bed as a spontaneous process l eadi ng to
equi l i brati on of concentrati on di fferences i n concentrati on gradi ents. I f a concentrati on
gradi ent ari ses i n sol uti on, the sol ute starts to move from areas of hi gh to those of
l ower concentrati on. The rate of di ffusi on i s proporti onal to the concentrati on gradi ent,
but al so depends on the properti es of the di ffusi ng parti cl es. I f di ffusi on occurs i n one
di recti on onl y, the process i s termed l i near di ffusi on.
Consi deri ng l i near di ffusi on to a pl ane el ectrode (cross secti on q), the concentrati on
of depol ari zer decreases i n the di recti on perpendi cul ar to the el ectrode E owi ng to an
el ectrochemi cal change at the el ectrode (Eq. 2). The number of mol es dN of the substance
that di ffuses across the area q at a di stance x i s proporti onal to the area q, to the
concentrati on gradi ent de/ dx and to the ti me i nterval [Fi cks fi rst l aw].
dN = Dq
dc
dx
dt ...(2)
Types of Currents 59
I n thi s expressi on the proporti onal i ty constant i s the di ffusi on coeffi ci ent D, i ndi cati ng
the number of mol es of the substance that passes by di ffusi on through uni t area at a
concentrati on gradi ent of one i n uni t ti me.
5.2.2 Diffusion-Controlled Current
Ficks Law : Di ffusi on may be descr i bed as a spontaneous pr ocess l eadi ng to
equi l i brati on of concentrati on di fferences i n concentrati on gradi ent. I f a concentrati on
gradi ent ari ses i n sol uti on, the sol ute starts to move from areas to hi gh to those of
l ower concentrati on. The rate of di ffusi on i s proporti onal to the concentrati on gradi ent,
but al so depends on the properti es of the di ffusi ng parti cl es. I f di ffusi on occurs i n one
di recti on onl y the process i s termed l i near di ffusi on. Consi der a cyl i nder wi th a cross
secti on q. Fi g. 5.1.
The concentrati on of depol ari zer decreases i n the di recti on perpendi cul ar to the
el ectrode E owi ng to an el ectrochemi cal change at the el ectrode. The number of mol es
dN of the substance that di ffuses across the area q at di stance x i s proporti onal to the
area q, to the concentrati on gradi ent dc/ dx to the ti me i nterval dt
dN = Dq
dc
dx
dt ...(3)
(Fi cks Fi rst Law deri ved i n 1855). I n thi s expressi on
the proporti onal i ty constant i s the di ffusi on coeffi ci ent
D, i ndi cati ng the number of mol es of the substance that
passes by di ffusi on through uni t area at concentrati on
gradi ent of one i n uni t ti me. Di ffusi on coeffi ci ents are
normal l y of the order, 10
6
10
5
cm
2
. sec
1
.
Th e di ffu s i on cu r r en t i s deter mi n ed by th e
concentrati on gradi ent at the surface of the el ectrode,
i.e., (c/x)
x=0
, whi ch i s ti me-dependent (as ar e the
concentrati on gradi ents at al l other di stances). Thus
i =
0
q
x
dN dc
nF nF D
dt dx
=
| |
=
|
\ .
...(4)
Thi s concentrati on gradi ent may be cal cul ated from Fi cks Second Law:
2
2
c c
D
t
x

=
...(5)
Spherical diffusion : When determi ni ng the concentrati on gradi ent towards a
stati onary spheri cal el ectrode the deri vati on must be based an Fi cks Second Law,
whi ch i n spheri cal co-ordi nates has the form;
2
2
2 2 c c
D
t r r
r
(

= +
(

(

...(6)
Note : For detai l s more books be consul ted.
Fig. 5.1 : Li near di ffusi on
to Pl ane El ectrode
c
qx X
x + dx
c + dc
qx + dx X
E
x = 0
I f the depol ari zer i s transported to the el ectrode by di ffusi on al one, the val ue
dN/ dt can be cal cul ated from Fi cks Second Law and the equati on for di ffusi on current
can be der i ved.
5.2.3 Linear Diffusion to a Growing Dropping Electrode
The Ilkovic Equation : Cal cul ati on of the concentrati on gradi ent towards a growi ng
droppi ng el ectrode i s qui te compl i cated. I n 1934, I l kovi c [1] sol ved thi s probl em. He
assumed that the droppi ng el ectrode behaves as a pl ane el ectrode wi th an area equal
to that of the surface of the drop, i.e., area i ncreasi ng wi th ti me. Consi deri ng the
growth of the drop by the decrease i n thi ckness of the di ffusi on l ayer as i t spreads out
over the growi ng surface of the drop.
Experi mental fi ndi ngs of Kemul a [2] hel ped I l kovi c i n deri vi ng the di ffusi on current
equati on that capi l l ari es wi th equal fl ow-rates gi ve approxi matel y equal l i mi ti ng currents
and that the dependence of the di ffusi on cur r ent on the hei ght of the mer cur y col umn
i s parabol i c.
5.2.4 Diffusion Coefficient
The val ues of the di ffusi on coeffi ci ents for the depol ari zers must be known i n order to
cal cul ate the magni tude of di ffusi on currents:
Ner nst [3] Ner nst W.; Z. Physi k, Chem., 2, 613 (1988)
deri ved the formul a:
2
RT
D A
nF

=
...(7)
Substi tuti ng R = 8.317 V, Coul ., deg.
1
and F = 96500 coul ., then at 25C :
7
26710 . .
D
n
= ...(8)
The fol l owi ng Tabl e 5.1 as taken from the fol l owi ng books gi ve some val ues of
di ffusi on coeffi ci ents:
[Tabl e 5.1 from Pri nci pl es of Pol arography by Heyrovsky & Kuta, p. 105]
TABLE 5.1
Diffusion Coefficients for Ions at Infinite Dilution at 25C
I on
. 10
5
I on
. 10
5
1
. cm
2
cm
2
. sec
1

1
. cm
2
cm
2
. sec
1
H
+
350 9.34 OH
196 5.23
Li
+
39 1.04 Cl
76 2.03
K
+
74 1.98 NO
3
72 1.92
Na
+
50.5 1.35 I O
3
41 1.09
NH
4
+
73.4 1.96 I O
4
54.4 1.45
Cs
+
79 2.11 BrO
3
54 1.44
Ag
+
61.9 1.65
2
SO
4
81 1.08
Tl
+
75 2.00
2
CrO
4
80 1.07
Mg
2+
53.06 0.71 CH CO
3 2
41 1.09
Ca
2+
59.5 0.79 C H CO
6 5 2
32.3 0.86
Sr
2+
59.46 0.79 HC O
2 4
40.2 1.07
Ba
2+
63.64 0.85
2
C O
2
4
74.1 0.99
Cd
2+
54 0.72
( )
3
Fe CN
6
100 0.89
Zn
2+
54 0.72
( )
4
Fe CN
6
110.5 0.74
Cu
2+
54 0.72
Ni
2+
52 0.69
Pb
2+
73 0.95
As a matter of fact di ffusi on coeffi ci ents are normal l y of the order, 10
6
10
5
cm
2
.
sec
1
.
The di ffusi on current i s determi ned by the concentrati on gradi ent at the surface of
the el ectrode, i.e., (c/x)
x=0
, whi ch i s ti me dependent (as are the concentrati on gradi ents
at al l other di stances). Thus
0
dN c
i nF nF D
q
dt x
x
| |
= =
|
\ .
=
...(9)
Thi s concentrati on gradi ent may be cal cul ated from Fi cks Second Law; (al ready
gi ven)
2
2
c c
D
t
x

=
...(10)
From equati on (9) current i s obtai ned towards a pl anar stati onary el ectrode:
i = nF
q
D
( )
0
C* C
Dt
...(11)
For the l i mi ti ng di ffusi on current
(C
0
= 0); i
1
= nF
q
D
( )
C*
Dt
...(12)
Accordi ng to thi s equati on the current decreases wi th ti me as requi red by the
rel ati onshi p i = kt
1/2
. The expressi on ( ) Dt i s the so cal l ed di fferenti al thi ckness of
the di ffusi on l ayer and i s a functi on of ti me.
5.2.5 Spherical Diffusion
When determi ni ng the concentrati on gradi ent towards a stati onary spheri cal el ectrode
the deri vati on must be based on Fi cks Second Law, whi ch i n spheri cal coordi nates has
the form
2
2
2
c
c c
D
t r r r
(

= +
(
(

...(13)
The sol uti on of thi s equati on i s carri ed out for the appropri ate i ni ti al and boundry
condi ti ons: for t = 0, c = c*, i.e., at the begi nni ng of the el ectrol ysi s the same i ni ti al
concentrati on of depol ari zer i s present both i s the bul k of the sol uti on and at the
el ectrode. Duri ng el ectrol ysi s (for l i mi ti ng di ffusi on current, i.e., for t = 0 and for r =
r
0
, where r
0
i s the radi us of the spheri cal el ectrode). The concentrati on i n zero, c = 0.
The di fferenti al equati ons when si mpl i fi ed, the sol uti on l eads to the rel ati on for the
ori gi nal vari abl e:
c = f (r, t) = c* .
0
0 0
2
1
2
r r r r
erf c*
r r Df
| |
| |
+
| |
\ .
\ .
...(14)
1 2 3 4
Fig. 5.2 : Pol arogram i l l ustrati ng the dependence of the di ffusi on current on the mercury head.
Zn
2+
i n 1 M NH
3
, 1 M NH
4
Cl (gel ati n + Sul phi te). Mercury head : 1h = 90, 2 58, 3 40, 4 27 cm
I t fol l ows from thi s equati on that when r appr oaches r
0
, the sol uti on of the equati on
resembl es that for di ffusi on towards a pl ane el ectrode. Thus di ffusi on wi thi n a short
di stance from the surface of a spheri cal el ectrode may be regarded as l i near.
5.3 INFLUENCE OF VISCOSITY AND OF COMPLEX FORMATION ON
DIFFUSION CURRENT
Referri ng to the quanti ti es i n I l kovi c equati on i t i s to be noted that the drop-ti me,
the di ffusi on coeffi ci ent and to a l arge extent the rate of mercury fl ow (through the
change i s back-pressure) may be affected by a change i n composi ti on of the sol uti on.
Moreover, the drop-ti me may vary consi derabl y i s di fferent medi a, but si nce onl y 6th
root appears i n the equati on i ts i nfl uence on the observed phenomena i s negl i gi bl e.
Further, the drops-ti me i s easi l y measured. However, the charge i n di ffusi on coeffi ci ent
i s gi ven by Stokes-Ei nstei n l aw, whi ch states that the di ffusi on coeffi ci ent i s i nversel y
proporti onal to the vi scosi ty of the sol uti on:
D =
k
...(15)
The rel ati on for dependence of di ffusi on current on vi scosi ty
i
d
= const. ...(16)
The val i di ty of thi s rel ati on i s l i mi ted by that of Stokes-Ei nstei n l aw, whi ch assumes
a sati sfactory state that the di ffusi ng parti cl es are spheri cal and are consi derabl y
l arger than the sol vent parti cl es.
5.4 FACTORS AFFECTING THE DIFFUSION CURRENT
The Concentration of the Electroactive Substance : The r ate at whi ch the
el ectroacti ve substance reaches the el ectrode surface, and consequentl y the current
resul ti ng from i ts reducti on or oxi dati on as rapi dl y as i t arri ves there i s proporti onal
to i ts concentrati on i n the bul k of the sol uti on. The shape of the el ectrode does not
matter. I t may be pl ane, spheri cal , cyl i ndri cal or some other. I t may be stati onary or
movi ng. I ts area may be or may not be constant, or, the mass transfer of the el ectroacti ve
substance occurs by di ffusi on, Lami nar fl ow or convecti on. Two thi ngs are general l y
r equi r ed: (i) the suppl y of el ectroacti ve substance at the el ectrode surface must not be
affected by any chemi cal or physi cal process. Thi s i ncl udes ki nds of sl ow chemi cal
reacti ons, or adsorpti on on the el ectrode surface, and (ii) i s that the thermodynami cs
and mechani sm of the mass-transfer process must be i ndependent of the concentrati on
of el ectroacti ve substance. I n al l vol tammetri c techni ques, thi s proporti onal i ty between
the mass-transfer control l ed current and concentrati on i s observed and i s the basi s of
the vast majori ty of the practi cal anal yti cal methods and physi co chemi cal appl i cati on
whi ch are based on these techni ques.
From the I l kovi c equati on, i t fol l ows that for gi ven val ues of m and t
1
i.e., i f the
some capi l l ary i s used wi th a constant hei ght of the mercury head, the di ffusi on current
i s di rectl y proporti onal to the anal yti cal concentrati on of depol ari zer i n the sol uti on :
i
d
= kc ...(17)
where k i s the I l kovi c constant;
k = 0.627
1 2 1 6 2 3
1 D
nF m t ...(18)
h
I
d
Fig. 5.3 : Dependence of di ffusi on current
on the square-root of the mercury head.
Thi s equati on forms the basi s of quanti tati ve determi nati ons i n pol arographi c anal ysi s.
I f the l i mi ti ng di ffusi on current val ues or wave hei ghts i n mm are pl otted agai nst
concentrati on of a gi ven compound, a strai ght l i ne passi ng through the ori gi n i s obtai ned.
Thi s coul d be used as a cal i brati on curve for determi ni ng the concentrati on of the
compound i n unknown sampl es.
I t has been repeatedl y veri fi ed that the di ffusi on current i s proporti onal to the
concentrati on of el ectroacti ve substance.
The l i near dependence of di ffusi on current on concentrati on does not hol d exactl y
when the drop-ti me i s short. The most sui tabl e drop-ti me i s from 3 to 5 sec (as al ready
stated).
Dependence on the Height of the Mercury Head, Capillary Characteristics and
Potential: The di ffusi on current depends on the capi l l ary characteri sti cs mand t, and
i s therefore affected by varyi ng them and thus how the numerous factors i nfl uence them
[mi s the average rate of fl ow of mercury i n mi l l i grams per second and t i s the drop-
ti me i n seconds].
I f the hei ght of mercury head i s changed at constant concentrati on of the substance,
the fl ow rate m and drop-ti me t changes si mul taneousl y. Accordi ng to the equati on m
i s di rectl y proporti onal and t
1
i nversel y proporti onal to the corrected hei ght h of the
mer cur y head:
m = k' h; t
1
= k"
1
h
...(19)
substi tuti ng i n I l kovi c equati on
i
d
= K m
2/3
( )
1 6
2 3 1 6
1
k"
t K k' h
h
| |
=
|
\ .
...(20)
and combi ni ng al l constants:
i
d
= k
h
...(21)
i .e., the di ffusi on cur r ent i s di r ectl y
pr opor ti onal to the squar e r oot of the
cor r ected hei ght of the mer cur y head
(r eser voi r ) Fi g. 5.2 and 5.3. The l i near
dependence as shown i n the fi gur es not
onl y represents a further veri fi cati on of
the val i di ty of the I l kovi c equati on but i t
al so provi des an easy test for veryfyi ng
di ffusi on control l ed currents.
For majori ty of i nvesti gati ons i nto the
ch ar acter of l i mi ti n g cu r r en ts i t i s
suffi ci ent to pl ot the l i mi ti ng cur r ent
agai nst the square root of the actual hei ght
of mer cur y head, i.e., the di stance from
the capi l l ary ori fi ce to the mercury l evel
i n the reservoi r. When the current i s di ffusi on control l ed, the pl ot gi ves a strai ght l i ne
(Fi g. 5.3) but thi s l i ne wi l l not pass through the ori gi n. I t cuts a smal l i ntercept on the
current axi s.
Si nce di ffusi on currents depend on m
2/3
t
1/6
, further cauti on i s necessary i n practi cal
quanti tati ve determi nati ons. When the di ffusi on currents for the same substance are
recorded wi th two di fferent capi l l ari es the di ffusi on currents are i n the rati o:
( ) ( )
( ) ( )
2 3 1 6
1 1
1
2 3 1 6
2 1
2
m t
m t
...(22)
Thus, when concentrati ons obtai ned wi th di fferent capi l l ari es are to be compared
the fl ow rates and drop-ti mes for the capi l l ari es must be known. Consequentl y, i t i s
desi rabl e for the compari son of resul ts to i ncl ude m and t
1
val ues characteri si ng the
capi l l ary i n an account of the experi mental data.
As al ready gi ven earl i er, fl ow rate i s i ndependent of potenti al except i n the correcti on
term for back pressure, where i ts i nfl uence i s negl i gi bl e, but drop-ti me depends on
potenti al i n the same way as does surface tensi on. For thi s reason i t i s expected that
at potenti al s more negati ve than the maxi mum of the el ectrocapi l l ary parabol a0.56 V
vs NCE i n chl ori des a decrease i n the di ffusi on current wi th i ncreasi ng negati ve potenti al
wi l l occur si nce the surface tensi on and al so the drop-ti me decrease. The maxi mum
val ue of the di ffusi on current i s attai ned at the potenti al of the el ectrocapi l l ary zero
then i t decreases at more posi ti ve potenti al s. Except at rather negati ve potenti al s a
change of drop-ti me wi th potenti al , exerts but a smal l i nfl uence on the di ffusi on current
(si nce the di ffusi on current i s a functi on of the si xth root of drop-ti me
( )
1 6
1 d
i kt = . I f the
di ffusi on current i s recorded i n the potenti al regi on from 0.56 to 2.0 V (vs NCE) and
the drop-ti me decreases to one hal f, the di ffusi on current wi l l fal l to (1/2)
1/6
i.e., by about
11%. The decrease i n the di ffusi on current wi th i ncreasi ng negati ve potenti al s must be
taken i nto account speci al l y when compari ng the di ffusi on currents of two di fferent
substances of equal concentrati ons but havi ng di fferent hal f-wave potenti al s.
Influence of Temperature on the Diffusion Current : An i ncr ease i n
temperature causes an i ncrease i n the di ffusi on coeffi ci ent. The effect of temperature
on the di ffusi on current may be deri ved theoreti cal l y as shown by I l kovi c [4]. Among
the quanti ti es i n the I l kovi c equati on:
i
d
= 0.627n F
c
D
1/2
m
2/3 1 6 2 3
1
m t ...(23)
onl y D, m and t
1
depend on temperature. Further detai l s can be obtai ned by di fferenti ati ng
I l kovi c equati on and the above factors i nto account. On varyi ng vari ous factors i t i s
concl uded that the temperature must be kept constant wi thi n at l east 0.5C i n order
to keep the error i n the determi nati on of di ffusi on current bel ow 1%. I f the temperature
coeffi ci ent i s much l arger than about 2% deg., the current i s probabl y at l east partl y
ki neti c or catal yti c, for the rates of most chemi cal reacti on i ncrease much more rapi dl y
wi th temperature than rates of di ffusi on do. Thi s may or may not be al ways true.
5.4.1 The Limiting Current
The total or l i mi ti ng current that fl ows on the pl ateau of a wave i ncl udes contri buti ons
from several di fferent process. I t i ncl udes the current that woul d fl ow under the same
condi ti ons but i n the absence of the substance responsi bl e for the wave i s cal l ed the
resi dual current. The wave hei ght i s defi ned as the di fference between the current and
the resi dual current, and i s the current due to the presence of the substance of i nterest.
I f the substance i s i oni c, there wi l l be an el ectrostati c force between i ts i ons and the
el ectrode. The force may be ei ther attracti on or repul si on and i n ei ther case i t affects
the rate at whi ch the i on, reaches the el ectrode surface and undergoes reducti on or
oxi dati on. The di fference between the l i mi ti ng current actual l y obtai ned and the l i mi ti ng
current that woul d be obtai ned i n the absence of any el ectrostati c force i s cal l ed the
migration current. For al l pol arographi c experi ments the mi grati on current i s rendered
negl i gi bl e by the presence of a rel ati vel y l arge concentrati on of an i ndi fferent el ectrol yte,
supporti ng el ectrol yte, whose i ons serve to conduct current through the sol uti on and
thus di ssi pate the el ectrostati c force but are not reduced or oxi di zed over the range of
potenti al s that i s bei ng studi ed.
Galvanometer
G
Mercury reservoir
oxygen free
nitrogen
solution of unknown subs.
with excess inert salt
+
+
Fig. 5.4 : The Pol ar ogr aphi c set up.
5.4.2 The Residual Current
The nature of the l ayer of an el ectrol yte sol uti on i mmedi atel y adjacent to the surface
of a mercury drop depends on the potenti al appl i ed to the drop. I f a droppi ng mercury
el ectrode di sconnected from the external ci rcui t i s i mmersed i n a pure sol uti on of say
potassi um chl ori de, the chl ori de i ons wi l l be preferenti al l y adsorbed on the surface of
the drop, and as a resul t the mercury i n the reservoi r wi l l acqui re a negati ve charge.
Thi s, i n turn, wi l l be i mparted to the succeedi ng drops, whi ch wi l l , therefore, adsorb
fewer and fewer chl or i de i ons unti l equi l i br i um i s attai ned. The negati ve char ge
accumul ated by the mercury wi l l then be just great enough to counter-bal ance the
tendency for adsorpti on of excess chl ori de i ons to occur on the surface of the drop.
Consi der i ng the equati on ic = 0.00853
2
(E
max
E) m
2/3
t
1/3
...i t i s gi ven that the
equati on descr i bes sever al i mpor tant pr oper ti es of the char gi ng cur r ent. I t i s
approxi matel y l i nearl y depended on potenti al , both at potenti al s more posi ti ve than
E
max
and at potenti al s more negati ve than E
max
. Wi th a typi cal capi l l ary, whi ch has the
characteri sti cs m and t 2 mg/sec and 4 sec, respecti vel y, the chargi ng current curve
woul d have a sl ope of about 0.35 amp./V i n the fi rst of these regi on and a sl ope of about
0.15 amp./V i n the second. These val ues are di fferent because the val ues of x are
di fferent. The majori ty of practi cal pol arographi c anal yses are performed by recordi ng
a pol arogram of the sol uti on bei ng anal ysed, and extrapol ati ng the porti on of the resi dual
current curve that precedes the wave of i nterest, thus measuri ng the verti cal di stance
from the pl ateau to the extrapol ated l i ne. The pl ateau coul d be extrapol ated backwards
and the hei ght measured at the hal f-wave potenti al . I t i s to be noted that nei ther m
2/
3
t
1/3
nor x i s qui te i ndependent of potenti al , the l i near extrapol ati on i s not perfectl y
accurate, even though the error i s negl i gi bl y smal l unl ess the sol uti on bei ng i nvesti gated
i n extremel y di l ute or unl ess the extrapol ati on crosses E
max
.
The above equati on as wel l be wri tten as:
ic = (kt
1/2
) m
2/3
t
1/6
for a parti cul ar sol uti on and a parti cul ar appl i ed potenti al . I t wi l l be shown i n the
secti on of di ffusi on current that the average di ffusi on current duri ng the l i fe of a drop,
i
d
, i s proporti onal to m
2/3
t
1/6
. Hence the rati o i
d
/ ic i s proporti onal to t
1/2
. Decreasi ng the
drop-ti me by i ncreasi ng the hei ght of the col umn of mercury above the capi l l ary, therefore
decreases thi s rati o because i t causes the chargi ng current to i ncrease more rapi dl y
than the di ffusi on current, and so attai nabl e sensi ti vi ty becomes poorer even though
the di ffusi on current i ncreases.
5.4.3 Migration Current
I f a droppi ng el ectrode i s i mmersed i n pure di l ute sol uti on of a sal t l i ke l ead perchl orate,
and i f a potenti al on the pl ateau of the l ead wave i s appl i ed to i t, l ead i ons wi l l be
reduced as fast as they reach the surface of the drop. A current wi l l therefore fl ow
through the cel l . Some anodi c reacti on wi l l occur at whi ch ever reference el ectrode i s
bei ng used, and the i ons wi l l move through the sol uti on to conduct the current from one
el ectrode through the other. Lead i ons wi l l move toward the droppi ng el ectrode and the
perchl orate i ons wi l l move towards the reference el ectrode. Thi s moti on of l ead i ons
causes them to arri ve at the drop surface more rapi dl y than they woul d i f el ectri cal
mi grati on di d not occur, and thi s i s the cause of the mi grati on current.
The val ue of mi grati on current depends on the transference number of the i ons
bei ng reduced or oxi di sed at the drop surface. The l arger thi s transference number, the
greater the fracti on of the current carri ed by the moti on of that i on. The addi ti on of
supporti ng el ectrol yte, whose i ons contri bute to the conductance but do not contri bute
to the current because they cannot be oxi di zed or reduced to any si gni fi cant extent
when they arri ve at the drop surface, causes the transference number of the el ectroacti ve
i on to decrease. I f the concentrati on of the supporti ng el ectrol yte i s very hi gh, the
transference number of the el ectroacti ve i on becomes practi cal l y zero. Current i s then
carri ed across the drop sol uti on i nterface by the reducti on or oxi dati on of the el ectroacti ve
i on. I t i s thus carri ed through the sol uti on by the moti on of the i ons of the supporti ng
el ectr ol yte.
I n such a sol uti on when the transference number i s smal l , the el ectroacti ve i on
pl ays onl y a negl i gi bl e part i n el ectrol yti c conducti on through the sol uti on and i ts
moti on i s affected by the di ffusi ve force al one.
The si gn of the mi gr ati on cur r ent depends on the si gn of the char ge on the
el ectroacti ve i on. Cati ons are attracted to a cathode, and therefore the mi grati on current
i ncreases the wave hei ght when a cati on i s reduced at the droppi ng mercury el ectrode.
Ani ons mi grate away from the cathode and therefore the mi grati on current decreases
the wave hei ght when ani on l i ke i odate or chromate i s reduced at the droppi ng el ectrode.
On exami ni ng the fi gur es fr om l i ter atur e i t can be obser ved that the addi ti on of
supporti ng el ectrol yte decreases the wave hei ght of cadmi um i on whi l e i t i ncreases that
of i odate i on.
I t i s assumed that the mechani sm of di ffusi on i s the same i n a pure sal t sol uti on
as i n the presence of excess of supporti ng el ectrol yte, so that the di ffusi on current i s
the same i n the two cases and that the mi grati on current i s gi ven by the product of the
total l i mi ti ng current by the transference number of the el ectroacti ve i on [5, 2]
i
l
= i
d
+ i
m
= i
d
+ i
l
t
+
= i
d
/(1 t
+
) ...(1)
for the reducti on of a cati on, and for the reducti on
i
l
= i
d
i
m
= i
d
i
l
t
= i
d
/(1 + t
) ...(2)
of an ani on. Equi val ent expressi on are easi l y wri tten for the oxi dati on of cati ons and
ani ons, for whi ch the mi grati on currents are opposi te i n si gn to those for cathodi c
waves. Thus, for exampl e, the hei ght of the anodi c wave of a cati on woul d i ncrease as
supporti ng el ectrol yte was added.
Al l practi cal pol arographi c work i s done under condi ti ons that serve to render the
mi gr ati on cur r ent negl i gi bl e. Ther e ar e sever al r easons for thi s. One of the most
i mportant one i s that i t woul d be qui te undesi rabl e to cal cul ate the concentrati on of the
substance (one whi ch i s of i nterest) a wave hei ght that depended not onl y on that
concentrati on but al so on the concentrati on and nature of every one of the other i ons
present. I t i s pl ai n that the wave hei ghts of l ead i ons woul d be qui te di fferent i n
sol uti ons of l ead chl ori de and had perchl orate even though the concentrati on of the two
sal ts were the same, for the equi val ent conductances of the chl ori de and perchl orate
i ons are suffi ci entl y di fferent to change the transference number of l ead i on by about
3% even i f compl exti on wi th chl ori de i on i s negl ected. I t i s observed that traces of
sodi um ni trate or potassi um ni trate woul d affect the l i mi ti ng current obtai ned wi th any
gi ven concentrati on of l ead i on, and woul d do so to di fferent extents because the equi val ent
conductance of these sal ts are not at al l the same.
Another reason for usi ng a consi derabl e excess of supporti ng el ectrol yte i n practi cal
pol arographi c work i s di rectl y rel ated to these consi derati ons.
I t i s to be noted that the addi ti on of supporti ng el ectrol yte produces smal l er vari ati ons
of the l i mi ti ng currents than i t shoul d accordi ng to the above equati ons. Thi s i s because
a few tenths of a mi l l i mol e per l i ter of el ectrol yte entered the sol uti on from the sal t
bri dge duri ng the preparati on and deaerati on of the sol uti ons. Thi s woul d be i mmateri al
i f a l arge excess of el ectrol yte were al ready present.
Al so, the sl opes of the waves i ncrease and that the hal f-wave potenti al s becomes
l ess negati ve as the el ectrol yte concentrati on ri ses. Thi s i s because the resi stance of the
sol uti on i s fai rl y hi gh i n the absence of added el ectrol yte and so an appreci abl e fracti on
of the vol tage appl i ed by the pol arograph i s di ssi pated as iR drop through the cel l . I t
i s certai nl y easy to decrease the resi stance by addi ng el ectrol yte whenever i t i s possi bl e.
A useful rul e i n order to suppress the mi grati on current to nearl y compl etel y, that
further vari ati ons of the el ectrol yte concentrati on wi l l have no effect, the concentrati on
of the supporti ng el ectrol yte shoul d be at l east 50 ti mes that of the el ectroacti ve i on.
Thi s i s based on the conductance equati on. The transference number:
j j j i i
i
t c / c =
of the jth i on i n a sol uti on i s al so gi ven by the equati on.

Wher e i n conductance equati on, the cs are the concentrati ons i n equi val ents per
l i ter and the s are the equi val ent i oni c conductances.
The concentrati ons must be expressed i n equi val ents per l i ter. Thi s wi l l decrease
the transference number of the el ectroacti ve i on to about 0.01. A hi gher concentrati on
of suppor ti ng el ectr ol yte i s needed i f the el ectr oacti ve i on has an unusual l y hi gh
equi val ent conductance (as does hydr ogen i on).
A l ower one wi l l suffi ce i f i t has an unusual l y l ower one wi l l suffi ce i f i t has an
unusual l y l ow equi val ent conductance (as i n l ar ge or gani c i ons).
Most pol arographi c work can be carri ed out wi th the concentrati on of supporti ng
el ectrol yte between 0.1 M and 1 M. I n some cases of i norgani c pol arography even much
hi gher concentrati ons are often useful . These are other cases where the use of a very
concentrated medi um may serve to mask an i nterferi ng i on. Take for exampl e, thal l us
i on whi ch yi el ds a wave i n al most every known suppori ng el ectrol yte but i s masked i n
concentrated hydrochl ori c aci d because of the formati on of a chl oro compl ex.
Non-i oni c substances shoul d not gi ve mi grati on currents. Supporti ng el ectrol ytes
are sti l l used for two reasons. One i s to decrease the iR dr op thr ough the cel l ; and the
other i s to buffer the sol uti on.
The resi stance of the sol uti on i s fai rl y i n the absence of added el ectrol yte and so an
appreci abl e fracti on of the vol tage appl i ed by the pol arograph i s di ssi pated as iR drop
through the cel l . I t i s certai nl y easy to decrease the resi stance by addi ng el ectrol yte
whenever i t i s possi bl e.
The si gn of the mi gr ati on cur r ent depends on the si gn of the char ge on the
el ectroacti ve i on. Cati ons are attracted to a cathode, and therefore the mi grati on current
i ncreases the wave hei ght when a cati on i s reduced at the droppi ng mercury el ectrode.
Y is
0
Y
C , thi s rate i s equal to k
f
0
Y
C . Very l i ttl e Y wi l l be consumed si nce the reacti on
i s very sl ow. So
0
Y
C wi l l be vi rtual l y i denti cal wi th C
Y
, the concentrati on of Y i n the
bul k of the sol uti on. Addi ti onal l y, the current at any i nstant wi l l be proporti onal to the
area of the el ectrode at that i nstant. I t wi l l al so be affected by the rate of the backward
reacti on because thi s competes wi th reducti on of O. Consi deri ng the deri vati on
ik = 493
n
D
1/2
C
Y
m
2/3
t
2/3
( )
1 2
f b
k / k (3)
where ik i s the average ki neti c current duri ng the l i fe of the drop and D i s the di ffusi on
coeffi ci ent of Y or O. I t i s reasonabl y assumed that these are equal because mol ecul es
of these substances wi l l probabl y have nearl y equal si zes. The val ue of ik wi l l be gi ven
i n mi croampere of C
Y
i s expressed i n mi l l i mol es per l i ter.
I t i s easy to recogni ze a ki neti c current wi th the hel p of the Eq. (3) si nce m
2/3
t
2/3
does not vary wi th the hei ght of the col umn of mercury above the capi l l ary. I f al l other
condi ti on are kept constant, the hei ght of ki neti c wave i s i ndependent of h
cor r
. Thi s
behavi our i s qui te di fferent from the behavi our of a di ffusi on current ( )
1 2
1 d corr
i / h k =
. I t
consti tutes the fundamental test for ki neti c control of the wave hei ght.
There are a number of di fferences between the ki neti c and di ffusi on-control l ed
waves gi vi ng suppor ti ng evi dence. However , no concl usi ve evi dence i s obtai ned about
the nature of the unknown wave whi ch i s suspected to be ki neti c.
The hei ght of the ki neti c wave i s l arger than the di ffusi on current that woul d
correspond to the equi l i bri um concentrati on of O i n the sol uti on. But i s smal l er than
the di ffusi on current that woul d correspond to the reducti on of the O and Y together.
I n case n i s known, Y can be appr oxi mated by appl yi ng I l kovi c equati on. I t i s not safe
to concl ude that a wave i s ki neti c due to i ts unexpectedl y smal l hei ght, because i t al so
happens wi th those of adsorpti on waves. The hei ght of a ki neti c wave i s i nfl uenced by
the experi mental condi ti on that affect the reacti on rates. These i ncl ude pH, temperature,
and i oni c str ength. The effect of i oni c str ength depends on the char ges bor ne by the
speci es i nvol ved.
By changi ng the composi ti on of the supporti ng el ectrol yte i n order to di spl ace the
equi l i bri um i n favour of O a sol uti on can be obtai ned i n whi ch the concentrati on of Y
i s negl i gi bl e and i n whi ch O gi ves a di ffusi on contr ol l ed wave. When Y i s reduci bl e at
a more negati ve potenti al than O, the total current on the pl ateau of the wave of Y can
be measured.
When the equati on (3) appl i cabl e, the var i ati on of ki neti c cur r ent wi th the
composi ti on of the sol uti on can be used to el uci date the stoi chi ometry of the rate-
determi ni ng chemi cal step.
Vari ous other ki nds of behavi ours are possi bl e whi ch have al so been observed by
many workers. I f the pseudo-fi rst order rate constant k
f
i s extremel y smal l , then onl y
little Y wi l l be transformed i nto O duri ng the l i fe of the drop and as such the ki neti c
current wi l l be too smal l to detect. I n such a case the wave hei ght of O wi l l be di ffusi on
control l ed and proporti onal to the concentrati on of O i n the bul k of the sol uti on. On the
other hand, i f k
f
i s extremel y l arge the wave hei ght wi l l agai n be di ffusi on-control l ed but
wi l l be proporti onal to the sum of the concentrati ons of O and Y because actual l y al l of
the Y reachi ng the drop surface wi l l be transformed i nto O and r educed. I n case, wher e
bul k of the sol uti on contai ns appreci abl e concentrati on of both O and Y and wher e the
transformati on of Y i nto O i s nei ther + i nstantaneous nor sl ow, the wave hei ght wi l l be
the sum of the di ffusi on current of the O al ready present. A ki neti c current refl ecti ng
the formati on of addi ti onal O at the expense of part of the Y at the drop surface as the
equi l i bri um between them i s di spl aced by reducti on. The di ffusi on current wi l l be
proporti onal to m
2/3
t
1/6
wi thi n the l i mi ts of error. The wave hei ght may sl ow any behavi our
i ntermedi ate between that of a pure di ffusi on current at one extreme and that of a pure
ki neti c current at the other. Thi s depends on the posi ti on of the equi l i bri um between Y
and O i n any parti cul ar sol uti on and on the rate at whi ch i t i s attai ned.
I t i s not advi sabl e to use ki neti c waves i n practi cal anal ysi s for two reasons: (i) They
afford poorer sensi ti vi ti es than di ffusi on-control l ed waves, and (ii) an i mpur i ty may
al ter the hei ght of the ki neti c wave by catal ysi ng the rate-determi ni ng step. I t i s better
to expl ore condi ti ons to obtai n di ffusi on-control l ed wave. These can be obtai ned by
i nvesti gati ng the effects of vari abl es such as pH and temperature.
5.4.5 Catalytic Currents
Catal yti c waves ari se from mechani sms l i ke
O + ne R ...(1)
R + Z t
k
O ...(2)
i n whi ch a substance Z, whi ch woul d not be reduci bl e at a certai n potenti al i f i t were
pr esent al one, causes the cur r ent obtai ned fr om the r educti on of an el ectr oacti ve
substance O at that potenti al to i ncrease by reacti ng wi th the product R to regenerate
O or to form some other substance that i s reduci bl e.
Catal yti c waves are obtai ned i n many mi xtures of transi ti on metal i ons, such as
tangstates, vanadate, mol ybdate and ti tani um (v), wi th oxi di zi ng agents l i ke ni trate,
hydrogen peroxi de, chl orate. The behavi our of the l i mi ti ng current i n any parti cul ar
case depends on the rel ati ve magni tudes of the di ffusi on and catal yti c currents. The
hei ghts of catal yti c waves are as sensi ti ve to vari ati ons of pH, temperature, and other
experi mental condi ti ons as those of ki neti c ones. The use of a catal yti c wave for anal yti cal
purposes may often be advantageous because of hi gh sensi ti vi ty that may be attai ned.
For exami ni ng the catal yti c current of ni trate take for exampl e ni trate i on (= Z)
does not gi ve a wave i n a supporti ng el ectrol yte contai n 0.1 F sul phuri c aci d and 0.2
F sodi um sul phate. Mol ybdenum (vi) gi ves a doubl e wave. The fi r st wave r epr esenti ng
reducti on to mol ybdenum (v), and the second represents reducti on to mol ybdenum (iii).
Mol ybdenum (iii) reacts fai rl y rapi dl y wi th ni trate i n an aci di c sol uti on. At a potenti al
on the pl ateau of the second wave of mol ybdenum (vi) i n a sol uti on contai ni ng ni trate,
the mol ybdenum (iii) formed by the el ectrode reacti on i s parti cul arl y reoxi di zed by
ni trate and the oxi di zed mol ybdenum speci es i s then reduced wi th more ni trate and so
on. The i ncrease of current resul ti ng from the presence of the ni trate that i s the
di fference between the total hei ght of the wave and the di ffusi on current obtai ned i n the
absence of ni trate i s the catal yti c current of ni trate.
I n cases wher e the di ffusi on cur r ent of O i s appreci abl e i t may be measured
separatel y i n the absence of Z and the catal yti c cur r ent can then be obtai ned by
di fference. Li ke ki neti c currents, catal yti c currents can be i denti fi ed by the fact that
they do not vary wi th h
cor r
. I n general these two ki nds of currents behave very si mi l arl y,
but they are easi l y di sti ngui shed because of the pecul i ar chemi cal ci rcumstances i n
whi ch catal yti c waves appear.
Another i mportant type of catal yti c current i s observed i n sol uti ons contai ni ng a
base B that i s not reduci bl e but that can catal yze the reducti on of protons by the
fol l owi ng mechani sm:
B + HA HB
+
+ A
...(3)
HB
+
+ C HB ...(4)
2HB H
2
+ 2B ...(5)
where HA may be hydroni um i on or another proton doner. Such catal yti c waves are
obtai ned wi th many or gani c compounds, i ncl udi ng ami nes, ami no aci ds, pr otei ns,
al kal oi ds. These di spl ay compl ex behavi our. At very l ow concentrati ons of catal yst B,
the bi -mol ecul ar reacti on represented by Eq. (5) may be rate determi ni ng on the pl ateau
of the wave, wher e the el ectr on tr ansfer r eacti on (4) i s ver y fast and then the wave
hei ght wi l l i ncrease very rapi dl y than C
B
, the bul k concentr ati on of B. But as C
B
is
i ncreased the proton transfer reacti on (3) tends to become rate determi ni ng. Thus the
observed behavi our depends on whether thi s reacti on occurs at the surface of the drop
or i s the bul k of the sol uti on and thi s i n turn depends l argel y on the extent to whi ch
B can be adsorbed on the drop surface. Most often the rati o of wave hei ght to the
concentrati on of B decreases i n the manner of an adsorpti on i sotherm. The dependence
on aci di ty i s qui te compl ex. At moderate aci di ti es the wave hei ght may be proporti onal
to the concentrati on of aci d because the proton-transfer reacti on i s rate-determi ni ng,
but at hi gh aci di ti es the regenerati on of the catal yst, e.g.,
2HB H
2
+ 2B
may become rate determi ni ng step. Then the wave hei ght i ncreases l ess rapi dl y than
the concentrati on of aci d.
Catal yti c hydrogen waves are al so observed wi th some i norgani c substances. I n
cases as wi th the i ons of several of the pl ati num metal s they are probabl y due to the
effects of the deposi ted metal s on the over potenti al for hydrogen evol uti on.
5.5 ADSORPTION WAVES
An adsorpti on wave may be observed i n case ei ther the el ectroacti ve speci es or the
product of the el ectrode reacti on i s adsorbed onto the surface of the drop. Suppose that
the product R of the el ectrode reacti on O + ne R i s adsorbed, i ts acti vi ty i s l ower i n
the adsorbed state than i n sol uti on whi ch faci l i tates the reducti on of O. There i s onl y
a si ngl e wave at a very l ow concentrati c of O representi ng the reducti on of O to adsorbed
R. The hei ght of thi s wi l l be di ffusi on-control l ed, whi ch wi l l be proporti onal to the
concentrati on of O and al so to
1 2
corr
h . I n case as the concentrati on of O i s i ncreased, a
poi nt i s reached at whi ch suffi ci ent R i s formed duri ng the l i fe of the drop cover the
enti re surface. More than thi s amount of R can be formed onl y i f excess remai ns i n
sol uti on. The reducti on of the excess O wi l l produce a second wave at a more negati ve
potenti al because i t i s more di ffi cul t to reduce O to di ssol ved R than to reduce i t to
adsorbed R. The ori gi nal wave i s the adsorpti on wave, whose hei ght wi l l be constant and
i ndependent of any fur ther i ncr ease i n the concentr ati on of O. The second wave whi ch
represents the reducti on of O to di ssol ved R i s the normal wave. The total hei ght of
the doubl e wave corresponds to the reducti on of al l of the O di ffusi ng to the surface of
the drop, and i s therefore di ffusi on-control l ed and proporti onal to both the concentrati on
of O and
1 2
corr
h . I ndi vi dual l y these waves do not fol l ow exactl y.
A si ngl e wave i s obtai ned at very l ow concentrati ons of O represents the reducti on
of adsor bed O. Thi s i s the case when O i s adsorbed and R i s not. Thi s wi l l reach a
l i mi ti ng hei ght when the amount of O di ffusi ng up to the surface of each drop i s just
suffi ci ent to cover the drop surface. Thi s happens on i ncreasi ng the concentrati on of O.
At a sti l l hi gher concentrati on, the excess of O remai ni ng di ssol ved at the drop surface
produce a normal wave at a l ess posi ti ve potenti al .
The adsorpti on i s due to surface forces. The range of whi ch usual l y does not exceed
mol ecul ar di mensi ons, so that as a rul e the adsorbed parti cl es form a monomol ecul ar
l ayer. The parti cl es of the di ssol ved substances may be bound to the surface by physi cal ,
chemi cal or el ectri cal for a capi l l ary forces causi ng adsorpti on i n sol uti ons are regarded
as physi cal forces.
Adsorpti on at a DME causes charges i n the capaci ty current and may al so i nfl uence
the faradai c currents.
The pol arographi c currents may be i nfl uenced by adsorpti on by two mechani sms:
(i) The depol ari zer or i ts el ectrode reacti on product i s adsorbed. I n such a case, a
separate wave, the so-cal l ed adsorpti on wave i s formed.
(ii) When some other component of the sol uti on i s adsorbed and by i ts presence at
the el ectrode surface i nfl uence the depol ari zati on process spl i tti ng the wave for
the depol ari zer.
(iii) Pol arographi c Currents I nfl uenced by Adsorpti on of El ectroacti ve Substances.
(a) Reversible Processes : Adsorpti on currents of thi s type were fi rst
obser ved by Brdi cka and Knobl och [6] i n the r educti on of r i bofl avi n and
methyl ene bl ue respecti vel y. Both compounds formed reversi bl e oxi dati on-
reducti on systems.
At very l ow concentrati on of methyl ene bl ue (l ess than 6.10
6
M) onl y a
si ngl e r educti on wave i s obser ved. At hi gher concentr ati ons a mor e
negati ve wave appear s whi ch i ncr eases l i near l y wi th concentr ati on.
Whereas the hei ght of the ori gi nal posi ti ve wave remai ns constant after
attai ni ng a certai n l i mi ti ng val ue. [7]
Consi deri ng the adsorpti on of depol ari zer, i t i s assumed that the oxi di zed
form whi ch i s subject to a reversi bl e reducti on i s adsorbed at the droppi ng
mercury el ectrode whereas the reduced form i s not. The reducti on of
adsorbed mol ecul es requi res more energy than that of free mol ecul es
because the energy of adsorpti on has to be overcome. The resul t i s that
the reducti on of adsorbed mol ecul es must take pl ace at a more negati ve
potenti al s.
(b) Irreversible Processes : I n some i rreversi bl e reducti on two waves are
observed. The fi rst one i s whi ch i s concentrati on i ndependent above a
certai n l i mi ti ng concentrati on. The shape of the current-ti me curve may
resembl e the adsorpti on pre-wave for the adsorpti on of the reducti on
product i n reversi bl e systems. I n an i rreversi bl e reducti on, however, i t i s
not expected that the adsorpti on of the reducti on product wi l l faci l i tate
the reducti on process. The doubl e-wave may be due to the i nhi bi ti on of
the el ectrode process by a fi l m of the reducti on product and the second
whi ch i s mor e negati ve may cor r espond to r educti on wi th a hi gher
overvol tage at the covered el ectrode surface. Such process resembl es the
i nhi bi ti on by adsorpti on of el ectro-i nacti ve substances.
The effect of sur face-acti ve substances on the el ectr ode pr ocesses al so pl ays a
suffi ci ent r ol e. The sur face acti ve substances that effect the el ectr ode pr ocess ar e
cl assi fi ed accordi ng to thei r charge. Non-i oni c more commonl y i n these are camphor,
thymol , gel ati ne charge dependi ng on the pH val ues of the sol uti on. Among cati oni c
compounds are the tetra-al kyl ammoni um, and tri benzyl ammoni um cati ons whi ch
have been speci al l y i nvesti gated.
A current whi ch at a free surface i s control l ed by di ffusi on, may be retarded by a
surface-acti ve substance to such an extent that the el ectrode process becomes rate-
control l i ng. Someti mes, the el ectrode process i s onl y accel erated suffi ci entl y at much
more negati ve potenti al s (consi deri ng reducti on case) for di ffusi on to become agai n, the
control l i ng process. I n thi s way, the i ncreased i rreversi bi l i ty i n the presence of a fi l m
i s expl ai nabl e as evi denced by the decrease i n l i mi ti ng current. The shi ft of the wave,
or the formati on of a new di ffusi on-control l ed wave at a more negati ve potenti al , though
before the desorpti on potenti al of the surface-acti ve substance takes pl ace.
On the other hand, i t al so someti me happens that the el ectrode process takes pl ace
at a greater rate when a fi l m i s present than when the surface i s free. The absorbed
substances faci l i tate the el ectron transfer, speci al l y wi th surface acti ve substances of
the i oni c types.
References
1. I l kovi c, D. : Col l ecti on Czechosl ov. Chem. Communs. 6, 498 (1934).
2. Kemul a W. : Trabojos I X Congr. i nter. qui m. puray apl i cada; Tomo I I 297 Madri d (1934).
3. Nernst, W. : Z Physi k Chem. 2, 613 (1888).
4. I l kovi c D. : Col l ecti on Czechosl ov. Chem. Communs. 10, 249 (1938).
5. Heyr ovsky J. : Ar hi v. Hemi Far m, 8, 11 (1934).
6. Bri di cka R., Knobl och E. Z. El ectrochem. 47, 721 (1941).
CHAPTER 6
POLARIZATION
6.1 POLARIZATION OF THE DROPPING MERCURY ELECTRODE AND
DEPOLARIZATION PROCESSES
When a cur r ent passes t hr ough an elect r ode syst em immer sed in a solut ion cont aining
a common elect r olyt e, t he following r elat ion holds :
E P
i
R
=
...(1)
wher e E
denot es t he applied volt age, R t he r esist ance of t he polar ogr aphic cell and P
t he polar izat ion, i.e., t he elect r oact ive for ce act ing against t he elect r omot ive for ce of t he
sour ce. Polar izat ion is caused by chemical or physical changes at t he elect r odes due t o
t he passage of cur r ent . In t he example given above, it is defined as t he differ ence
bet ween t he pot ent ials of t he t wo elect r odes :
P = E
a
E
k
...(2)
wher e k
a
is t he pot ent ial of t he st at ionar y mer cur y elect r ode (mer cur y pool on t he
bot t om of t he cell) and E
k
t he pot ent ial of t he dr opping mer cur y elect r ode r egar dless
of whet her it funct ions as a cat hode or as an anode.
The r elat ion (3) given in t he equat ion ahead is not as t he simple Ohms law i.e.,
E
i
R
=
...(3)
Polar izat ion r efer s only t o t he dr opping mer cur y elect r ode, since t he pot ent ial of t he
st at ionar y mer cur y elect r ode (i.e., t he non-polar izable r efer ence elect r ode) is const ant .
This means t hat t he t ot al polar izat ion of t he cell can be obser ved only wit h a dr opping
mer cur y elect r ode, which is r egar ded as per fect ly polar izable.
Fr om t he above equat ion (2) it follows t hat :
P = E
iR ...(4)
This for mula shows t hat t he polar izat ion P is smaller t han t he applied volt age by
a value t hat is given by t he pot ent ial dr op, i.e., iR. While wor king wit h mor e concent r at ed
elect r olyt es (so called indiffer ent or suppor t ing elect r olyt es) t he r esist ance of t he
elect r olyt e may be as low as 100. Unless t he cur r ent exceeds 10
5
A, t he pr oduct iR
is about 1 mV and may be neglect ed.
P E
...(5)
On combining t his r elat ion wit h equat ion (6) we obt ain
78 Introduction to Polarography and Allied Techniques
E
k
= E
+ E
a
...(6)
which shows t hat an ext er nal volt age when applied t o bot h elect r odes oper at es only at
t he dr opping mer cur y elect r ode. To which it impar t s a pot ent ial t hat equals t he differ ence
bet ween t he pot ent ial of t he r efer ence elect r ode and t hat of t he applied volt age. In
cases wher e t he cur r ent volt age cur ves ar e r efer r ed t o t he same r efer ence elect r ode, t he
const ant E
a
may be by convent ion made equal t o zer o and hence we get
E
k
= E
...(7)
i.e., except for it s sign, t he pot ent ial of a complet ely polar ized dr opping mer cur y elect r ode
equals t he ext er nal applied volt age.
A sepa r a t e r efer ence elect r ode is usua lly t a ken. This is for mor e a ccur a t e
det er minat ion of pot ent ials on cur r ent -pot ent ial cur ves. Secondar y elect r odes, e.g.,
calomel, silver chlor ide ar e t he ones nor mally used as non-polar izable r efer ence
elect r odes. Ot her successful elect r odes which have been used at higher cur r ent densit ies
ar e amalgam elect r odes, e.g., 1% cadmium amalgam in a cadmium sulphat e solut ion,
or oxidat ion-r educt ion elect r odes like plat inum elect r ode in a mixt ur e of fer r ic and
fer r ous ions in 1 : 1 r at io have also been used.
The sur face ar ea of mer cur y pool must be sufficient ly lar ge t o t he ext ent of sever al
squar e cms in or der t hat it r emains non-polar ized. It s pot ent ial depends on t he kind and
t he concent r at ion of anions in t he solut ion t o be elect r olized. In such cases, t he pot ent ial
of t he mer cur y pool can be est imat ed fr om t he composit ion of t he solut ion.
6.2 REDUCTION OF HYDROGEN IONS AND HYDROGEN OVER VOLTAGE
Among t he most t ypical and most fr equent ly st udied examples of an ir r ever sible pr ocess
is t he r educt ion of hydr ogen ions. The over volt age of t his pr ocess var ies gr eat ly wit h
t he nat ur e of t he elect r ode. The differ ence bet ween t he half-wave pot ent ial of t he
ir r ever sible wave and t he st andar d pot ent ial E
0
(vir t ually equal t o t he half-wave pot ent ial
of a r ever sible wave) is t he polar ogr aphic over pot ent ial (over volt age)
1/2
i.e.,
1/2
= (E
1/2
)
ir r ev
E
0
...(8)
Hydr ogen over volt age is usually invest igat ed at const ant cur r ent densit y j and is
defined as t he differ ence bet ween t he elect r ode pot ent ial E, at which hydr ogen is
r educed at t his cur r ent densit y, and t he pot ent ial E
r
of a r ever sible hydr ogen elect r ode
in t he same solut ion,
i.e., = E E
r
...(9)
Heyr ovsky [3] suggest ed t he following r eact ion mechanism :
H
+
+ e H ...(10)
wher e H
+
is wr it t en inst ead of H
3
O
+
, for t he sake of simplicit y.
It is supposed t hat t he upt ake of a single elect r on by a hydr ogen ion occur s ver y
r apidly and t hat t he r at e det er mining st ep is t he r eact ion :
2
H
+
+ e H
2
...(11)
This mechanism is in accor dance wit h t he dischar ge of hydr ogen on some elect r odes.
In or der t o explain t he shape of t he cur r ent volt age cur ve at a dr opping mer cur y
elect r ode, Heyr ovsky assumed (Ref. as above) t hat t he sur face of t he elect r ode is occupied
by t he evolved molecules of hydr ogen, which r educe at t he fr ee sur face on which t he
following r eact ion t akes place :
H + H
+
2
H
+
...(12)
Kut a [4], der ived an equat ion for t he polar ogr aphic wave of hydr ogen ions based on
t his assumpt ion.
Kut as exper iment s wit h a st r eaming mer cur y elect r ode [Kut a ] [4] collect ion
Czechoslov. Chem. Communs 23, 383 (1958) showed t hat t he concept of sur face cover age
by hydr ogen molecules was not just ified.
The best agr eement wit h polar ogr aphic r esult s is obt ained by assuming t he r eact ion:
H
+
+ e H ...(13)
This is supposed t o be t he slowest st ep in t he pr oposed mechanism. In fact t he
influence of t he elect r ode double layer on t he dischar ge of hydr ogen ions must also be
t aken int o account .
A br ief sur vey of t he exper iment s on t he dischar ge of hydr ogen ions at t he dr opping
mer cur y and t he st r eaming mer cur y elect r ode is descr ibed below :
(i) Cur r ent -volt age cur ves for hydr ogen ions wit hout concent r at ion polar izat ion.
Wor ker s at about t he same per iod found t hat in mor e concent r at ed solut ions of
st r ong acids (e.g., 0.010.1 N HCl) and in t he absence of neut r al salt s t he above
defined r educt ion pot ent ial of hydr ogen shift s in accor d wit h t he r elat ionship :
E = const + ln H
RT
F
+
(

...(14)
wher eas, wit h an excess of an indiffer ent elect r olyt e t he dependence is given by
E = const +
2RT
F
ln [H
+
] ...(15)
In buffer solut ions, wit h one unit incr ease in t he buffer pH shift s t he r educt ion
pot ent ial of hydr ogen by 116 mV t o mor e negat ive pot ent ial.
On adding small amount s of neut r al salt s, t he over -volt age is mar kedly incr eased.
In ot her wor ds t he r educt ion pot ent ial is displaced t o mor e negat ive pot ent ials,
wher eas, wit h incr easing concent r at ion of t he neut r al salt , t he r educt ion pot ent ial
appr oaches a const ant value t hat depends on t he hydr ogen ion concent r at ion.
The valency of t he neut r al salt is also t o be t aken int o account .
(ii) Polar ogr aphic Waves for Hydr ogen Ions Given by St r ong Acids : Examining t he
shape t he cur r ent -volt age cur ve and it s dependence on t he hydr ogen ion
concent r at ion, it had been infer r ed t hat t hese ar e t he t wo fundament al quant it ies
in t he t heor y of hydr ogen over volt age. It has been st at ed t hat t he hydr ogen
wave is asymmet r ic (Tomes [6],) and t hat it s half-wave pot ent ial depends on t he
hydr ogen ion concent r at ion (Tamamushi [5]).
(iii) The behaviour of weak non-r educible acids which give r educt ion waves for
hydr ogen ions is quit e complicat ed. The limit ing cur r ent is diffusion cont r olled
for acids wit h pK
a
25. The half-wave pot ent ial is displaced t o mor e negat ive
Polarizat ion 79
values wit h incr easing concent r at ion of t he acid and, par t icular ly of it s anions.
At t he same t ime, t he slope of t he wave decr eases. Only wit h ver y weak bor ic
acid a kinet ic limit ing cur r ent cont r olled by dissociat ion r at e was obser ved by
past wor ker s.
6.3 DOUBLE LAYER
The layer of negat ive char ge at t he sur face of t he elect r ode and t he layer of posit ively
char ged solut ion adjacent t o it const it ut e t he so-called double layer .
To char ge t he double layer upt o any pot ent ial E, a cer t ain quant it y of elect r icit y is
r equir ed. For an elect r ode of const ant ar ea A (in cm
2
) t his is given by
q = xA (E
max
E) ...(16)
wher e q is t he quant it y of elect r icit y in micr ocoulombs, x is t he differ ent ial capacit y of
t he double layer in micr ofar ads/squar e cent imet er , and E
max
is t he pot ent ial of t he
elect r ocapillar y maximum. The value of x is not independent of pot ent ial. In dilut e
solut ions of hydr ochlor ic acid or alkali met al halides it is appr oximat ely 40f/cm
2
at
pot ent ials mor e posit ive t han E
max
but only about 18 f/cm
2
at pot ent ials mor e negat ive
t han E
max
and in each of t hese r egions t her e ar e definit e fur t her var iat ions wit h
pot ent ial [1].
It is evident t hat t he quant it y of elect r icit y descr ibed by t he above equat ion is
posit ive when E is mor e negat ive t han E
max
, zer o when E and E
max
ar e equal, and
negat ive when E is mor e posit ive t han E
max
.
The r ever sal of sign occur s because of t he polar it y of t he double layer is r ever sed in
going fr om one side of t he elect r ocapillar y maximum t o t he ot her , and t he signs ar e so
chosen as t o accor d wit h t he cust omar y polar ogr aphic convent ion, in which t he flow of
elect r ons int o t he dr opping elect r ode is t aken t o const it ut e a posit ive cur r ent . It can as
well be said t hat t he cur ent is t aken t o be posit ive when t he dr opping elect r ode is t he
cat hode, and negat ive when it is t he anode.
When a r eact ion is said t o t ake place at t he sur face of an elect r ode, it is not implied
t hat t he elect r oact ive species must come int o act ual physical cont act wit h t he elect r ode.
Ther e is a pot ent ial gr adient ar ound an elect r ode immer sed in an elect r olyt e solut ion.
The pot ent ial differ ence bet ween t he elect r ode and t he bulk of t he solut ion may be
r epr esent ed by (E E
max
) wher e E is t he pot ent ial of t he elect r ode and E
max
is t he
elect r ocapillar y maximum pot ent ial or pot ent ial of zer o char ge. If t his is negat ive, t hen
any sur face near t he elect r ode will be at a mor e negat ive pot ent ial t han t he bulk of t he
solut ion and t he pot ent ial will become mor e and mor e negat ive as t he elect r ode sur face
mor e closely appr oached. An ion a molecule diffusing t owar d t he elect r ode will r each a
point (whose dist ance fr om t he elect r ode sur face is always negligible compar ed wit h t he
t hickness of t he diffusion layer under polar ogr aphic condit ion) at which t he pot ent ial is
sufficient ly negat ive t o br ing about it s r educt ion. All t hese point s will lie on a spher ical
sur face wit h a dr opping elect r ode at any inst ant . Ther e is a simple case in which t her e
is no specific adsor pt ion at t he elect r ode sur face and in which t he pot ent ial var ies
mont onically wit h dist ance fr om t he elect r ode. In mor e complicat ed cases specific
adsor pt ion does occur and in which t he dependence of pot ent ial on dist ance fr om t he
el ect r ode i s n o mon ot on i c.
These ar e depict ed schemat i-
cally in t he Figur e 6.1.
Fig. 6.1 schemat ic diagr ams
of t he elect r ical double layer at
an elect r ode whose pot ent ial is
mor e n ega t i ve t h a n t h e
pot ent ial of t he elect r ocapillar y
ma xi mu m. (a) No s peci fi c
adsor pt ion, and (b) when t he
specifica lly a dsor bed ca t ions
a r e pr es en t i n t h e i n n er
Helmholt z plane.
On t h e ba s i s of t h e
polar ogr aphic obser vat ions it
can be qualit at ively descr ibed
t hat t he sur face at which t he
r eact ion occur s coincides wit h t he boundar y bet ween t he Helmholt z layer and t he diffuse
double layer . Influence of st r uct ur e of t he elect r ode double layer on t he r at e of on
ir r ever sible pr ocess.
The double layer affect s t he r at es of elect r ode pr ocesses by it s influences on t he
sur face concent r at ion of t he depolar izer and on t he kinet ics of t he elect r ode r eact ion.
This effect was fir st consider ed by Fr umkin [1] in t he case of hydr ogen ions.
Accor ding t o Fr umkin [1], t he elect r ode pr ocess involves only ions in dir ect cont act
wit h t he elect r ode and t hat elect r on t r ansfer t o mor e dist ant ions is not likely. Thus, t he
elect r ochemical r eact ion occur s only in t hat par t of t he double layer , which does not
exceed t he effect ive ionic r adius.
Sever al examples of ir r ever sible pr ocesses in which t he double layer plays an
impor t ant r ole ar e being descr ibed on t ime t o t ime.
6.4 REDUCTION OF CATIONS
(a) Red u ct i on of Hyd r ogen I on s a n d Hyd r ogen Over Volt a ge : Among t he most
t ypical and most fr equent ly st udied examples of an ir r ever sible pr ocess is t he
r educt ion of hydr ogen ions [4]. The over volt age of t his pr ocess var ies gr eat ly
wit h t he nat ur e of t he elect r ode. The differ ence bet ween t ha half-wave pot ent ial
of t he ir r ever sible wave and t he st andar d pot enit al E
0
(which is vir t ually equal
t o t he half-wave pot ent ial of a r ever sible wave) is t he polar ogr aphic over pot ent ial
(over volt age)
1/2
,
i.e.,
1/2
= (E
1/2
)
ir r ev
E
0
...(17)
Hydr ogen over volt age is usually invest igat ed at const ant cur r ent densit y j and
is defined as t he differ ence bet ween t he elect r ode pot ent ial E, at which hydr ogen
is r educed at t his cur r ent densit y, and t he pot ent ial E
r
of a r ever sible hydr ogen
elect r ode in t he same solut ion, i.e., = E E
r
.
Fi g. 6.1
Polarizat ion 81
+
+
+
+
+
+
+
+
+
+
+
+ +
+
+
+
+ +
+ +
+ +
+ +
+

+
+
+
+

Electrode
Electrode
Helmholtz
layer
Diffuse
layer
Helmholtz
double
layer
Diffuse
double
layer
(a) (b)
The sequence of r eact ion could be
2H
+
+ 2e 2H ...(i)
2H H
2
...(ii)
Heyr ovsky [3] suggest ed t he following r eact ion mechanism. For t he sake of
simplicit y, H
+
is wr it t en inst ead of H
3
O
+
.
H
+
e H ...(18)
H + H
+
2
H
+
...(19)
2
H
+
+ e H
2
...(20)
It is supposed t hat t he updat e of a single elect r on by a hydr ogen ion occur s ver y
r apidly and t hat t he r at e det er mining st ep is r eact ion (19).
This mechanism is in accor dance wit h t he dischar ge of hydr ogen on some
elect r odes.
(b) P ol a r ogr a p h i c Wa ve s for Hyd r oge n I on s a s gi ve n b y St r on g Aci d s : As
r egar ds t he shape of t he cur r ent -volt age cur ve and it s dependence on t he hydr ogen
ion concent r at ion. These t wo ar e ver y impor t ant and fundament al quant it ies in
t he t heor y of hydr ogen over volt age. It has been st at ed, for example, t hat t he
hydr ogen wave is asymmet r ic [1] and it s half-wave pot ent ial depends on t he
hydr ogen ion concent r at ion [6].
(c) Polar ogr aphic Waves for Hydr ogen Ions Given by Weak Non-Reducible Acids:
The behaviour of weak non-r educible acids t hat give r educt ion waves for hydr ogen
ions is quit e complicat ed. For acids which have k
a
bet ween 25, t he r esult ing
limit ing cur r ent is diffusion cont r olled. The half-wave pot ent ial is displaced t o
mor e negat ive values wit h incr easing concent r at ion of t he acid and par t icular ly
of it s anions and at t he same t ime, t he slope of t he wave decr eases.
A fur t her example char act er ized by t he st r ong influence of t he double layer on
polar ogr aphic behaviour could be r epr esent ed by t he syst em
3
Eu
e
+
+
Eu
2
+ ...(21)
The st andar d oxidat ion r educt ion pot ent ial for t his syst em is 0.601 V (in 1 M
NaClO
4
) so t hat t he influence of t he double layer may be st udied on eit her side of t he
elect r o-capillar y zer o.
References
1. Fr umkin A. N. : 2, Physik. Chem. 164 A, 121 (1933).
2. Gr aham, D.C., J . Elect r ochem. Soc., 98, 343 (1951) and J . Am. Chem. Soc., 71, 2975
(1949).
3. Heyr ovsky, J ., Chem. List y 31, 440 (1937).
4. Kut a J ., Chem. List y 50, 991 (1956).
5. Tamamushi R. : Bull Chem. Soc., J apan 25, 287, 293 (1952) : 26, 56 (1953).
6. Tomes J ., Collect ion Czechoslov. Chem. Communs. 9, 1950 (1937).
CHAPTER 7
AMPEROMETRIC TITRATIONS
A convent ional amper omet r ic t it r at ion is one whose cour se is followed by measur ing a
cur r ent almost always a limit ing cur r ent at a volt ammet r ic indicat or elect r ode.
Depending on t he pot ent ial of t he elect r ode and t he volt ammet r ic char act er ist ics of t he
chemical subst ances involved, t he cur r ent may be pr opor t ional t o t he concent r at ion of
t he subst ances being t it r at ed, t o t he concent r at ion of t he excess of r eagent , or t o t he
concent r at ion of one of t he pr oduct s of t he r eact ion, or it may depend on t wo of t hese
concent r at ions. The t it r at ion cur ve is a plot of t he limit ing cur r ent against t he volume
of t he r eagent added. If necessar y it may be cor r ect ed for t he r esidual cur r ent and for
dilut ion by t he r eagent . Ideally it consist s of t wo st r aight lines int er sect ing at t he
equivalence point . Amper omet r ic t it r at ions can be used t o det er mine many subst ances,
such as phosphat e and sulphat e t hat ar e not elect r oact ive besides amper omet r ic t it r at ions
ar e usually less t edious and mor e pr ecise.
7.1 TYPES OF AMPEROMETRIC TITRATIONS
7.1.1 Theory of Amperometric Titration Curves
The shape of an amper omet r ic t it r at ion cur ve depends on t he subst ance being t it r at ed,
t he r eagent used, and t he pot ent ial applied t o t he indicat or elect r ode. Many differ ent
combinat ions ar e possible but t he feat ur es common t o most t it r at ions cur ves can be
explained by t aking t he t it r at ion of lead ion in weakly acidic suppor t ing elect r olyt e wit h
st andar d pot assium chr omat e, using dr opping elect r ode at a pot ent ial wher e bot h lead
ion and chr omium (vi) yield t heir diffusion cur r ent s. For t he sake of simplicit y it is
assumed t hat t he solubilit y of lead chr omat e is negligibly small in t he medium employed
and t hat t he concent r at ion of suppor t ing elect r olyt e is so high t hat t he migr at ion cur r ent
can be ignor ed. The chemical equilibr ium is at t ained bet ween t he addit ion of each
aliquot of r eagent and t he measur ement of t he cur r ent , and t hat t he diffusion cur r ent
of each ion is pr opor t ional t o it s concent r at ion.
An amper omet r ic t it r at ion cur ve is a plot (i ir) [V
0
+ v] against v, wher e V
0
is t he
volume of solut ion t it r at ed and t he volume of r eagent added. The fact or (V
0
+ v)/V
0
ser ves as a cor r ect ion for dilut ion by t he r eagent . In case t he r eact ion pr oceeds vir t ually
t o complet ion at ever y point dur ing t it r at ion, t he plot consist s of t wo st r aight lines
which int er sect t he equivalence point . The slope of t he line pr eceding t he equivalence
point depends on t he value of k i.e., t he r at io of diffusion cur r ent t o concent r at ion for
t he subst ance being t it r at ed; t hat of t he line following t he equivalence point depends on
t he value of k for t he r eagent .
The example of lead being t it r at ed wit h chr omat e (t hat has been t aken) (i) bot h ks
ar e posit ive at pot ent ials wher e bot h ions can be r educed and in t his case t he plot is V
shaped. (ii) In t he same t it r at ion when it is per for med at a pot ent ial wher e chr omat e
ion is r educed but lead ion is not . In t his case k
cr
would be posit ive while k
pb
would be
zer o. Then t he cur r ent would r emain equal t o r esidual cur r ent unt il t he equivalence
point is r eached, t he t it r at ion cur ve would be _/-shaped. (iii) If t he chr omat e ion would
be t it r at ed wit h lead ion at t he lat t er pot ent ial, t he cur r ent would decr ease unt il
equivalence point is r eached and r emain zer o aft er it had been passed. The cur ve would
be\ _-shaped. On t it r at ing lead ion wit h sulphide at a pot ent ial wher e lead ion gives a
cat hodic cur r ent while sulphide gives anodic one so t hat k
Pb
would be posit ive while k
s
negat ive. The cat hodic cur r ent would decr ease t o zer o at t he equivalence point , and t he
anodic cur r ent would incr ease t her eaft er if t he t wo k
s
wer e numer ically equal. A single
st r aight line int er sect ing t he zer o cur r ent axis at t he equivalence point would be obt ained.
Ther e is a pr obabilit y t hat t heir values would differ slight ly. In such a case t he cur ve
would consist of t wo st r aight lines int er sect ing each ot her (at a ver y obt use angle) and
t he zer o cur r ent line at t he equivalence point .
For t he t it r at ion of lead ion wit h chr omat e, t he point of int er sect ion of t he t wo line
segment s is descr ibed by t he r ear r anged equat ion:
0 0
ib Pb
cr
cr
V C
v
C
=
...(1)
which is exact ly t he volume of t he r eagent r equir ed t o r each t he equivalence point . This
is t r ue of all amper omet r ic t it r at ions. No mat t er what kind of chemical r eact ion may be
involved, or what shape of t he t it r at ion cur ve is at t ained and no mat t er what values of
k
s
may be t her e. The line segment should always int er sect at t he equivalence point .
Sour ces of er r or do r emain in amper omet r ic t it r at ion as well.
Amper omet r ic t it r at ions ar e useful in cases wher e pot ent iomet r ic t it r at ions fail.
Ther e ar e t wo kinds of int er fer ences in amper omet r ic t it r at ion. (i) subst ances t hat
consume t he r eagent , t hat co-pr ecipit at es, (ii) t hat t ake par t in induced r eact ions wit h
t he subst ance being det er mined. Int er fer ence in amper omet r ic t it r at ions t akes place as
is t her e in any ot her t echnique.
Amper omet r ic t it r at ions have oft en been employed t o evaluat e solubilit y pr oduct s
and ot her equilibr ium const ant s. For example, if a r educible ion M
n+
is t it r at ed wit h an
iner t one X
n
t o give t he pr ecipit at e Mx, and if t he concent r at ion of bot h solut ions ar e
known t he value of k
t
under condit ions of t he t it r at ion is easily obt ained by appr opr iat e
use of t he equat ions. The equilibr ium-const ant expr ession would be :
[M
n+
] [X
n
] = 1/k
t
...(2)
The appar at us and t echnique ar e descr ibed ahead.
7.2 KINDS OF AMPEROMETRIC TITRATIONS
(i) (a) Redox Tit r a t ions, (b) Complexomet r ic and Chelomet r ic Tit r at ions, (c)
Compensat ion and Diffusion-Layer Tit r at ions.
(ii) Amper omet r ic Tit r at ions wit h Two Polar ized Elect r odes.
7.2.1 Redox Titrations
The t it r at ion cur ve obt ained in an amper omet r ic r edox t it r at ion may have any of a
fair ly lar ge number of shapes. The possibilit ies ar e mor e numer ous t han in a pr ecipit at ion
t it r at ion because t her e ar e four subst ancest he oxidized and r educed for ms of each of
t he t wo couples involved which may cont r ibut e t o t he cur r ent . Each of t he four may give
a cat hodic cur r ent (k > 0) or an anodic one (k < 0), or may be elect r olyt ically iner t
(k = 0), at t he pot ent ial select ed. (k denot es t he r at io of diffusion cur r ent t o concent r at ion).
However , t wo cases ar e mor e common t han ot her s. In one of t hem, only one of t hese
four subst ances yields a cur r ent , which may be eit her cat hodic or anodic. In t he ot her ,
t he oxidized for m of one couple yields a cat hodic cur r ent while t he r educed for m of t he
yields an anodic one.
For t he fir st case example which can be fur nished is t he t it r at ion of vanadium (iv)
wit h vanadium (ii) in 1 F sulphur ic acid, using t he dr opping mer cur y elect r ode as t he
indicat or elect r ode. The following equat ion descr ibes t he r eact ion :
VO
++
+ V
++
+ 2H
+
= 2V
+++
+ H
2
O ...(3)
The second kind of r edox t it r at ion cur ve could be exemplified in a t it r at ion of ir on
(111) wit h vanadium (11) in a neut r al cit r at e medium. At 0.8V vs SCE ir on (111) is
r educed t o ir on (11) giving a cat hodic cur r ent while vanadium (11) is oxidized t o vanadium
(111) giving an anodic cur r ent .
Mer cur y elect r odes ar e specially advant ages in t it r at ions wit h st r ong r educing agent s
because ver y negat ive pot ent ials can be at t ained and because t he elect r ode sur face does
not cat alyze t he oxidat ion of t he r eagent by wat er or hydr ogen ion.
The r ot at ing plat inum wir e elect r ode in par t icular has been ver y widely used in
amper omet r ic t it r at ions.
7.2.2 Complexometric and Chelometric Titrations
Amper omet r ic t echniques cna be used t o find t he end point of a complexomet r ic or
chelomet r ic t it r at ion in sever al ways. If t he met al ion is elect r oact ive and t he complex
or chelonat e is fair ly st able, it may be possible t o find a pot ent ial at which t he unr eact ed
met al ion yields it s limit ing cur r ent while t he r eact ion pr oduct is iner t [6]. The t it r at ion
of cupr ic ion wit h et hylene diamine t et r a acet at e may be per for med wit h a dr opping
elect r ode at a pot ent ial wher e cupr ic ion is r educed but t he chelonat e is not can be t aken
as an example. The cur r ent due t o t he r educt ion of unr eact ed cupr ic ion decr eases as
t he equivalence point is appr oached and becomes ver y small aft er it has been passed.
In a r edox t it r at ion, e.g.,
1
x
O + Red
2
= Red
1
+
2
x
O ; t he measur ement of t he diffusion
cur r ent of
1
x
O appr eciable kinet ic cur r ent s will be obt ained near t he equivalence point
unless t he r ever se r eact ion is quit e slow, alt hough such a sit uat ion is quit e r ar e.
One can t it r at e an ion giving a chelonat e mor e st able t han t hat of t he indicat or in
t he pr esence of ot her giving less st able ones by appr opr iat e select ion of t he indicat or .
Amperomet ric Tit rat ions 85
7.2.3 Compensation and Diffusion-Layer Titrations
Compensat ion t it r at ions ar e t hose t it r at ions in which t he r eagent and t he subst ance
being t it r at ed give cur r ent s of opposit e signs at some pot ent ial, but ideally do not r eact
wit h each ot her at all. The end point of such a t it r at ion is t he point wher e t he cat hodic
cur r ent due t o t he r educt ion of one of t hem is just equal t o t he anodic cur r ent due t o
t he oxidat ion of t he ot her . In such a case t he measur ed cur r ent is just equal t o t he
r esidual cur r ent .
This occur s when t he elect r ode it self is oxidized in t he anodic half-r eact ion. This is
quit e likely t o be possible if t he elect r ode is made of mer cur y, aluminium, silver , or some
ot her r elat ively base met al [4] t he t it r at ion of oxygen wit h sulphide at a mer cur y elect r ode
[3] is a t ypical example.
In pr inciple, a compensat ion t it r at ion could be per for med even if no net chemical
r eact ion could occur at all. Example could be ir on (iii)ir on (ii). The couple behaves
r ever sibly at a dr opping mer cur y elect r ode in a weakly acidic solut ion cont aining cit r at e,
et hylene diamine t et r a acet at e, oxalat e or t ar t r at e. In any of t hese media fer r ic ir on
could be t it r at ed wit h fer r ous ir on at any pot ent ial on t he r ising par t of t heir waves,
wher e fer r ic ir on would give a cat hodic cur r ent and fer r ous ir on an anodic one.
Diffusion-layer t it r at ions can be exemplified by t he t it r at ion of oxygen wit h a st r ong
acid [2]. The t it r at ion can be per for med wit h a dr opping mer cur y elect r ode at a pot ent ial
( 1.8 V vs SCE) wher e bot h oxygen and hydr ogen ar e r educible. A neut r al but unbuffer ed
suppor t ing elect r olyt e should be used t o suppr ess t he migr at ion cur r ent of hydr ogen ion.
When oxygen is r educed, hydr oxyl ions ar e for med at t he elect r ode sur face by t he half
r eact ion
O
2
+ 2H
2
O + 4e = 4OH
As t hese diffuse away fr om t he elect r ode sur face t hey r eact wit h hydr ogen ions
diffusing t owar ds it . Hydr ogen ions ar e t hus pr event ed fr om r eact ing t he elect r ode
sur face unt il t heir flux equals t hat of hydr oxyl ion, when D
1/2
H +
2
+ 1 2
O
H 2
C 4D CO = .
Upt o t his point t he value (i i
r
) r emains const ant aft er cor r ect ion is made for dilut ion.
Aft er t his it incr eases linear ly wit h t he volume of t he acid added in excess.
7.3 AMPEROMETRIC TITRATIONS WITH TWO POLARIZED ELECTRODES
In such a case qualit at ively differ ent cur ves ar e obt ained wit h t wo polar ized elect r odes,
also known as dual-elect r ode amper omet r ic t it r at ions. These ar e t it r at ions in which t he
cur r ent -pot ent ial cur ve for each of t he t wo elect r odes changes as t he composit ion of t he
t it r at ion mixt ur e changes. Case is easy t o discuss in which t wo elect r odes ar e ident ical,
because t hen t he behaviour of bot h can be explained wit h t he aid of a single cur r ent -
pot ent ial cur ve. It is not necessar y for t hese t o be ident ical, t hey may have differ ent
ar eas, t he efficiencies of st ir r ing at t heir sur faces may differ , and t hey may even be
made fr om differ ent mat er ials. In such an ar r angement t he differ ence bet ween t he
pot ent ials of t he t wo indicat or elect rodes must be equal t o t he applied pot ent ial (neglect ing
iR dr op t hr ough t he cell), and t he cur r ent flowing t hr ough t he indicat or cat hode must
be equal t o (but have t he opposit e sign fr om) t hat flowing t hr ough t he indicat or anode.
The cur r ent var ies as t he t it r at ion pr oceeds and t he shape of t he t it r at ion cur ve depends
on t he r ever sibilit ies of t he couples involved and on t he magnit ude of t he pot ent ial
differ ence applied.
In pr inciple t hese t it r at ions can be made wit h elect r odes of any kind, but st at ionar y
plat inum wir e elect r ode in st ir r ed solut ions ar e much t he most commonly used.
Amper omet r ic t it r at ion wit h t wo polar ized elect r odes have somet imes been claimed
t o be mor e sensit ive t han t hose employing one polar ized elect r ode. For t his r eason t hey
have been widely used in coulomet r ic and ot her t it r at ions in which high sensit ivit y is
needed.
The pr inciples and applicat ions of t hese t it r at ions have been r eviewed by St ock [7],
Delahay [10] and Lingane [5].
7.4 APPARATUS AND TECHNIQUES
Exper iment ally, amper omet r ic t it r at ions ar e much simpler t han ot her polar ogr aphic or
volt ammet r ic t echniques. Since t he cur r ent has t o be measur ed at only a single pot ent ial,
simple appar at us is needed. Fewer var iables need t o be cont r olled because t he exact
value of t he cur r ent at any point is not impor t ant : all t hat mat t er s is, how it var ies as
t he r eagent is added. The t emper at ur e, t he composit ion of t he suppor t ing elect r olyt e,
t he height of t he mer cur y column above a dr opping mer cur y elect r ode or t he r at e of
r ot at ion or st ir r ing of anot her elect r ode is used. Ot her fact or s which ar e ver y impor t ant
in ot her volt ammet ric t echnique are, t herefore, of lit t le concern in amperomet ric t it rat ions,
what is necessar y t o avoid significant var iat ions dur ing t he cour se of any one t it r at ion.
All amper omet ic t it r at ions ar e per for med by measur ing t he cur r ent aft er t he addit ion
of each of a fair ly small number of aliquot s of t he r eagent . In or der t o avoid r educt ion
wave of dissolved oxygen, iner t gas is bubbled for sufficient t ime aft er each addit ion.
Mor e useful would be t o use a micr obur et t e equipped wit h a t hr ee-ways st opcock. If t he
solut ion is sensit ive t o air pr ecaut ions must be t aken.
Mixing aft er each addit ion is necessar y even when deaer at ion is not . A st r eam of
iner t gas can be used for st ir r ing even if it is not r equir ed for deaer at ion. St ir r ing must
be st opped befor e t he cur r ent is measur ed except in t he case of r ot at ing wir e and st ir r ed
pool elect r odes.
Amper omet r ic t it r at ion can be per for med wit h any volt ammet r ic indicat or elect r ode.
Widely used ar e r ot at ing plat inum wir e elect r odes.
In amper omet r ic t it r at ions concent r at ed r eagent s ar e t o be employed. Ther e ar e t wo
r easons for it . One, as is alr eady indicat ed is t o minimize t he impor t ance of t he
t heor et ically necessar y cor r ect ion for dilut ion. The ot her is t o minimize var iat ions in t he
concent r at ions of t he suppor t ing elect r olyt e, which would affect t he diffusion cur r ent
const ant s of t he subst ances t hat cont r ibut e t o t he measur ed cur r ent . Regar dless of t he
shape of t he t it r at ion cur ve, failur e t o cor r ect for dilut ion always causes t he end point
found by t he usual ext r apolat ive pr ocedur e t o occur a lit t le ear lier t han it should changes
in t he concent r at ion of t he suppor t ing elect r olyt e may displace t he end point in eit her
dir ect ion. The simplest example could be of a solut ion cont aining high concent r at ion of
sodium per chlor at e as suppor t ing elect r olyt e which is being t it r at ed wit h a ver y dilut e
r eagent .
100 200
%c.p.
0
ic
ia
c
u
r
r
e
n
t
F i g. 7.1 : Amper omet r ic t it r at ion
curve for applied pot ent ial at E
1
and
E
2
M
+
Most amper omet r ic t it r at ions ar e per for med
wit h r eagent s having nor malit ies at least 10 or
20 t imes as lar ge as t hose of t he solut ions t it r at ed.
Compr ehensive r eviews of t he applicat ions of
amper omet r ic t it r at ions in pr act ical analysis have
been given in t he lit er at ur e cit ed.
As a lr ea dy st a t ed t ha t a n a mper omet r ic
t it r at ion is one in which t he end point is det er mi-
ned by t he cur r ent r esult ing fr om a pot ent ial
applied acr oss t he t wo elect r odes.
7.4.1 The Working Electrode : Reference
Electrode
In t he case in which t he pot ent ial of a wor king
elect r ode is cont r olled r elat ive t o a r efer ence
elect r ode, t he pot ent ia l is a pplied so t ha t a
limit ing cur r ent which is pr opor t ional t o t he concent r at ion of one or mor e of t he r eact ant s
or pr oduct s of t he t it r at ion is measur ed. As a r esult a t it r at ion cur ve is obt ained by
plot t ing t he limit ing cur r ent as a funct ion of
volume of t it r ant added. The shape of t he t it r at ion
cu r ve ca n be pr edi ct ed fr om h ydr odyn a mi c
volt ammograms of t he solut ion obt ained at various
st ages of t he t it r at ion.
The Fig. 7.1, shows r esult ing amper omet r ic
t it r at ion cur ves for t wo values of applied pot ent ial.
Their shapes ar e det er mined by t he behaviour of
t he limit ing cur r ent of t he volt ammogr am at t he
par t icular pot ent ial dur ing t he t it r at ion.
Fig. 7.2, descr ibed t he exper iment al set up of
t it r at ion assembly.
7.5 TWO WORKING ELECTRODES
In br ief, a useful var iat ion of t he amper omet r ic
t it r at ion involves meaning t he cur r ent r esult ing
fr om a small fixed pot ent ial applied acr oss t wo
wor kin g elect r odes. On e of t h ese elect r odes
funct ions as an anode and t he ot her as a cat hode.
The expect ed cur r ent behaviour dur ing a t it r at ion
can be explained by means of hydr odynamic volt ammogr ams. The advant age of t he t wo
wor king elect r ode var iat ion is t he eliminat ion of a r efer ence elect r ode, which can be
t r oublesome in non-aqueous solvent s.
One advant age of amper omet r ic t it r at ion is it ease of aut omat ion. A t it r at or can be
signaled t o shut off when a specified cur r ent level is r eached.
F i g. 7.2 : Wir ing diagr am for a
t it r at ion assembly wit hout an
ext er nal applied volt age (wit h a
r ot at ing elect r ode)
7.6 CHRONOAMPEROMETRY
The excit at ion signal in chr onoamper omet r y is a squar e-wave volt age signal. This is
shown in Fig. 7.3 (a) which st eps
t h e pot en t i a l of t h e wor k i n g
elect r ode fr om a value at which no
far adaic cur r ent occur s, E
i
, t o a
pot ent ial, E
s
, at which t he sur face
concent r at ion of t he elect r oact ive
species is effect ively zer o. The
pot ent ial can eit her be maint ained
at E
s
unt il t he end of t he exper i-
ment or be st epped t o a fina l
pot ent ial E
f
aft er some int er est of
t ime T ha s pa ssed. The la t t er
exper i men t i s t er med dou bl e-
pot ent ial-st ep chr onoamper omet r y.
Cur r ent as a funct ion of t ime
is t he syst em r esponse as well as
t h e mon i t or ed r es pon s e i n
ch r on oa mpe-r omet r y. A t ypica l
double pot ent ial-st ep chr onoam-
perogram is shown by t he solid line
in Fig. 7.3 (b) (t he dashed line shows t he backgr ound r esponse t o t he excit at ion signal
for a solut ion cont aining suppor t ing elect r olyt e only. This cur r ent decays r apidly when
t he elect r ode has been char ged t o t he applied pot ent ial). The pot ent ial st ep init iat es an
inst ant aneous cur r ent as a r esult of t he r educt ion of O t o R. The cur r ent t hen dr ops
as t he elect r olysis pr oceeds.
It is impor t ant t o not e t hat t he char ge Q passed acr oss t he int er face is r elat ed t o
t he amount of mat er ial t hat has been conver t ed, and t he cur r ent i is r elat ed t o t he
inst ant aneous r at e at which t his conver sion occur s. Cur r ent is physically defined as t he
r at e of char ge flow. Ther efor e,
Q = nFN ...(1)
wher e N is t he number of moles conver t ed, and t he inst ant aneous cur r ent at t ime t is
i
t
=
t t
dQ dN
nF
dt dt
| | | |
=
| |
\ . \ .
...(2)
The r at e of conver sion, dN/ dt, is dir ect ly pr opor t ional t o t he elect r ode ar ea and t o
t he flux of mat er ial t o t he elect r ode as descr ibed by t he following equat ion (which is
der ived fr om Ficks fir st law) :
i
t
= nF AD
0
0
0 X , t
C
X
=
| |
|
\ .
...(3)
E
s
E
i
E
f
Ti me
P
o
t
e
n
t
i
a
l
0
C
u
r
r
e
n
t
Ti me
(a) Pot ent ial excit at ion
s i gn a l for dou bl e
pot ent ial st ep
(b) Cur r ent -t ime r esponse
s i gn a l (ch r on oa mper o-
gram)
Fig. 7.3 : Chr onoamper omet r y.
wher e i
t
= cur r ent at t ime t, A
n = number of elect r ons, eq/mol
F = Far adays const ant , 96,485 C/eq
A = elect r ode ar ea, cm
2
C = concent r at ion of O, mol/cm
3
(mol/L!)
D = Diffusion coefficient of O, cm
2
/s
t = t ime s
X = dist ance fr om t he elect r ode, cm
Chr onoamper omet r y has pr oven useful for t he measur ement of diffusion coefficient
of elect r oact ive species. An aver age value of
1 2
t
i over a r ange of t ime is det er mined at
an elect r ode t he ar ea of which is accur at ely known and wit h a solut ion of known
concent r at ion. The diffusion coefficient can t hen be calculat ed fr om
1 2
t
i via t he Cat t r ell
equat ion [8]. The elect r ode ar ea can be physically measur ed, but t he common pr act ice
is t o measur e it elect r ochemically by per for ming t he chr onoamper omet r ic exper iment as
a r edox species whose diffusion coefficient is known [1]. The value of A is t hen calculat ed
fr om
1 2
t
i .
If t he het er ogeneous elect r on t r ansfer of t he r edox species wit h t he elect r ode it self
is slow, t he cur r ent aft er t he pot ent ial st ep in necessar ily less t han in a syst em in which
t he elect r on t r ansfer is r apid. This aspect of chr onoamper omet r y has been used for t he
measur ement of het er ogeneous r at e const ant s [9] [7].
The behaviour of
1 2
t
i as a funct ion of t ime can be influenced subst ant ially by t he
pr esence of chemical r eact ions t hat ar e coupled t o t he elect r ode pr ocess. Consequent ly,
char act er ist ic var iat ions of
1 2
t
i vs t have been effect ively ut ilized for t he quant it at ive
st udy of such homogeneous chemical r eact ions. The ECE r eact ion in which a chemical
st ep exist s bet ween t wo elect r on t r ansfer st eps is one mechanism t hat has been
invest igat ed by means of chr onoamper omet r y :
E : O + e R
C : R
k
X
E : X + e P.
As shown in t he r eact ion sequence above, a r at e det er mining chemical st ep in
int er posed bet ween t he t wo elect r ode r eact ions. The t wo dashed lines in Fig. 7.3 (a)
show hypot het ical chr onoamper ogr ams for t he 1e r educt ion of O t o R and for dir ect 2e
r educt ion of O t o P wit h no kinet ic complicat ions. The solid line shows a t ypical
chr onoamper ogr am for an ECE mechanism. The cur r ent is int er mediat e bet ween t he 1e
and 2e r educt ions, since t he r educt ion of X t o P is cont r olled by t he r at e of t he chemical
r eact ion of R t o gener at e X. The exact posit ion of t he solid line is det er mined by t he
value of t he r at e const ant k.
Chr onoamper omet r y has been applied t o t he st udy of sever al elect r ode mechanisms
[12,13]. In such st udies differ ent mechanisms may exhibit similar r esponses [1, 6].
Double-pot ent ial st ep chr onoamper omet r y is par t icular ly suit ed for st udying syst ems
t hat follow EC [12] or dimer izat ion [16] mechanism.
References
1. Delahay, P., New Inst r ument al Met hods in Elect r ochemist r y, Int er science, N7. 1954.
pp. 258264.
2. Kemula, W., and Siekier ski, S., Collect ion Czechoslov. Chem. Communs. 15, 1069 (1950).
3. Kolt hoff, I.M., and Miller , C.S., J . Am. Chem. Soc. 62, 2171 (1940).
4. Kolt hoff, I.M., and Sambyct t i, C.J ., Anal Chem. Act a, 21 71 (1959); 22, 253, 351 (1960).
5. Lingane, J .J ., Elect r oanalyt ical Chemist r y, Int er science., N.Y., 2nd ed., 1958, pp. 280
295.
6. Pr ibil, R., and Mat yska, B., Collect ion Czechoslov. Chem. Communs., 16, 139 (1951).
7. St ock, J .T., Anal. Chem., 36, 355 R (1964).
8. Cot t rell eq. p. 58 Kissinger Pet er T., Heinman W.R., Laborat ory Technique Marcel Dekker
Inc. N.Y.
9. William R. Heinman, Dept . of Chemist r y Univer sit y of Cincinnat i, Ohio Kissinger Pet er
T., Dept . of Chem. Pur due Univer sit y, Inc., West Lafayet t e, Indiana.
10. Adams, R.N., Elect r ochemist r y at Solid Elect r odes, Mar cel Dekker , New Yor k, 1969.
11. Bard, A.J , and Faulkner, L.R., Elect rochemical Met hods : Fundament als and Applicat ions,
Wiley, New Yor k, 1980.
12. Alber t , G.S., and Shain I., Anal. Chem. 35 : 1859 (1963).
13. Hawley, M.D., and Feldber g, S.W., J . Phys. Chem. 70 : 3459 (1966).
14. Feldber g, S.J ., Phys. Chem., 73 : 1238 (1969).
15. Schwaz, W.M., and Shain I., J . Phys. Chem. 69 : 30 (1965).
16. Olmst ead, M.L., and Nicholson, R.S., Anal. Chem. 41 : 851 (1969).
CHAPTER 8
POLAROGRAPHY OF
METAL COMPLEXES
8.1 REVERSIBLE, DIFFUSION-CONTROLLED SYSTEMS DETERMINATION
OF FORMULAE AND STABILITY CONSTANTS OF COMPLEXED METAL
IONS
Effect s of Li ga n d s on P ola r ogr a p h i c Wa ves : When met al ions in solut ion undergo
complexat ion wit h ligands ot her t han wat er molecules, t heir polar ogr aphic r educt ion
waves appear in t wo quit e dist inct ways. Fir st ly, t he half-wave pot ent ial is shift ed t o
mor e nega t ive pot ent ia l. This ha ppens
almost invar iably. Secondly, t he diffusion
cu r r en t ch a r ges a n d u s u a l l y becomes
smaller (Fig. 8.1).
St u di es of t h e s t a bi l i t i es of met a l
complexes polar ogr aphically, involve t he
det er mi n a t i on of s h i ft s i n h a l f-wa ve
pot ent ials or limit ing cur r ent s of met al ions
in t he pr esence of incr easing amount s of
complexing ligands. The shift of half wave
pot ent ial of t he r educt ion of a met al ion
t aking place r ever sibly, bot h in t he absence
and pr esence of complexing agent s, shift s
t owar ds cat hodic dir ect ion. The shift incr eases wit h incr easing ligand concent r at ion.
The r at e of t he elect r on exchange pr ocess r emains r elat ively fast wit h r espect t o t hat
of diffusion so t hat t he lat t er is st ill r at e det er mining. It is also t o be not ed t hat in t he
pr esence of t he ligands, t he r educt ion wave has a shape indicat ive of a gr eat er degr ee
of r ever sibilit y t han t hat obser ved for t he r educt ion of t he aquo ion, which is at t enuat ed
and of lower slope t han expect ed for a 2-elect r on r ever sible r educt ion.
The decrease of diffusion current wit h increasing ligand concent rat ion is t o be expect ed
owing t o t he incr eased bulk of t he complexed ions r elat ive t o t hat of aquo ions. Such
var iat ions of diffusion coefficient have been used as t he basis of met hods of det er mining
st abilit y const ant s of complexes in solut ion.
Met hods for det er mining st abilit y const ant s of met al complexes by polar ogr aphic
met hod ar e being divided int o t hr ee cat egor ies :
(i) Met hods which ar e applicable t o r ever sible r educt ions only.
6
5
4
3
2
1
0.3 0.4 0.5 0.6 0.7 0.8
i
d
(
A
)
Fi g 8.1 : Effect of complexat ion on

r educt ion wave of a met allic ion
(ii) Met hods applicable t o ir r ever sible r educt ions.
(iii) Met hods which may be applicable t o bot h r ever sible and ir r ever sible syst ems.
The polar ogr aphic t echnique, involving t he dir ect measur ement of half-wave pot ent ials
of aquo and complexed met al ions may be used t o det er mine t he st abilit y const ant s of
met al-ligand syst ems of a var iet y of t ypes.
Cases wher e r ever sible r educt ions t ake place, t hr ee main t ypes of met al-ligand
syst ems ar e applicable.
(i) Those in which a single complex species is for med t o t he vir t ual exclusion of all
ot her s over t he ent ir e ligand concent r at ion wor king r ange.
(ii) Those in which sever al complexes ar e for med in st epwise manner , but whose
st a bilit ies differ sha r ply fr om one a not her bet ween t he limit s of liga nd
concent r at ion.
(iii) Cases in which a set of mobile equilibr ia exist s bet ween t he var ious complexes
and t he aquo ion. This is being r epr esent ed by t he following equat ion :
M(H
2
O)
n
MX(H
2
O)
n1
MX
2
(H
2
O)
n2
::: MX
4
...(1)
In such syst ems, sever al t ypes of complexes ar e pr esent at ever y ligand concent r at ion.
The pr opor t ion of higher species incr eases wit h incr easing concent r at ion of ligand. Finally,
t he pr edominent species is t hat wit h t he highest possible coor dinat ion number . Lar ge
number of syst ems have been st udied polar ogr aphically in t his cat egor y by pr evious
aut hor s.
8.2 DETERMINATION OF STABILITY CONSTANTS AND COORDINATION
NUMBERS OF METAL COMPLEXES
(i) The met hod of Lingane [3].
(ii) The met hod of DeFor d and Hume [1] for det er mining consecut ive over all st abilit y
const ant s.
(iii) The met hod of Schaap and McMast er s [5] Mixed ligand syst ems.
(i) Th e Me t h od of Li n ga n e : The r educt ion of a complexed ion t o t he met allic st at e
(as an amalgam) is being consider ed at t he dr opping mer cur y elect r ode. The elect r ode
r eact ion may be expr essed as :
( ) n jm
f
MX ne Hg
+
+ = M(Hg) + j (X
m
) ...(2)
wher e MX
f
is t he complex of met al ion M wit h ligand X car r ying a char ge (n j m).
The char ge on t he met al being n
+
and on t he ligand species as m
.
This over all pr ocess is r epr esent ed as being made up of t wo r eact ions. The fir st one
involving pr ior dissociat ion of t he complex ion int o aquo ions and ligand. The second one
is t he elect r ochemical r eact ion of t he aquo ion it self, t hus :
MX
f
(n j m)
+ n m
M j X
+ ...(3)
| ne, E
0
M
If t hese pr ocesses t ake place r ever sibly and much mor e r apidly t han t he r at e of
nat ur al diffusion of ions t o t he elect r ode sur face, t hen t he pot ent ial of t he DME at all
point s on t he polar ogr aphic wave may be given by :
Polarography of Metal Complexes 93
0
0
0
ln
A A
A
M M
C RT
E E
nF
C
...(4)
wher e CA
0
is t he concent r at ion of amalgam for med on t he sur face of t he DME and
A
it s act ivit y coefficient
0
M
C is t he concent r at ion of t he met al ion M in t he solut ion at t he
dr op sur face and
M
it s act ivit y coefficient .
0
A
E is t he st andard pot ent ial of t he amalgam.
The over all t her modynamic st abilit y const ant ,
X
M
+
, of t he complex MX
f
(omit t ing
t he char ges) is given by t he expr ession.
| |
| || |
f
f
MX
f
MX
M X
=
...(5)
her e t he br acket ed t er ms r epr esent act ivit ies. The concent r at ion of t he complex in t he
bulk of t he solut ion, for a given concent r at ion of met al ion and ligand may be wr it t en
as :
| |
f
f
f
f
MX M M
MX
MX
C X
C

=
...(6)
At t he elect r ode sur face t he met al ion will have a concent r at ion given by t he
expr ession :
| |
0
0 f
f
f
f
MX m M
MX
MX
C X
C

=
....(7)
wher e, as befor e, t he super scr ipt r efer s t o t he values at t he sur face. This equat ion is
valid if it be assumed t hat t he concent r at ion of t he ligand is lar ge and const ant t hr oughout
t he solut ion wit h t he same value of act ivit y coefficient bot h in t he bulk and at t he
elect r ode sur face.
The shift in t he half-wave pot ent ial, pr oduced by t he pr esence of an excess of ligand
X, is given by :
(E
1/2
)
S
(E
1/2
)
C
= E
1/2
=
| |
M 2303
log
f f
f
f
MX MX
M MX
I X
. RT
.
nF I

...(8)
If it is assumed t hat t he diffusion cur r ent const ant s I
M
, I
MX
ar e appr oximat ely equal.
Thus, t he equat ion in it s simplified for m as was or iginally used by Lingane [3] is
given as :
E
1/2
=
( )
2 3 0 3 00591 00591
log log log at 25 C
f f
MX X' MX x
. RT . .
C j c
nF n n
= +
...(9)
The equat ion :
E = (E
1/2
)
c

00591
log at 25 C
d
. i
n i i
...(10)
is seen t o be ident ical wit h t he Heyr ovsky- Ilkovic equat ion for t he r educt ion of an aquo
ion. The equat ion t hus holds bot h for simple and complexed ions pr ovided t hat t he
r educt ion of bot h pr oceeds r ever sibly.
A mor e simplified equat ion based on t he assumpt ion t hat t he half-wave pot ent ial is
independent of t he concent r at ion of t he complex species is given below :
(E
1/2
)
c
=
0
00591 00591
log log
f
A MX X
. .
E j C
n n

...(11)
It is evident t hat t he r at e of char ge of half-wave pot ent ial wit h ligand concent r at ion
may be expr essed as,
( ) 1 2
00591
log
c
X
d E
.
j
d C n
= at 25 C ...(12)
Thus, a plot of (E
1/2
)
c
ver sus log C
X
should be linear of slope j (0.0591/n) fr om which
t he coor dinat ion number , j, of t he complex,
f
X
M , may be found. Once j is found, it is
simple t o calculat e
Mx
f
fr om t he equat ion given below :
E
1/2
=
00591 00591
log l ogC 25 C
j
MX X
. .
j at
n n

...(13)
This equat ion was or iginally used by Lingane.
(ii) The method of DeFord and Hume [1] for determining consecutive overall
stability constants
DeFor d and Hume made t he fir st at t empt in polar ogr aphy, r egar ding t he st ep-
equilibr ia bet ween successfully for med complexes in solut ion.
The concent r at ion of each complex species, for a given fr ee ligand concent r at ion, is
given by t he expr ession of t he for m of equat ions (6 and 7) which ar e alr eady given. The
equat ion 7 on summing up over all possible (mononuclear ) species, now t akes t he for m:
| |
0 0
0 0
f
f
N N
MX
MX M
f
X
C C M
M X
=
...(14)
wher e j = 1, 2, 3, ..., N.
The shift in half-wave pot ent ial is now finally expr essed by :
E
1/2
=
| |
0
2 3 0 3
log
f
f
f
N
MX
C
M
M MX
X
I . RT
nF I
| |
|
|
\ .
...(15)
In or der t o calculat e t he individual over all const ant s, it is convenient t o r ear r ange
t he above equat ion and finally expr ess in t he for m :
F
0
[X] =
0
+
1
[X] | |
( )
| |
( )
2
2
2
2
X X
N
N
N M X M X M X
N
M MX M
X ... X

+ + +

...(16)
In t he equat ion (16) t he left hand side has been wr it t en as F
0
[X] which denot es t hat
it is a funct ion of t he fr ee ligand concent r at ion. The summat ion, on t he r ight hand side
has been given in t he expanded for m. The init ial t er m
0
, is t he st abilit y const ant of t he
zer o complex which by definit ion, has t he value unit y.
It is, t her efor e, possible in pr inciple t o calculat e t he N st abilit y const ant s for m N
values of t he funct ion F
0
[X] cor r esponding t o t he r ange of [X] values. In act ual pr act ice,
it is necessar y t o use many mor e values of [X] t han t he nor mal value of N.
8.2.1 Calculation of Individual Complex Stability Constants
In t he equat ion (16) t he funct ion F
0
[X] expr esses in t er ms of t he concent r at ion of fr ee
uncomplexed ligand and also a set of act ivit y coefficient s. Wor king in solut ions of const ant
ionic st r engt h, t he values of act ivit y coefficient s can be maint ained const ant . Not only
so, in condit ion of const ant ionic st r engt h, it is assumed t hat t he act ivit y coefficient in
t he equat ion (16) may be dr opped and finally t he lat t er t akes t he for m :
F
0
[X] = 1 +
1
[X] +
2
[X]
2
+ ... +
N
[X]
N
...(17)
In nor mal pr act ice it is desir able t o det er mine t he shift in half-wave pot ent ial of a
given met al ion for about t welve values of ligand concent r at ion in t he r ange of 0.1 t o
2.0 M depending upon t he ligands solubilit y. The met al ion concent r at ion which is
nor mally t o be used is 5 10
4
M t o 10
3
M. The choice has a lat it ude as t he half-wave
pot ent ial shift s ar e independent of it . It should, however , nor mally be maint ained st r ict ly
const ant over any par t icular r un of ligand concent r at ion in or der t o cor r ect ly and easily
allow for t he var iat ion of t he limit ing cur r ent . Aft er making suit able cor r ect ions t o t he
obser ved E
1/2
values, t he var ious F
0
[X] funct ions ar e calculat ed for each value of [X].
To det er mine
1
, ...,
N
, t he gr aphical ext r apolat ion met hod devised by Leden [2] is
applied.
On plot t ing t he der ived F
1
[X] values against cor r esponding values of X, a limit ing
slope is obt ained, as [X] t ends of zer o, of
2
and an int er cept , on t he F
1
[X] axis of
1
. Thus
a confir mat ive est imat ion of
1
is possible and in addit ion, a pr eliminar y value of
2
is
obt ained. A funct ion F
2
[X] can t hus be defined similar ly. In or der t o account for N
complexes, t his pr ocedur e is cont inued. As such t he F
N 1
[X] ver sus [X] plot gives is a
st r aight line and indicat ing dir ect ly, t hat t he penult imat e funct ion has been r eached.
It is a usual pr act ice t o at t empt measur ement of half-wave pot ent ials t o t he near est
0.1 mV.
8.3 MIXED LIGAND SYSTEMSTHE METHOD OF SCHAAP AND
MCMASTERS
The met hod signifies t he logical ext ension of t he DeFor d and Hume met hod. The met hod
was applied in cases wher e t he met al ions complex wit h t wo ligand species ar e
simult aneously pr esent in t he solut ion.
Consider ing a complexing r eact ion of t he t ype :
M + i X + jY
i
X f
M Y ...(18)
in which, i, j ar e st oichiomet r y number s and X, Y ar e t wo differ ent ligands species. In
t his met hod [Y] is r egar ded as maint ained const ant while [X] is var ied. A r elat ion of
ident ical for m holds under such condit ions t hat [X] is const ant and [Y] var ied.
This pr inciple was applied by Schaap and McMast er s t o t he copper and cadmium-
et hylene diamine-oxalat e syst ems. The oxalat e concent r at ion being held const ant while
t hat of et hylene diamine was var ied. For t his syst em, t hr ee mixed complexes ar e possible,
e.g., Cd (en) (OX), Cd (en)
2
(OX) and Cd (en)
( )
2
2
OX
. By using t he convent ional DeFor d-

Hume met hod values of t he t wo const ant s could be det er mined fr om st udies on t he
simple cadmium-et hylene diamine and cadmium oxalat e syst ems. The ot her const ant
could be found fr om F
10
funct ion by obt aining t he int er cept fr om a plot of F
10
(en, OX)
ver sus [en].
For mor e det ails t he r eader s ar e advised t o consult valid lit er at ur e on t he subject .
The polar ogr aphic t echnique, involving t he dir ect measur ement of half-wave pot ent ials
of aquo and complexed met al ions, may be used t o det er mine t he st abilit y const ant s of
met al-ligand syst ems of a var iet y of t ypes. All t hese met hods ar e applicable when t he
elect r ode pr ocess of bot h simple and complexed species occur r ever sible. Ir r ever sible
r educt ions have been t aken up lat er on. The met hod of Schwar zenbach [6] and Ringhbom
and Er iksson [4] have been quit e popular and useful.
References
1. Defer d, D.D., Hume, D.N., J . Am. Soc. 73, 5321 (1951).
2. Leden, I., Z. Phys. Chem. 188, 160 (1941).
3. Lingane, J .J ., Chem. Rev. 29, 1 (1941).
4. Ringbom, A., and Er iksson, L., Act a. Chem. Scand. 7, 1105 (1953).
5. Schaap, W.B., and McMast er s, D.L., J . Am. Soc. 83, 4699 (1961).
6. Schwar zenbech, G., and Aker mann, H., Helv. Chim. Act a. 35, 485 (1952).
CHAPTER 9
POLAROGRAPHY OF
ORGANIC COMPOUNDS
The polar ogr aphic act ivit y of or ganic compounds is due t o t he pr esence of one or mor e
funct ional gr oups in t he molecule. Out of t he mor e impor t ant compounds ar e aldehydes,
u n s a t u r a t ed ket on es , n it r o a n d n it r os o-compou n ds , dis u lph ides , polymer
hydr ocar bons, halides, and per oxides.
As a r ule, t he r educt ion waves of or ganic subst ances ar e gover ned by t he r at e of t he
elect r ode pr ocess and by diffusion.
In t he r educt ion of or ganic subst ances, t he hydr ogen ion concent r at ion has a similar
significance as t he concent r at ion of t he complex for ming agent in t he r educt ion of
complexes. For t his r eason, t he half-wave pot ent ial is usually a funct ion of pH, e.g.,
O
X
+ pH
+
H
P
P
X
O + ne H
1
Red. ...(1)
As alr eady descr ibed applicat ions of polar ogr aphy ar e based on t he measur ement
and int er pr et at ion of cur r ent volt age cur ves. In 1922, however . Dr . J ar oslov Heyr ovsky
of Char les Univer sit y, Pr ague, int r oduced t he dr opping mer cur y elect r ode. This elect r ode
consist s of mer cur y dr op, hanging for a few seconds at t he or ifice of a glass capillar y
fr om which t he mer cur y r egular ly dr ops out . The elect r ode and a r efer ence elect r ode ar e
immer sed int o t he solut ion t o be elect r olysed. When an ext er nal volt age is applied
acr oss t hese t wo elect r odes cont r olled pot ent ial elect r olysis can be car r ied out (Fig. 9.1).
The var iat ion of cur r ent wit h a cont inuously incr easing volt age can be measur ed by an
inst r ument in t he cir cuit . This measur ement gives cour r ent -volt age cur ves i.e., i vs E.
These cur ves, obt ained wit h a dr opping mer cur y elect r ode or even wit h any ot her
elect r ode wit h a per iodically r enewed sur face ar e complet ely r epr oducible and ar e called
polar ogr aphic cur ves. These cur ves depend only on t he composit ion of t he elect r olysed
solut ion, wit h exper iment al condit ions kept const ant . In t he pr esence of subst ances
which under go r educt ion or oxidat ion at t he sur face of t he dr opping elect r ode, or
subst ances t hat cat alyt ically effect t he elect r ode pr ocess, or t hose t hat for m st able
compounds wit h mer cur y, an incr ease in cat hodic or anodic cur r ent on t he cur r ent -
volt age cur ve is obser ved. The cur r ent r ises in a given pot ent ial r ange and t his incr ease
is followed by a r egion of pot ent ial in which t he cur r ent has r eached a limit ing value.
The S-shaped por t ion of t he cur r ent -volt age cur ve is called a polar ogr aphic wave.
The shape and posit ion of polar ogr aphic waves pr ovides us wit h infor mat ion on bot h
t he quant it at ive and qualit at ive composit ion of t he elect r olysed solut ion. The differ ence
bet ween t he limit ing cur r r ent and t he cur r ent befor e t he waves r ise, is called t he wave
height . This usually depends in t he concent r at ion of t he elect r oact ive subst ance in
solut ion. Most analyt ical applicat ions of bot h or ganic and inor ganic polar ogr aphy ar e
based on t he incr ease in wave height wit h concent r at ion.
Anot her impor t ant quant it y is known as half-wave pot ent ial. This is t he point on a
polar ogr aphic cur ve at which t he cur r ent r eaches half of it s limit ing value. The wave
height , alt hough, it depends on concent r at ion, t he half-wave pot ent ial is pr act ically
independent of t he concent r at ion of t he elect r oact ive species. But it s value does depends
on t he kind of or ganic compound involved. The half-wave pot ent ial is a quant it y t hat
can be used for qualit at ive char act er izat ion of or ganic subst ances because, t he half-wave
pot ent ial depends on t he nat ur e of elect r olysed solut ion and also on t he composit ion of
t he solut ion.
Measur ement s of bot h wave height s and half-wave pot ent ials ar e impor t ant in solving
pr oblems in fundament al or ganic chemist r y. The measur ement s of wave height s can be
applied t o t he st udy of some slowly est ablished equilibr ia, of r eact ion kinet ics and hence
of opt imum condit ions for any desir ed synt heses. The half-wave pot ent ials offer
infor mat ion about r apidly est ablished equilibr ia, r eact ivit y t owar ds nucleophilic at t ack
and similar r eact ions, and t he pr esence of cer t ain st r uct ur al gr oups in t he molecule.
Commonly used in chemical analysis, t he polar ogr aphic t echnique can solve some
pr oblems of st r uct ur e, r eact ivit y, mechanism and synt hesis in or ganic chemist r y.
9.1 STRUCTURAL EFFECTS
As alr eady indicat ed in Chapt er 1 t hat for syst ems in which t he equilibr ium bet ween t he
oxidised and r educed for ms is r apidly est ablished at t he sur face of t he elect r ode. These
ar e called r ever sible syst ems and t he half-wave pot ent ials measur ed polar ogr aphically
a r e pr a ct i ca l l y equ a l t o s t a n da r d oxi da t i on -r edu ct i on pot en t i a l s mea s u r ed
pot ent iomet r ically. In t hese cases t he half-wave pot ent ials ar e a funct ion of t he
equilibr ium const ant s of t he oxidat ion-r educt ion equilibr ium.
The possibilit y of char act er ising oxidat ion r educt ion pr oper t ies of numer ous syst ems
is offer ed by polar ogr aphy wher eas applicat ion of pot ent iomet r y is not possible. Syst ems
which involve a st ep wit h a high act ivat ion ener gy, ar e called ir r ever sible syst ems. The
half-wave pot ent ial is a funct ion of t he r at e const ant of t he elect r ode pr ocess involved.
It is not sur pr ising t o find cor r elat ions bet ween t he values of half-wave pot ent ials
and t he st r uct ur e of or ganic compounds. This is because of t he r elat ionship of half-wave
pot ent ials t o equilibr ium or r at e const ant s. Among st r uct ur al fact or s t hat effect half-
wave pot ent ials ar e : (i) t he nat ur e of t he elect r oact ive gr oup, i.e., t he gr oup wher e
cleavage or for mat ion of bond occur s dur ing elect r olysis, (ii) st er eochemist r y, and (iii)
t he nat ur e of subst it uent s. In gener al, t he shift t owar ds mor e posit ive pot ent ials of a
cat hodic wave, cor r esponding t o a r educt ion pr ocess, indicat es t hat t he r educt ion is
pr oceedings mor e r eadily. A shift t owar d mor e negat ive pot ent ial indicat es t hat t he
r educt ion is pr oceeding wit h gr eat er difficult y. Similar ly, for anodic waves, cor r esponding
t o an oxidat ion pr ocess, t he shift t owar ds mor e negat ive values indicat e t hat t he oxidat ion
pr oceeds mor e r eadily.
Polarography of Organic Compounds 99
9.2 NATURE OF ELECTROACTIVE GROUP
The decisive fact or s for det er mining t he polar ogr aphic behaviour of t he or ganic molecule
ar e : t he nat ur e of at oms in t he elect r oact ive gr oup, t heir ar r angement in space, and t he
t ype of bond cleaved or for med. The polar ogr aphic behaviour also depends on t he
molecular fr ame t o which t he elect r oact ive gr oup is bound, t he subst it uent s pr esent ,
and in par t icular on t he gr oups pr esent in t he immediat e vicinit y of t he elect r oact ive
gr oup.
Some such gr oups ar e mor e suscept ible t o t he effect s of t he molecular fr amewor k.
Valid quant it at ive compar ison of half-wave pot ent ial is possible when t he elect r ode
pr ocesses follow t he same mechanism for all t he syst ems t o be composed.
It is gener ally t r ue t hat r educt ion pr oceeds mor e easily when conjugat ion of double
or t r iple bonds of t he elect r oact ive gr oup wit h a mult iple bond or wit h an ar omat ic r ing
occur s. Taking t he example of t he r educt ion obser ved in
4
3 ket ost er oids is shift ed
t o mor e posit ive pot ent ial for
1.4
3 ket ost er oids by 0.15 t o 0.22 volt s. But for
4.6
3
ket ost er oids by 0.29 t o 0.45 volt . Similar ly as t he number of condensed ar omat ic r ings
incr eases, t he r educt ion is made easier . Single C X bonds ar e usually r educed at mor e
negat ive pot ent ials t han C = C CX, but at mor e posit ive pot ent ials t han C C = C
X (X is halogen).
A r igor ous compar ison of elect r oact ive gr oups is r est r ict ed t o a sequence of closely
r elat ed gr oups such as
C F < C Cl < C Br < C I
in which t he ease of r educt ion of t he C X bond incr eases wit h t he incr easing
polar izabilit y of t he halogen X. There are some ot her examples also. Examples of simplified
r educt ion pr ocesses ar e given in t he Table 9.1 and 9.2.
TABLE 9.1
Th ese bon d t ypes ca n be r edu ced a t a dr oppin g mer cu r y elect r ode
C C C N C O C S C X
C = C C = N C = O C = S
C C C N
N N N O N S
N = N N = O
O O O S O X
S S S X
X = Halogen
Condensed benzenoid r ings
Car bonium ions
Some het er ocyclic r ings
TABLE 9.2
A syst em of con ju ga t e mu lt iple bon ds r epr esen t s a sin gle elect r oa ct ive gr ou p
C = C C C C = O
Elect r oact ive Gr oup
< <
C = C C X C C = C X
+ +
Incr eased r eact ivit y Decr eased r eact ivit y
Incr ea sing t he number of condensed a r oma t ic r ings incr ea ses r ea ct ivit y. For
compounds wit h a car bon-halogen bond, an allylic gr oup incr eases r eact ivit y and a vinyl
gr oup decr eases r eact ivit y.
9.3 STERIC EFFECTS
St er ic effect s on half-wave pot ent ials ar e t hose in which t her e is a st er ic hindr ance of
coplanar it y. In t hese cases t he shift s of half-wave pot ent ials t owar d mor e negat ive
values ar e in agr eement wit h values obt ained by independent met hods. Hence t he shift
of 0.085 volt obser ved for 3 0-t olylsydnone is in good agr eement wit h t he value of 0.10
volt for t he r esonance cont r ibut ion of t he 3-phenyl gr oup. This is deduced fr om t he
deviat ion of half-wave pot ent ial of 3-phenyl sydnone fr om t he modified Taft [3] equat ion
for 3-subst it ut ed sydnones. The smaller value obt ained fr om st er ic hindr ance of
coplanar it y indicat es t hat t he met hyl gr oup is t he or t ho posit ion does not pr esent all
r esonance int er act ion bet ween t he phenyl and t he sydnone r ings.
Cis and trans isomer s in some cases differ in t heir half-wave pot ent ials. This differ ence
pr ovides a means of dist inguishing t he isomer s and analysing a mixt ur e of t hese.
The pr esence of bulky alkyl gr oups also somet imes shift t he half-wave pot ent ials
t owar ds mor e negat ive values.
TABLE 9.3
The molecular fr ame can det er mine t he polar ogr aphic behaviour of a gr oup
Independent of Limited dependence S trongly dependent
molecular frame on molecular frame on molecular frame
C = NNHCONH
2
C NO
2
C CN
C SH C CHO
C COCH
3
The pr esence of bulky gr oups also shift s t he half-wave pot ent ials t owar d mor e posit ive
values. This is explained by changes in t he mechanism of elect r ode pr ocess and also by
r elief of st er ic st r ain. An example cit ed in t his r egar d is t he r educt ion of alkyl and cyclo
alkyl br omides.
9.4 SUBSTITUENT EFFECTS
Hammet t [1] was t he fir st t o der ive an equat ion for t he linear dependence of t wo ser ies
of r at e and equilibr ium const ant s for ar omat ic subst ances subst it ut ed in t he par a-and
met a-posit ions wit h respect t o t he react ing group. The validit y of t he following relat ionship
has been confir med for a number of measur ed r eact ion r at es and equilibr ium const ant s
log k log k
0
= (log k log k
0
) ...(2)
log k log k
0
= ...(3)
or log k log k
0
= ...(4)
wher e k ar e t he r at e const ant s for a homogeneous chemical r eact ion, K are t he equilibrium
const ant , denot es t he const ant s for t he non-subst it ut ed subst ance, is a const ant
char act er ising t he subst it uent and is t he r eact ion coefficient , which is const ant for a
given r eact ion and does not change wit h individual der ivat ives. A similar equat ion for
subst it ut ion in t he aliphat ic ser ies has been der ived by Taft [3]. The values of and
have been t abulat ed for cer t ain r eact ions. Applying t he following equat ion : E
1/2
=
0
1 2
E =
; [5] in polar ogr aphy it can be wr it t en in view of t he equat ion.
The above equat ion r equir es D = D
0
and n = (n)
0
. A number of measur ement s
have confir med t he validit y of t his equat ion for half-wave pot ent ials so t hat it can be
assumed t hat t he het er ogeneous r at e const ant for an elect r ode pr ocess var ies wit h t he
nat ur e of t he subst it uent in t he same manner as t he const ant s for homogeneous chemical
r eact ions [6].
The effect s of subst it uent s on half-wave pot ent ials ar e usually t r eat ed quant it at ively
using r elat ions analogous t o t he Hammet t and Taft equat ions and cor r elat ing half-wave
pot ent ials (E
1/2
) wit h t he subst it uent const ant s (,
0
, and t he like). Such t r eat ment of
half-wave pot ent ials is bet t er sust ained t han t hat of most ot her physico-chemical dat a.
This is because t he half-wave pot ent ials ar e a single funct ion of t he logar it hms of t he
r at e const ant s of t he elect r ode pr ocesses (k
0
) or of t he equilibr ium const ant k for r ever sible
pr ocesses. Hence by plot t ing E
1/2
against we act ually plot log k
0
(or log k), just as in
homogeneous kinet ics we plot log k
0
(or log k). Ther e ar e a number of advant ages of t he
applicat ion of polar ogr aphic dat a. These ar e :
(i) The measur ement of half-wave pot ent ials is less t edious t han t he separ at ion of
t he simple r at e const ant s suit able for st r uct ur al cor r elat ions.
(ii) The values can be measur ed wit h good r epr oducibilit y.
(iii) The r eact ion condit ions do not var y subst ant ially.
(iv) One r eact ion par t ner , i.e., t he elect r ode, r emains t he same for all t he r eact ions
t hat ar e compar ed.
This above advant age enables us t o compar e quant it at ively t he suscept ibilit y of
var ious r eact ion cent r es (as expr essed by t he r eact ion const ant ) t owar ds subst it uent
effect s. Deviat ions fr om linear E
1/2
vs plot s may allow t he det ect ion of var iat ions in t he
mechanisms of t he elect r ode pr ocess and changes in t he adsor babilit y in t he st udied
r eact ion ser ies.
Polar ogr aphy can also be used t o det ect and follow int er mediat es in some r eact ions.
The r eact ive int er mediat es ar e oft en polar ogr aphically act ive and give separ at e waves.
Classical polar ogr aphy per mit s int er mediat es wit h life t imes lar ger t han about 15 seconds
t o be followed and special oscilloscopic t echniques will follow even t hese wit h life t imes
t wo or der s of magnit ude less. See Table 9.4.
It can, t her efor e, be concluded t hat polar ogr aphy cer t ainly deser ves mor e int er est
for or ganic chemist s and t hey can easily consider adopt ing t his met hod as an effect ive
wor king t ool.
TABLE 9.4
Int er mediat es can be det ect ed and followed by polar ogr aphy
RCOCH = CHR + OH
RCOCHCHR + HO
2
OH
()
RCOCH CHR + OH
2
OH
RCOCHCHR
OH
= 1
fast
RCOCH CHR + OH
2
OH
RCOCH CH R + H O
2 2
O()
fast
RCOCH CHR
2
O
()
RCOCH () + RCHO
2
RCOCH () + H O
2 2
RCOCH + OH
3
()
1
1
2
2
2
For t he r eact ion of chalcone in alkaline solut ion, t he det er minat ion of t he ket ol,
RCOCH
2
CH(OH)R, and measur ement of it s changes wit h t ime enable one t o separ at e
t he r at e const ant s k
1
, k
1
, k
2
, k
2
.
TABLE 9.5
Polar ogr aphically Reducible Funct ional Gr oups
C = O
CHO
CX
n
NO
2
C = O
C = N
X* NO
C = O
C N CX* NHOH
C = C C = C N = N ONO
C = C C = O
O O O = C CX ONO
2
O = C C = O
S S NO = N
Het er ocyclic double bond Polynuclear ar omat ic r ing syst em
*X is a halogen at om.
References
1. Hamet t , L.P., Physical Or ganic Chemist r y, McGr aw-Hill, N.Y. (1940).
2. Heyr ovsky, J . and Kut a, J ., Pr inciples of Polar ogr aphy, Aca. Pr ess, N.Y. (1966) p. 256.
3. Taft , R.W., J r ., St er ic Effect s in Or g. Chemist r y, M.S. Newman Ed., J .W., N.Y. (1956).
PART-II
ALLIED TECHNIQUES
7+,6 3$*( ,6
%/$1.
CHAPTER 10
MISCELLANEOUS
POLAROGRAPHIC METHODS :
PRINCIPLES, THEORY TECHNIQUES
AND ANALYTICAL APPLICATIONS
10.1 SQUARE WAVE POLAROGARPHY
In an at t empt t o over come t he int er fer ence fr om t he capacit y cur r ent encount er ed in
Br ayer s A.C. met hod, t his par t icular t echnique was developed. A small 225 c/s squar e
wave volt age of not mor e t han 30 mV was super imposed on a slowly changing applied
D.C. volt age by Bar ker and J enkins [20]. J ust befor e each change in sign of t he alt er nat ing
volt age, t he measur ement of A.C. component of t he cell cur r ent was made.
At t he end of each half cycle, t her e is a super ior far adaic t o non-far adaic cur r ent
r at io. This fact r emain t he basis of t he met hod. This par t icular sit uat ion ar ises because
t he component due t o t he capacit y cur r ent decays exponent ially wit h t ime and may
become negligibly small just pr ior t o t he change in t he sign of t he volt age.
Kalousek [23] compr ised a mechanical commut at or which alt er nat ively polar ised t he
dr opping mer cur y elect r ode t o a pot ent ial at which t he r educt ion occur ed and t o a mor e
posit ive pot ent ial at which oxidat ion of t he r educt ion pr oduct for med at t he elect r ode
was expect ed. The cor r esponding anodic cur r ent can be obser ved wit h t he Kalousek
cir cuit , in case t he pr oduct is elect r o-oxidizable.
Fig. 10.1 denot es t he per iod of swit ching (t he
fr equency f = 1/(T), t, t , t , t he t imes of
swit ching and E t he amplit ude of t he squar e-
wave volt age. The or iginal commut at or was so
designed t hat it gave squar e-wave volt age wit h
a const ant fr equency of 5 c/sec. Thus dur ing t he
dr op-life of a nor mal dr op (2 t o 4 sec), 10 t o 20
cycles of t he squar e-wave volt age occur ed. As in
nor mal polar ogr aphy a damped galvanomet er is
used for r egist er ing t he cur r ent which r ecor ds
t he mean cur r ent dur ing t he dr op-life of t he
individua l dr ops. The cur ve is r ecor ded on
applying t he volt age because of t he cont inuous
F i g. 10.1 : Time-dependence of a
squar e-wave volt age applied t o an
elect r ode. t, t , t , t imes of swit ching,
T per iod of squar e-wave volt age, E
amplit ude of squar e-wave volt age
t
E
t t
incr ease of volt age fr om t he polar ogr aph, t he act ual volt age obt ained by t his met hod is
t r apezoidal. However , t he change in volt age dur ing one cycle is so small t hat bot h
volt age may be consider ed const ant .
a b
E
t
Fig. 10.2 : Time-dependence of t he polar izing volt age at t he elect r ode,
a cir cuit as in schemes I and II, b as in scheme III
1. Select ion of t he commut at ed volt age and t he char act er of t he r ecor ded cur r ent
volt age cur ves.
The shape of t he cur r ent volt age cur ve depends on t he choice of t he commut at ed
volt age wit h r espect t o t he half-wave pot ent ial of t he depolar izer . This is t r ue
when only t he oxidized for m of t he depolar izer is pr esent in t he solut ion.
(a) If t he const ant auxiliar y volt age applied t o t he dr opping mer cur y elect r ode
dur ing t he pr oducing ha lf-cycle is mor e nega t ive t ha n E
1/2
for t he
depolar izer . (i.e., at t he pot ent ial of t he limit ing cat hodic cur r ent ) and if
dur ing t he r ecor ding half-cycle t he volt age applied fr om t he pot ent iomet r ic
br idge of t he polar ogr aph changes fr om values consider ably mor e posit ive
t han E
1/2
(i.e., fr om t he pot ent ial of t he limit ing anodic cur r ent t o mor e
negat ive values (Fig. 10.2), t he shape of t he waves cor r esponds t o t he
cur ve in Fig. 10.3.
While pr oducing t he half cycles r educt ion of t he subst ance st udied occur s
at t he D.M.E. The r educed for m of t he subst ance as a pr oduct of t he
elect r ode pr ocess accumulat es close t o t he elect r ode sur face. If t his for m
can be r eoxidized at t he elect r ode, an anodic cur r ent cur ve 1 and 2 below
t he zer o line (Fig. 10.4) flows t he galvanomet er in t he r ecor ding cycles at
mor e posit ive pot ent ials t han t he half-wave pot ent ial. The height of t his
anodic wave exceeds t hat of t he nor mal polar ogr aphic wave at t he same
concent r at ion. This is due t o t he for mat ion of depolar izer i.e., t he r educed
for m at t he elect r ode sur face while pr oducing t he half-cycle.
1 2
3
Fig. 10.3 : Wave-shapes for different degrees of irreversibility recorded with the Kalousek
commut at or scheme I. 1. Rever sible elect r ode pr ocess. 10
3
M Cd
2+
, 1 M NH
3
, 1 M
NH
4
Cl, 0.01% gelat in. Auxiliar y pot ent ial E
2
= 1.1 V (vs SCE), from 0.3 t o 1.3 V (vs
SCE). 2. Par t ly ir r ever sible elect r ode pr ocess. 10
3
M Zn
2+
, 1 M NH
3
, 1 M NH
4
Cl, 0.01%
gelat in. Auxiliar y pot ent ial E
2
= 1.6 V (vs SCE), fr om 0.7 t o 1.7 V (vs SCE) 3.
Tot ally ir r ever sible elect r ode pr ocess. 10
3
M Co
2+
, 0.1 m KCl, 0.01% gelat in. Auxiliary
pot ent ial E
2
= 1.5V (vs SCE), fr om 0.7 t o 1.6 V (vs SCE). 200 mV/scale unit , sens
1 : 150, t
1
= 2.6 sec, f = 12.5 c/sec
1
2
3 E
Fi g. 10.4 : Dependence of t he shapes of Kalousek polar ogr ams upon t he degr ee of
r ever sibilit y of t he elect r ode pr ocess. 1. Complet ely r ever sible elect r ode pr ocess, 2.
Par t ially ir r ever sible pr ocess. 3. Complet ely ir r ever sible pr ocess
Miscellaneous Polarographic Methods : Principles... 109
No cur r ent flows, of cour se, in t his pot ent ial r ange of t he r educed for m
and cannot be r e-oxidized at t he elect r ode (a t ot ally ir r ever sible elect r ode
pr ocess, see cur ve 3 (Fig. 10.3). If t he r educed for m is capable of oxidat ion
at t he elect r ode, but t he oxidat ion pot ent ial of t he r educt ion pr oduct does
not agr ee wit h t he r educt ion pot ent ial, t hen dur ing t he r ecor ding half-
cycle, t he anodic cur r ent falls t o zer o when t he pot ent ial is t oo negat ive
t o facilit at e oxidat ion but t oo posit ive for r educt ion, cur ve 2 (Fig. 10.3).
The limit ing value of t he cat hodic cur r ent is one half of t hat for t he
nor mal polar ogr aphic wave for bot h r ever sible and ir r ever sible pr ocesses.
This is due t o t he fact t hat r educt ion pr oceeds over t he whole dr op-life,
but t he cur r ent passes t hr ough t he galvanomet er only dur ing one-half of
t his t ime. In t he case of a r ever sible elect r ode pr ocess and anodic wave
is for med a t t he sa me pot ent ia l a s t he r educt ion wa ve in nor ma l
polar ogr aphy, see cur ve 2 in Fig. 10.5.
1
2
Fig. 10.5 : Wave-shapes for reversible and irreversible elect rode processes recorded
wit h t he Kalouseks commut at or cir cuit as in scheme II. 10
3
M Cd
2+
, 10
3
M Co
2+
in 0.1 M KCl. Cur ve 1 convent ional polar ogr aphic cur ve; 2. commut at ed cur ve,
const ant auxiliar y pot ent ial =0.2 V (vs SCE), f = 12.5 c/sec, fr om 0.2 t o 1.6 V
(vs SCE), 200 mV/scale unit , sens. 1:150.
Fig. 10.6 shows schemat ic squar e wave polar ogr ams Kalouseks [5]
commut at or met hod was or iginally devised as a means of assessing t he
r ever sibilit y of polar ogr aphic elect r ode pr ocesses. However , it also for ms
t he basis of t he squar e-wave and pulse-polar ogr aphic t echniques. In
convent ional polar ogr aphy, coincidence of t he half-wave pot ent ials of
cat hodic and anodic waves was r egar ded as t he accept ed cr it er ion of
r ever sibilit y. Wit h t he aid of Kalousek cir cuit , it is possible t o t est t he
r ever sibilit y wit h only one for m of t he r edox syst em.
pr odu ct of t h e el ect r ode pr oces s i s
r econ ver t ed, by a fi r s t or der ch emi ca l
r eact ion, t o t he or iginal depolar izer . The
ca lcula t ion of t he mea n cur r ent for t he
complet e cycle leads t o a simpler and final
expr es s i on s for t h e cu r r en t t h a n t h e
calculat ion of t he cur r ent in t he r ecor ding of
half-cycle followed by t he calculat ion of t he
aver age value over t he complet e cycle of t he
squar e-wave volt age.
(c) Me a n Cu r r e n t s i n I r r e ve r s i b l e
Elect r od e P r ocesses : The calculat ion of t he
mean cur r ent s has been car r ied out for t he
case when t he mean value over a complet e
cycle of t he squar e-wave volt age is t aken for
t he cur r ent flowing in t he r ecor ding of half-
cycle, and for t he case of t he so-called quasi-
st at ionar y st at e, i.e., for t he st at e aft er t he
passage of a number of cycles at t he dr opping
mer cur y elect r ode. Mat sudas t r eat ment for
t he dependence of t he shape of t he cur r ent -
volt age cur ve on t he magnit ude of t he r at e
const ant
0
e
k for t he elect r ode pr ocess (at
s t a n da r d pot en t i a l a l s o pr es en t s t h e
possibilit y of a useful quant it at ive est imat ion
of t he value of t his const ant , nicely demon-
st r at ed in Fig. 10.8.
It can be obser ved in t he figur e t hat at
h i gh va l u e of
0
e
k , t h e a n odi c cu r r en t
incr eases in t he vicinit y of t he r ever sible half-
wave pot ent ial and t he shape of t he cur ve
a ppr oa ches t he r ever sible pr ocess. Wit h
decr easing values of
0
e
k , t he anodic cur r ent r apidly falls and pr act ically
vanishes at
0
e
k < 10
3
cm sec
1
. It is evident t hat for given exper iment al
condit ions, an est imat e of t he magnit ude of
0
e
k can be made up t o values
appr oaching unit y. For t his r eason, t he r elat ively simple met hods of a
per iodically changing squar e-wave volt age pr ovides us wit h t he same
oppor t unt ies for est ima t ing
0
e
k a s t he ot her exper iment a lly mor e
complicat ed met hods.
(d) Ch a r gi n g Cu r r e n t s : The cur r ent measur ed by t he per iodically changing
square-wave volt age met hod consist s of t wo component s : (i) The elect rolyt ic
and t he (ii) char ging cur r ent .
At t he abr upt change in pot ent ial at t he beginning of each half-cycle, at
t he inst ant , t he elect r ode behaves appr oximat ely as a condenser of capacit y
A
0.5
0
0. 5
40
t
5
6
1
2
3
4
7
100 0 100 200 300 mV
E E
Fi g. 10.8: Shapes of commut at ed waves for
differ ent const ant s of t he elect r ode pr ocess.
Values of r at e const ant s
0
= , 2.
0
=
10
1
cm. sec
1
, 3.
0
= 3. 10
2
cm. sec
1
, 4.
0
= 10
2
cm. sec
1
, 5.
0
= 10
3
cm. sec
1
, 6.
0
= 10
4
cm. sec
1
, 7.
0
= 10
5
cm. sec
1
. Scheme
III, comput ed for = = 0.5, n = 2, sur face-
ar ea of t he dr op at t he end of dr op-life q
1
=
10
2
cm
2
/sec
1
, = 10
5
cm
2
sec
1
, c = 5.10
4
M,
t
1
= 4 sec, f = 50 c/sec, E
2
E
1
= 10 mV, t =
25C. The mean cur r ent (A) is plot t ed on
t he or dinat e, and t he differ ence E E
0
[E =
1/2 (E
1
+ E
2
) and E
0
is t he st andard pot ent ial]
on t he abscissa.
C in ser ies wit h r esist ance R. The char ging cur r ent in one half-cycle
follows t he equat ion:
i =
exp
E T
R RC
| |
|
\ .
...(2)
wher e E is t he amplit ude of t he squar e-wave volt age and t is t he t ime,
measur ed fr om t he beginning of t he half-cycle. The capacit y C is also a
funct ion of t ime since it changes wit h t he sur face ar ea of t he elect r ode.
The mean value of t he char ging cur r ent i
c
over t he r ecor ding half-cycle
is given by t he equat ion :
i
c
=
1
2
0
2
i dT
T
; ...(3)
it incr eases wit h incr easing fr equency of t he squar e-wave volt age mor e
r apidly t han t he elect r olyt ic cur r ent and it may exceed it at higher
fr equencies. At t his st age T is decr easing.
By decr easing t he amplit ude of t he squar e-wave volt age E and t he t ot al r esist ance,
in t he elect rode circuit R t his char ging cur r ent can be suppr essed, which makes evaluat ion
of t he elect r olyt ic cur r ent difficult . Also, we can
r est r ict our cur r ent measur ement s t o t he r egion
t owar ds t he end of t he half-cycle. This last
pos s i bi l i t y fol l ows fr om t h e fa ct t h a t t h e
inst ant aneous char ging cur r ent decr eases mor e
r apidly t han t he elect r olyt ic one in t he half-cycle
aft er t he pot ent ial jump.
The dr opping mer cur y elect r ode is polar ized
by a squar e-wave volt age applied over t he whole
per iod of t he dr op-life, but t he elect r olyt ic
cur r ent s ar e only r ecor ded wit hin a ver y shor t
per iod of t ime, i.e., 30 m sec dur ing a cer t ain
phase of t he gr owt h of t he dr op which is usually
2 sec, aft er t he beginning of t he dr op-life. Over
t his shor t int er val t he gr owing mer cur y dr op
beha ves in a ver y good a ppr oxima t ion a s a
st at ionar y mer cur y elect r ode wit h a const ant
sur face ar ea. The capacit y cur r ent s ar e suppr essed by r ecor ding t he elect r olyt ic cur r ent s
only dur ing 100200 sec at t he end of each half-cycle of squar e-wave volt age. The
r ecor ding appar at us measur es t he amplit ude of t he alt er nat ing component of t he cell-
cur r ent as a funct ion of t he linear ly incr easing volt age E. The squar e-wave polar ogr am
has t he shape of a der ivat ive polar ogr am.
The r educt ion of an ir r ever sible depolar izer is much mor e complicat ed [2]. It
demonst r at es t hat t he cur r ent given by an ir r ever sibly r educed depolar izer is much
Cu
2+
Pb
2+
Cd
2+
In
3+
TI
+
Zn
2+
0. 2 0. 4 0. 6 0. 8 1. 0
Fi g. 10.9 : 1. Squar e-wave polar ogr am
of a solut ion cont ainig, 2. 10
5
M Cu
2+
,
Pb
2+
, Tl
2+
, Zn
2+
and 4. 10
6
M ln
3+
.
As alr eady indicat ed, a small amplit ude alt er nat ing pot ent ial is super imposed on t he
D.C. pot ent ial which is var ied linear ly wit h t ime. The r esult ing fundament al har monic
alt er nat ing cur r ent is r ecor ded as a funct ion of dir ect pot ent ial. This appr oach was
ent it led A.C. polar ogr aphy. The for m of t he fundament al har monic A.C. polar ogr aphic
wave obt ained upon r ecor ding t he alt er nat ing cur r ent as a funct ion of dir ect pot ent ial
is shown in Fig. 10.10.
Far adaic alt er nat ing cur r ent flows only when bot h oxidized and r educed for ms ar e
pr esent simult aneously at t he int er face, t hat is, on t he r ising por t ion of t he D.C.
polar ogr aphic wave. Thus a polar ogr am is obt ained wit h a maximum cor r esponding
r oughly t o t he shape of t he der ivat ive of t he D.C. wave. The det ails r egar ding shape and
magnit ude of t he A.C. polar ogr aphic wave ar e influenced mar kedly by kinet ics of t he
var ious r at e pr ocesses associat ed wit h t he elect r ode r eact ion. Her ein lies t he basis for
t he applicat ion of A.C. polar ogr aphy in kinet ic st udies. For kinet ic invest igat ions, t he
st udy of t he quasi-r ever sible fundament al har monic as pr ocess has r eceived consider ably
gr eat er int er est t han any ot her t ype of kinet ic scheme. Much of t his wor k was car r ied
out by employing t he classical far adaic-impedance measur ement at t he equilibr ium
pot ent ial (i = 0) consider able kinet ic dat a for t he char ge t r ansfer por cess has been t he
r ewar d of such effor t s (Br eyer and Bauer ). Elect r ode pr ocesses in which cur r ent s ar e
influenced by kinet ics of coupled homogeneous chemical r eact ion ar e well known fr om
st udies of t he D.C. polar ogr aphic wave.
Quant it at ive t heor y for A.C. polar ogr aphic influenced in any way be adsor pt ion
pr ocess is not in exist ence. This is because when het er ogeneous char ge t r ansfer and
adsor pt ion occur simult aneously Few t heor ies char act er izing adsor pt ion pr ocess at t he
elect r odes in t he absence of alt er nat ing cur r ent s have been widely accept ed and ext ending
t hese ideas t o A.C. met hods is t eaching.
Adsor pt ion pr ocess may influence A.C. polar ogr aphic dat a in t he following ways :
(1) Adsor pt ion of elect r oact ive sur fact ant s has a pr ofound effect on t he double layer
capacit y leading t o consider able depr essions of t he double layer char ging cur r ent in t he
r egion of t he elect r ocapillar y maximum and oft en a shar p peak at pot ent ials (bot h
posit ive and negat ive) well r emoved fr om t he elect r ocapillar y maximum, wher e t he
coulombic for ces bet ween t he elect r ode and ions of t he elect r olyt e lead t o desor pt ion
[33]. (2) Adsor bed elect r oact ive sur fact ant s can have a pr ofound influence on kinet ics or
char ge t r ansfer and ot her st eps associat ed wit h t he elect r ode pr ocess [34]. (3) Adsor pt ion
of elect r oact ive species may mar kedly influence t he char act er ist ics of far adaic alt er nat ing
cur r ent t hr ough alt er at ins of t he mass t r ansfer pr ocess by chemical r eact ions occur ing
only on t he elect r ode sur face. The example could be hydr ogen at om combinat ion on
plat inum [35] and, as wit h elect r o inact ive sur fact ant s, t he double layer capacit y can be
alt er ed.
And accur at e model for adsor pt ion kinet ics and t he isot her m, t oget her wit h pr oper
t r eat ment of t he mass t r ansfer pr ocess, is sufficient of develop a t heor y for t he
t ensammet r ic pr ocess in A.C. polar ogr aphy t hat is, t he influence of adsor bed species on
differ ent ial capacit y of t he elect r ical double layer :
Adsor pt ion of t he elect r oact ive species pr obably r epr esent t he most impor t ant
adsor pt ion scheme in A.C. polar ogr aphy. Applicat ion of simple qualit at ive concept s t o
develop sa me idea r ega r ding how such phenomena might influence t he fa r a da ic
impedance. The most convincing ar gument in t his r egar d t hat could be applied is t he
phase angle. A well known r elat ion in A.C. cir cuit t heor y is for example, [40]
= EI cos ...(2)
wher e P is t he aver age power dissipat ion in t he A.C. pr ocess, E is t he amplit ude of
alt er nat ing volt age, I is t he amplit ude of alt er nat ing cur r ent , and is t he phase angle.
A phase angle of 0 r epr esent s t he maximum power dissipat ion. The mor e conser vat ive
of ener gy t he A.C. pr ocess, t he closer t he phase angle appr oaches 90. In t he t heor y
developed shown t hat a diffusion cont r olled pr ocess yields a pr edict ed phase angle of
45. This implies t hat t he mass-t r ansfer pr ocess leads t o some but not t ot al, ener gy
dissipat ion. This is expect ed r esult qualit at ively. Because, alt hough some oxidized or
r educed species gener at ed on one half-cycle can be dissipat ed t hr ough t he diffusion
pr ocess which means t hat diffusion int o t he solut ion t o be lost t o t he elect r ode pr ocess,
same can also be made available t hr ough diffusion for t he r ever se elect r ode r eact ion on
t he following cycle. These ideas ar e in agr eement wit h t he concept t hat addit ional slow
st eps lead t o a far adaic pr ocess which is less efficient in t he passage of alt er nat ing
cur r ent , t hat is, less conser vat ive of ener gy. Applying t hese ideas t o t he pr ocesses
involving adsor pt ion of t he elect r oact ive for m, t he conclusion t hat could be dr awn is t hat
t he over all mass-t r ansfer pr ocess in t he pr esence of adsor pt ion will be mor e conser vat ive
of elect r ical ener gy, because t he adsor pt ion leads t o excess sur face concent r at ions and
less fr eedom for t hese sur face concent r at ions t o be dissipat ed by t he diffusion pr ocess.
For ver y r apid elect r ode pr ocess and or low fr equencies, t he possibilit y suggest ed is
t hat t he phase angle may exceed 45, a phenomena not pr edict ed by any of t he mechanism
consider ed ear lier . Alt hough a quant it at ive t heor y for A.C. polar ogr aphy (A.C. and D.C.
flow) has not been for t hcoming, sever al wor ker s have pr esent ed t heor et ical equat ions
for t he far adaic impedance at t he equilibr ium pot ent ial.
It should be not ed t hat adsor pt ion and double-layer effect s cannot be consider ed on
a separ at e basis. Char act er ist ics of adsor pt ion pr ocesses on met als in elect r olyt e solut ion
ar e influenced int imat elay by t he elect r ical double layer and vice-ver sa. However , in t he
absence of st r ong int er act ion bet ween t he elect r ode mat er ial and species in solut ion i.e.,
specific adsor pt ion, elect r ode pr ocesses may st ill be per t ur bed significant ly by for ces
oper at ive wit hin diffuse double-layer .
Fr umkin 1933 [37] made t he ear liest at t empt t o int er pr et t he influence of double-
layer st r uct ur e by point ing out t hat t he concent r at ion of r eact ing par t icles in t he double-
layer is differ ent fr om t he bulk of t he solut ion, and t he elect r ical ener gy available for
assist ing or r et ar ding t he elect r ode r eact ion is less t han t he pot ent ial differ ence bet ween
elect r ode and solut ion. It has also been point ed out t hat cor r ect ion for t he double-layer
by t he Fr umkin t heor y is valid only when t he t hickness of t he diffuse double-layer is
negligible in compar ison wit h t he diffuse layer . Also it was shown t hat t he double-layer
effect s would be negligible if t he r eact ion-layer t hickness is much lar ger t han t he diffuse-
layer t hickness.
Because Kout eckys t r eat ment is applicable only t o r ever sible pr ocesses, t her e is no
dispar it y bet ween t he wor k of Kout ecky and Mat suda. The dr op gr owt h cont r ibut ion
pr edict ed by Mat suda appear s t o ar ise because t he far adaic impedance is mar kedly
dependent on t he magnit udes of t he D.C. concent r at ion of oxidized and r educed for ms
at t he int er face. When t he D.C. pr ocess is cont r olled solely by diffusion, t he Ner nst
equat ion is obeyed and t he int er face concent r at ion ar e independent of elect r ode gr owt h.
However , if non-ner nst ian condit ions exist , der ivat ions of D.C. concent r at ions fr om
equilibr ium ar e influenced by t he mot ion of t he elect r ode sur face int o t he solut ion which
aids mass t r ansfer .
It is t her efor e suggest ed t hat , if t he D.C. int er face-concent r at ion component s ar e in
a non-equilibr ium st at e, any fact or , influencing t he D.C. mass t r ansfer pr ocess, can, in
t ur n, affect t he magnit ude of t he A.C. wave.
Elect r ode geomet r y would fall in t his cat egor y. In addit ion one is led t o conclude
t hat t he non-equilibr ium st at e need not be concer ned only wit h t he char ge t r ansfer st ep.
Non-equilibr ium condit ions r elat ed t o coupled homogeneous chemical r eact ions and
adsor pt ion may int r oduce elect r ode geomet r y and gr owt h cont r ibut ions.
The hypot hesis t hat elect r ode geomet r y can be impor t ant is r eadily subject ed t o
t heor et ical examinat ion by examining equat ions for t he A.C. polar ogr aphic wave wit h
a quasi-r ever sible pr ocess for diffusion t o a st at ionar y spher e.
As a r esult of t he fact s st at ed above, it can be concluded t hat accur at e A.C.
polar ogr aphic wor k t he DME will r equir e incor por at ion of cont r ibut ions of dr op gr owt h
and geomet r y int o t heor et ical expr essions whenever invest igat ions ar e concer ned wit h
syst ems exhibit ing amalgam for mat ion and/or non-equilibr ium condit ions in t he D.C.
pr ocess wit h r espect t o eit her t he elect r ochemical char ge-t r ansfer st ep or coupled chemical
r eact ions. Appar ent ly t he only t ype of syst em immune t o t hese effect s is one in which
bot h for ms of t he r edox couple ar e soluble in t he solut ion phase and t he D.C. pr ocess
is cont r olled solely by diffusion, pr ovided diffusion coefficient s of t he t wo r edox for m do
not differ mar kedly. These conclusions r epr esent a consider able depar t ur e fr om t he
or iginal concept t hat t he A.C. polar ogr aphic wave would not be significant ly influenced
by elect r ode gr owt h and geomet r y. However , t he lat t er t hinking neglect s subt le aspect s
of t he coupling bet ween t he D.C. and A.C. pr ocesses in t he A.C. polar ogr aphic
exper iment .
10.2.1 The Technique and Instrumentation
Four exper iment al t echniques ar e possible for combining cont r ol of dir ect cur r ent or
pot ent ial wit h cont r ol of sinusoidal alt er nat ing cur r ent or pot ent ial t o st udy t he small-
amplit ude far adaic impedance. A.C. polar ogr aphy r epr esent s one combinat ion. A.C.
chr onopot ent iomet r y employs cont r ol of t he dir ect and alt er nat ing component s of cur r ent
while measur ing t he r esult ing alt er nat ing component of pot ent ial as a funct ion of t ime.
(or , alt er nat ively, as a funct ion of dir ect pot ent ial). These t echniques ar e r elat ed closely,
bot h in pr inciple and t heor y. In ot her wor ds, t he impedance of a polar ogr aphic cell can
be st udied as a funct ion of D.C. pot ent ial by cont r olling eit her t he alt er nat ing cur r ent
or pot ent ial and measur ing t he uncont r olled A.C. par amet er . The D.C. pot ent ial can be
scanned eit her by cont r olling t his pot ent ial or cont r olling dir ect cur r ent , per mit t ing t he
nor mal chr onopot ent iomet r ic pr ocess t o pr oceed.
The t heor et ical equat ion for t he measur ed alt er nat ing cur r ent or pot ent ial is t hen
obt ained for t he t echnique of int er est fr om t he gener alized for m of Ohms law (E = i )
and by subst it ut ing t he appr opr iat e for m of dir ect cur r ent for t he
0
(t) t er m.
It is seen t hat t he st at us of t he D.C. polar ogr aphic pr ocess is of major concer n her e,
just as in t he discussion of t ime dependance and cont r ibut ions of elect r ode geomet r y and
gr owt h. This emphasizes t he point t hat t he A.C. polar ogr aphy ser ves not only as an
appr oach t o examining t he r apid elect r ode, but also as effect ive pr obe for invest igat ing
t he D.C. pr ocess.
The oper at ional-amplifier met hod confines t o a single inst r ument al concept . The
A.C. polar ogr aph const r uct ed fr om oper at ional amplifier pr ovides a number of advant ages.
For emost among it is dr ast ic r educt ion of ohmic r esist ance. Wit h a t hr ee elect r ode
configur at ion, t he oper at ional amplifier pot ent ial cont r ol loop pr ovides for aut omat ic
compensat ion of much of t he ser ies r esist ance nor mally associat ed wit h t he elect r olyt ic
cell and exper iment al cir cuit r y. This is par t icular ly impor t ant in A.C. polar ogr aphy,
wher e t he low impedance of elect r ode-solut ion int er face enhances such pr oblems. In
br ief, it ca n be sa id t ha t wit h t ypica l oper a t iona l-a mplifier cir cuit r y, t he only
uncompensat ed r esist ance is t he ohmic dr op bet ween t he t ip of t he r efer ence elect r ode
pr obe and t he summing point of t he cur r ent measur ing amplifier .
An unfor t unat e disadvant age of oper at ional amplifier s employed in most exist ing
elect r oanalyt ical inst r ument at ion is limit ed fr equency r esponse. This has r est r ict ed A.C.
polar ogr aphic invest igat ions wit h oper at ional amplifier inst r ument at ion t o fr equencies
of ~ 1 k
c
or less. Highly
select ive t uned amplifier s
ar e useful in A.C. polar o-
gr a ph y. A con ven t i on a l
(fu n da men t a l h a r mon ic)
A.C. polar ogr aph can be
con s t r u ct ed fr om t h e
pot en t i a l -con t r ol l oop,
pot ent ia l sour ces, t uned
amplifier , and r ect ifier as
s h own t h e s ch ema t i c
dia gr a m wit h a suit a ble
r ecor der . The schema t ic
diagr am is given below [3].
A.C. P ola r ogr a p h : Three
t ypes of signal sour ces ar e
r equir ed in A.C. pola r o-
gr a phy. (a) a D.C. pot ent ial sour ce whose out put can be var ied convenient ly t o ser ve as
sour ce of t he init ial pot ent ial. (b) A sour ce of a linear scanning D.C. pot ent iala r amp
gener at or whose scan r at e and dir ect ion can be alt er ed convenient ly, (c) a sinusoidal
Initial Voltage
D.C. Ramp
Sinusoidal
Oscillator
Tuned
Amplifier
Rectifier
To Recorder
100 K
100 K
100 K
100 K
C
F
ref
aux
CELL
ind
I
R
m
C
m
Fi g. 10.11 : Schemat ic of fundament al-
har monic A.C. polar ogr aph
oscillat or . High-qualit y signal sour ce of t hese t ype can be const r uct ed fr om oper at ional
amplifier s.
The A.C. polar ogr aphic signal cont ains quit e a number of infor mat ion in t he for m of
t he D.C. polar ogr aphic cur r ent , t he component s of which manifest t he impedance of t he
polar ogr aphic cell at D.C. and over a r ange of A.C. fr equencies. Finally it is t aken t o be
desir able for measur ing many of t he component s (not ment ioned her e) simult aneously,
alt hough it may need some mor e complicat ed elect r ode pr ocesses.
10.3. COULOMETRY
Invest igat ing t he mechanism of an elect r ode pr ocess, it is desir able t o det er mine t he
number of elect r ons n t hat ar e consumed by a single ion or a molecule of t he depolar izer
on r educt ion or oxidat ion. In t he case of a r ever sible diffusion-cont r olled pr ocess, n can
easily be det er mined by polt t ing log i/(i i) against E. Consider ing t he equat ion (1)
( ) 1 2
log
0058
n i
E E
. i i
=
...(1)
it is assumed t hat log i/(i i) on t he pot ent ial E, must be a st r aight line wit h a slope
of n/0.058. The pot ent ial, at which t he value of log i/(i
d
i) is zer o, gives t he half-wave
pot ent ial Fig. 10.12 (a), (b) and, (c).
In mult i-elect r on pr ocess and, in par t icular in t he case of complicat ed and bulky
compounds, t he number of elect r ons has t o be det er mined by coulomet r y. If follows fr om
Far adays laws t hat :
n =
M
G F
...(2)
wher e G is t he quant it y of subst ance wit h molecular weight , M t r ansfor med by t he
passage of an elect r ic char ge Q, F has t he significance (96500 coul). Consequent ly n, G
in or G in mole and Q in coul. must be measur ed. Besides sever al ot her met hods
log
I
I I
d
In
3+
0. 65 0. 70 V
c
E
0. 60
19 mV
log
I
I I
d
TI
+
0. 45 0. 50 0. 55V
a
E
58 mV
log
I
I I
d
Pb
2+
0. 50 0. 60 0. 65 V
b
E
0. 45
Cd
2+
29 mV
29 mV
Fi g. 10.12 : Logar it hmic analysis of polar ogr aphic cur ves. log i/(i i) E
plot s : (a) Tl
+
, (b) Pb
2+
and Cd
2+
, (c) In
3+
in polar ogr aphy, elect olysis wit h a lar ge ar ea mer cur y elect r ode
at a cont r olled pot ent ial and in ser ies wit h a coulomet er is
employed. In addit ion, a number of met hods have been wor ked
out t hat make direct use of elect rolysis wit h a dropping mercury
elect r ode.
Li n ga n e [28] wa s t h e fi r s t t o a ppl y cou l omet r y i n
polar ogr aphy, number of aut hor s also applied t his met hod for
det er minat ion of n for bot h or ganic and inor ganic subst ances.
10.3.1 Coulometry with Large Area Mercury Electrodes
A known volume of t he same solut ion as t hat subject ed t o
polar ogr aphic invest igat ion can be elect r olysed wit h a lar ge
ar ea mer cur y elect r ode. This is done at a cont r olled-pot ent ial
cor r esponding t o t he limit ing cur r ent of t he subst ance t o be
st udied. Cont r ol of t he pot ent ial is effect ed by means of a
pot ent iost a t a nd t he pot ent ia l is r efer r ed t o a st a nda r d
r efer ence elect r ode wit h no cur r ent pa ssing. The second
wor king elect r ode is usually made of plat inum (Fig. 10.13). Tr anspor t of t he depolar izer
t owar ds t he elect r ode is acceler at ed by st ir r ing. The decr ease in t he concent r at ion of t he
depolar izer due t o elect r olysis may be obt ained by dir ect polar ogr aphic measur ement s
in t he elect r olysis cell. If i
10
is t he limit ing cur r ent befor e and i, t hat aft er elect r olysis,
v t he volume of t he solut ion in lit er s and c
=0
t he init ial concent r at ion of t he subst ance
in mole, lit er
1
, t hen t he eqn. (1) may be wr it t en in t he for m :
n =
( )
10
10 1 0
i Q
i i c v F
=
...(3)
and t he r esult s of t he polar ogr aphic invest igat ions can be dir ect ly sunst it ut ed in t his
for mula. The condit ion is t hat elect r olysis cont inues unt il t he solut ion is vir t ually t r ue
fr om t he depolar izer . The t er m G is given dir ect ly by t he pr oduct c
=0
.v. To det er mine
t he char ge Q passed t hr ough t he solut ion, a coulomet er is placed in t he cir cuit in ser ies
wit h t he elect r olysis cell.
10.3.2 Coulometry with a Dropping Mercury Electrode
Polar ogr aphic appar at us can be ut ilized in dir ect coulomet r y wit h a dr opping mer cur y
elect r ode, wit h all polar ogr aphic condit ions. Such an ar r angement is also named as
milli-or microcoulomet ry. In normal polarographic analysis, t he consumpt ion of depolarizer
is so significant t hat t he concent r at ion in t he solut ion r emains vir t ually unchar ged aft er
elect r olysis. On decr easing t he volume of t he solut ion t o a fr act ion of a ml. and car r ying
out t he elect r olysis wit h a D.M.E at const ant pot ent ial for a sufficient ly long per iod of
t ime, for about t en t o hundr eds of mins. On t his t he decr ease in depolar izer concent r at ion
becomes polar ogr aphically measur able, Fig. 10.14. The solut ion needs t o be st irred before
each measur ement as t he depolar izer is mor e r eadily exhaust ed in t he vicinit y of t he
Fi g. 10.13 : Apparat us
for elect r olysis wit h a
l a r ge a r e a me r cu r y
elect r ode [28]
i = nF
dN
dt
...(4)
or i = nF
( ) d cv
dt
...(5)
wher e N, may be wr it t en as t he pr oduct of concent r at ion c and volume v.
Hence for r epr esent ing, t he decr ease in concent r at ion t he equat ion (5), could be
wr it t en as
v
dc i
dt nF
=
Dur ing elect r olysis, concent r at ion c decr eases and so also i; i becoming t he limit ing
cur r ent i
1
. It t her efor e holds t hat
10 1
0 t
i i
c c
=
=
...(6)
wher e t = 0.
The final equat ion now t akes t he for m :
log i
10
log i
l
=
0
10
2 3
t
c
i
t
. n F v
=
...(7)
Since all t wo ot her const ant s ar e known
Fig. 10.15 t he for egoing equat ion per mit t he
gr aphical det er minat ion of t he number of
elect r ons n fr om t he slope of t he log i
l
t plot .
This par t icular simple met hod was fir st
employed by Gilber t and Rideal [26] and lat er
used by many aut hor s.
10.3.4 Determination of n by Electro-
lysis at Constant-Current
Mar k, Smit h and Reilley [29] pr oposed a
met hod for t he dr opping mer cur y elect r ode.
The elect r ode is polar ized by a const ant
cu r r en t , wh i ch over t h e wh ol e t i me of
elect r olysis is kept lower t han t he limit ing
diffusion cur r ent of t he depolar izer under
st u dy. Ext r eme n ega t ive pot en t ia l fr om
r eact ions pr event ed t he fir st inst ant s by
connect ing a condenser (capacit y 20F) in
par allel t o t he elect r odes. This may happen
at t he fir st inst ant s of t he dr op-life because
of high cur r ent densit y, because at t hese
log T
1
1.25
1.20
1.15
1.10
2000 4000 6000 8000
t(s)
Fi g. 10.15 : Plot of log i
d
against t he
dur at ion of elect r olysis in t he r educt ion
of Pb
2+
in 0.1 N KCl. Fr om t he slope of
t he st raight line, n = 2.2 is obt ained [33].
pot ent ia ls, t he suppor t ing elect r olyt es a r e likely t o be decomposed. In such a n
ar r angement , t he change in elect r ode pot ent ial does not exceed 20 mV dur ing t he dr op-
life and all cur r ent supplied is consumed in elect r olyzing t he depolar izer . The met hod
t hus allowed t he aut hor s t o det er mine t he number of elect r ons in t he r educt ion of
sever al or ganic as well as inor ganic subst ance.
10.4 COULOMETRY IN POLAROGRAPHIC ANALYSIS
Meit es [30] pr oposed a combinat ion of polar ogr aphic and coulomet r ic measur ement s for
analyzing a solut ion cont aining t wo subst ances giving polar ogr aphic waves at t he same
pot ent ial. The example of t he combined waves of lead and t hallium wer e t aken in acid
solut ion. The r esult s showed accur acy upt o a r at io of 1 : 50.
10.5 CONTROLLED-POTENTIAL ELECTROLYSIS
When, in an exper iment , t he indicat or elect r ode in a volt ammet r ic cell is maint ained at
a pot ent ial on t he plat eau of a wave, t he
elect r oact ive subst ance r esponsible for t he
wave is r educed or oxidized as r apidly as it
a r r i ves a t t h e el ect r ode s u r fa ce. I t s
concent r a t ion in t he bulk of t he solut ion
decr eases, and t her efor e t he wave height also
decr eases. Wit h most volt ammet r ic indicat or
elect r odes t he bulk concent r at ion decr eases so
slowly t hat t he wave height r emains near ly
con s t a n t over lon g per iods of t ime. For
example, if 25 ml. of a solut ion of an elect r o
act ive subst ance for which I = 4.0 and n = 2
is elect r olyzed at a pot ent ial on t he plat eau of
it s wave wit h a dr opping elect r ode for which
m
2/3
t
1/6
= 2.5, t he r a t e of decr ea se of bulk
con cen t r a t i on wi l l be on l y 0. 8 % / h r .
Pol a r ogr a ms of s t a bl e s ol u t i on s ca n be
r ecor ded over and over again wit hout sensible
change. Var iat ions of wave height wit h t ime
ar e easily cor r ect ed wit h t he r at es of chemical
r eact ions occur r ing in t he bulk of t he solut ion.
Ther e ar e many r easons for which it is
desir able t o per for m quant it at ive elect r olyses
in r easonable lengt hs of t ime. For doing t his
a la r ge elect r ode like mer cur y pool or a
cylinder of plat inum gauze ar e useful in an efficient ly st ir r ed solut ion. This is because,
t he pr ocesses t hat occur at t he elect r ode-solut ion int er face under any given condit ion
ar e mainly dependent on t he pot ent ial of t he elect r ode. Volt ammet r ic dat a can easily be
used t o find t he pot ent ial t hat is best suit ed t o car r ying out any desir ed elect r ode
1.0
0.5
0
0 50 100 150
P
o
t
e
n
t
i
a
l
,
v
.
v
s
.
S
.
C
.
E
.
Fig. 10.16 : Chronopot ent iogram obt ained
wit h a mer cur y elect r ode having an ar ea
of appr oximat ely 1 cm
2
for a solut ion
cont aining 10 mM copper (II) and 10 mM
cadmium (II) in 2F per chlor ic acid, using
a cur r ent of 0.50 m amp
r eact ion. The r esult s of such
analysis ar e ver y useful in
int er pr et ing t he volt amme-
t r ic obser vat ion.
The elect r ogr a vimet r ic
det er minat ion of met als [31]
at solid elet rodes is t he most
fr equ en t a ppl i ca t i on of
cont r olled-pot ent ial elect r o-
lysis.
The familiar t echnique of
separ at ion in t he elect r olysis
of st ir r ed solut ion wit h lar ge
mer cur y cat hodes employing
near ly const ant elect r olysis
cur r ent . This is because in
analyt ical labor at or ies it is
oft en r equir ed t o separ at e
element s such as ir on, chr omium, cobalt , copper and nickel. These ar e deposit ed int o t he
mer cur y fr om acidic solut ions. Ot her s like aluminium, t it anium, t ungst en and vanadium
r emain in solut ion. Such const ant -cur r ent separ at ions depends on t he fact t hat , t he
pot ent ial of t he mer cur y elect r ode must always assume a value det er mined by t he
composit ion of t he solut ion at t he inst ant under consider at ion.
If t he elect r oact ive species is consumed in a cont r olled-pot ent ial elect r olysis t he
cur r ent must decr ease.
In polar ogr aphic wor k it is usually possible t o employ a t wo-elect r ode cell in which
t he elect r olysis cur r ent flows t hr ough a r efer ence elect r ode. This is because t he iR dr op
t hr ough t he cell is usually so small t hat t he applied volt age is near ly ident ical wit h
differ ence bet ween t he pot ent ials of t he elect r odes, and also because t he pot ent ial of a
pr oper ly designed r efer ence elect r ode is vir t ually unaffect ed t he flow of a few micr o-
amper es of cur r ent t hr ough it . Hovever , t he sit uat ions is quit e differ ent in cont r olled
pot ent ial elect r olysis. The iR dr op may be as lar ge as 100 V, or even lar ger while
wor king in non-aqueous solut ions, and sever al amper es may flow t hr ough t he elect r olysis
cir cuit .
A t ypical cell is shown in Fig. 10.18. Slight modificat ion may be r equir ed in pr olonged
exper iment wit h air sensit ive solut ions. The elect r olysis cur r ent flows t hr ough t he
mer cur y-pool wor king elect r ode and an auxiliar y elect r ode which may be eit her a helix
of plat inum wir e as shown or in gr aphit e r od. Unless t he solut ion being elect r olyzed is
ext r emely dilut e, which is unusual, it is t her efor e necessar y t o employ a t hr ee elect r ode
cell. In or der t o avoid anodic at t ack on t he plat inum, it is advisable t o add a lit t le
hydr azine or hydr oxylamine t o t he auxiliar y-elect r ode compar t ment . In some applicat ions
of cont r olled-pot ent ial elect r olysis it is feasible t o place t he wor king and auxiliar y
elect r odes in t he same solut ion. As such, a beaker can be used as t he elect r olysis cell.
Diaphr agm cells like t he one alr eady shown ar e quit e useful, in t he sense t hat t hey
0.4
0.2
0
0.2
0.4
0.6
0.8
15 Sec.
E
.
V
o
l
t
s
v
s
.
S
.
C
.
E
.
Time
F i g . 10.17 : Ch r on opot en t iogr a m of 0.01 M
pot assium fer r ic cyanide in 1 M pot assium chlor ide
pr event t he pr oduct s for med at t he auxiliar y elect r ode fr om
r eact ing t he wor king elect r ode. It is because t hat t hey might
consume cur r ent or r eact wit h t he desir ed pr oduct . Also t o
pr event t he cyclic oxidat ion and r educt ion t hat might some-
t imes occur ; if t he lat t er comes in cont act wit h t he auxiliar y
elect r ode. The cell r esist ance depends on t he suppor t ing
elect r olyt e used. The cell is allowed t o st and for a while
wit h t he elect r olyt e solut ion (in t he cent er compar t ment )
because t he r esist ance of a dr y fit t ed disc is ver y high. It is
desir able t o exclude fr om t he wor king elect r ode compar t ment
by cont inuously passing a r apid st r eam of nit r ogen.
The wor king elect r ode pot ent ial is monit or ed wit h t he
aid of a r efer ence-elect r ode.
Many impor t ant applicat ions ar e available by use of
cont r olled pot ent ial elect r olysis:
A br ief account of t hese ar e descr ibed below :
1. I t i s u s ed i n effect i n g s epa r a t i on s pr i or t o
polar ogr aphic analyses. Ver y complex solut ions can
r eadily be analysed. A polar ogr am of t he solut ion is
r ecor ded at a sensit ivit y so chosen as t o give an easily measur able height for t he
fir st wave. The solut ion is elect r olysed wit h a mer cur y cat hode whose pot ent ial
is maint ained const ant at a value on t he plat eau of t his wave, if it is r ever sible
or on it s r ising par t of it is ir r ever sible and poor ly separ at ed fr om t he wave t hat
follows. When t he elect r olysis is complet ed a second polar ogr am is r ecor ded and
t he height of t he second wave is measur ed and so on. It is also convenient t o
inser t a dr opping elect r ode dir ect ly int o t he wor king-elect r ode compar t ment of
t he elect r olysis cell. The elect r olyses can t hen be per for med wit hout any t r ansfer
of solut ion and t he polar ogr am could be r ecor ded. Like t his t he wave-or der
pr oblem is pr act ically over .
2. It is used in r ecover ing elect r oact ive impur it ies fr om suppor t ing elect r olyt es by
using elect r odes such as hanging dr op or t he st ir r ed mer cur y pool and applying
t echniques such as squar e-wave polar ogr aphy and st r ipping analyses, it has
been possible t o analyse solut ion in t he r ange of concent r at ion down t o about
10
10
or ever up 10
11
M.
3. Elect r oact ive species t hat ar e ver y sensit ive t o air oxidat ion can be pr epar ed
and st udied wit h gr eat ease.
The peculiar vir t ue of t he t echnique is t hat it not only gives an essent ially
equant it at ive yields of t he desir ed pr oduct , but does so wit hout int r oducing for eign
r educing or oxidizing agent s. Above all t he ext r eme select ivit y t hat is achieved is of
special impor t ances.
The most common applicat ions of t he t echniques has been in elucidat ing t he pr oduct s
and n values of t he half-r eact ions t hat occur in volt ammet r y. An example could be of
mer cap t o benzot hiazole gives an anodic wave at D.M.E.
For mor e det ails t he or iginal lit er at ur e may be consult ed.
F i g . 10. 18 : Ch r on o-
pot ent iomet r ic cell wit h
shielded plat inum working
elect rode
AUX. REF.
Worki ng
El ectrode
Cel l
10.6 CHRONOPOTENTIOMETRY
Chr onopot ent iomet r y is an elect r ochemical met hod char act er ized by t he applicat ion of
a const ant cur r ent t hr ough a st at ionar y indicat or elect r ode in an unst ir r ed solut ion and
subsequent measur ement of t he wor king-elect r ode pot ent ial as a funct ion of t ime. The
r esult ing chr onopot ent iogr am showing t he var iat ion of pot ent ial wit h t ime can be used
for a var iet y of analyt ical pur pose. It also includes t he measur ment of concent r at ion of
elect r oact ive species, as well as elect r ode or solut ion kinet ics.
Ther e have been some analyt ical applicat ions of chr onopot ent iomet r y, but it can not
be r egar ded as a ver y pr omising analyt ical t echnique, alt hough it is capable of good
precision under favourable condit ions. It s limit of det ect ion is even inferior t o polarography
due t o t he double layer char ging and, at solid elect r odes, oxide for mat ion.
A t ypical chr onopot ent iogr am, t aken as an example, is obt ained wit h a small mer cur y
pool in a per chlor ic acid solut ion cont aining copper (II) and cadmium (II). This is shown
in Fig. 10.1 The zer o cur r ent pot ent ial is shown by t he shor t hor izont al line at t he left
hand side of t he figur e. When t he cur r ent how is st at ed, t he pot ent ial shift s t owar ds
mor e negat ive values on t he r ising par t of t he copper wave. The shift is r aped at fir st ,
t hen slows down as t he concent r at ion of copper (II) decr eases while t he concent r at ion
of copper (O) incr ease at t he elect r ode sur face unt il t he point of maximum poisioning
capacit y is r eached. These aft er again acceler at es as t he concent r at e of copper (II)
becomes st ill smaller.
Event ually, t he flux of copper (II) at t he elect r ode sur face becomes t oo small t o
consume all t he cur r ent . The pot ent ial shift s r apidly t o t he value at which cadmium (II)
is r educed. The t ime (in seconds) r equir ed t o r each t he point of maximum slope is t he
t ransit ion t ime T. Sand equat ion [19]
iT
1/2
= 1/2 (
1/2
nFD
1/2
AC) ...(1)
( )
1 2 1 2 1 2
1
2
ir nFD AC =
wher e i is t he cur r ent in micr oamper es, A is t he ar ea of elect r ode in squar e cent imet er s,
and C is t he bulk concent r at ion of t he elect r oact ive subst ance descr ibes appr oximat ely
for linear diffusion t o plane elect r ode. Her e t he double-layer char ging is ignor ed.
A second t r ansit ion t ime is obser ved, when cadmium ions ar e mor e and mor e r emoved
complet ely fr om diffusion layer on pr olonged elect r olysis. The differ ence bet ween t he
t wo t r ansit ion t imes is longer t han t he single t r ansit ion t ime if t he cadmium ions had
been pr esent alone. This is because t he r educt ion of copper (II) cont inue while t hat of
cadmium (II) is t aking place. In a mixt ur e of t wo subst ances t he fir st t r ansit ion t ime r
1
is given by t he for egoing equat ion (1). The sum of t he t wo t r ansit ion t imes, (r
1
' + r
2
), is
given in t he following equat ion :
( )
( )
1 2 1 2 1 2 1 2
1 2 2 2 1 2
1 2 i r r r / n FD AC
(
+ =
(

...(2)
Sand, as alr eady r epor t ed, showed t hat in an unst ir r ed solut ion and under condit ions
of linear diffusion, t he t r ansit ion t ime t (in secs) is r elat ed t o t he concent r at ion
1 2 1 2 0
1 2
2
nF AD C
i
i
= ...(3)
wher e F is t he number of far adays per molar unit of r eact ion, i is t he const ant cur r ent
in amper es, A is t he elect r ode ar ea (in squar e cent imet er s), F is t he far aday. (96, 493
coulombs), D is t he diffusion coefficent (in squar e cent imet er s per second) and C
0
is t he
bulk concent r at ion in moles per cubic cent imet er s.
But t er and Ar mst r ong [4], aft er t he wor k of Sand coined t he t er m t r ansit ion t ime.
Monogr aph of Delahay [7] expr essed a number of development s for it . The most int er est ing
feat ur e of Sand equat ion, given above is t hat t he squar e r oot of t he t r ansit ion t ime is
pr opor t ional t o t he bulk concent r at ion of t he elect r oact ive subst ance. This pr oper t y has
gr eat ut ilit y is analyt ical invest igat ions. Analysis involving oxidat ions can be car r ied out
chr onopot eniomet r ically wit h much bet t er r esult s t he polar ogr aphy wit h a r ot at ing
plat inum elect r ode, specially in t he milli molar concent r at ions r ange. Most r ecent
applicat ion of chr onopot ent iomet r y is kinet ic measur ement s involving bot h elect r ot r ansfer
and chemical t o st udies of adsor pt ion on t he elect r ode sur face. This can be r egar ded
as a gener al elect r ochemical t ool.
10.7 THEORY OF REVERSIBLE PROCESSES
The chr onopot ent iogr am as shown in t he Fig. 10.1, may be consider ed t o r esult fr om a
single elect r ochemical r eact ion. This is wit hout kinet ic or cat alyt ic complicat ions. The
exper iment al condit ions so select ed ar e such t hat t he diffusion is t he sole means of mass
t r ansfer . Also, t he elect r ode may be consider ed a plane, wit h bot h oxidized and r educed
species being soluble in t he solut ion. The Sand equat ion applies t o all such cases,
whet her r ever sible or ir r ever sible. But t he or iginal pot ent ial t ime r elat ion as given by
Kar aoglanoff [11] applies only t o t hose cases for which t he magnit ude of t he for war d and
r ever se elect r ochemical r at e const ant s is lar ge enough so t hat Ner nst equat ion i obeyed,
i.e., t he elect r ochemica l pr ocess ma y be consider ed t o be r ever sible. The usua l
symbolizat ion of t he pr ocess is given as :
O + ne R
The equat ion of Kar aoglanoff (11) for bot h O and R soluble is :
E = E
/4

1 2
1 2 1 2
ln
RT t
nF
r t
...(5)
wher e RT/nF has it s usual significance, t is t he t ime in seconds, and is t he t r ansit ion
t ime. This is analogous t o similar equat ion for polar ogr aphic waves. It may also be
shown t hat
E
t /4
= E
1/2
...(6)
(t he polar ogr aphic half-wave pot ent ial) pr ovided t he exper iment is done wit h mer cur y
elect r ode. Also E
t /4
is r elat ed t o t he st andar d pot ent ial of t he elect r oact ive couple by
E
r/4
= E
0

1 2
1 2
0
ln
R
R
f D RT
nF
f D
...(7)
The equat ion (5) indicat es t hat a plot of log [(t
1/2
t
1/2
)t
1/2
] ver sus E should yield a
st r aight line whose r ecipr ocal slope is 2.303 (RT/ nF) or 0.0591/n at 25C.
10.7.1 Irreversible Processes
The ir r ever sible elect r ode r eact ion is r epr esent ed by
O + ne R ...(8)
The r elat ionship given on eqn. (5) may be applied t o r elat e t r ansit ion t ime t o
concent r at ion, just as t he Ilkovic equat ion may be applied t o bot h r ever sible and
ir r ever sible polar ogr aphic pr ocesses.
The pot ent ial of t he wor king elect r ode dur ing a t ot ally ir r ever sible elect r ode r eact ion
has been r elat ed t o t he cur r ent [13] t hus
i = nAF
0 a
f
n FE
Ck exp
RT
| |
|
\ .
...(9)
wher e is t he t r ansfer coefficient of t he elect r ode pr ocesses, C is t he concent r at ion of
t he elect r oact ive species at t he elect r ode sur face, n
a
is t he number of elect r ons involved
in t he r at e, det er mining st ep, and
0
f
k is t he r at e const ant for t he ir r ever sible pr ocess
in cent imet ers per second at E = 0 (versus t he normal hydrogen elect rode). The assumpt ion
using t his equat ion is t hat t he r at e of t he r ever se pr ocess is negligible and t hat t he
kinet ics of t he elect r on t r ansfer r eact ion is cont r olled by a single r at e det er mining st ep.
By int r oducing t he t r ansit ion t ime fr om t he equat ion (3), t he following pot ent ial t ime
r elat ionship is obt ained [7].
Fr om t he pr oceeding equat ion (10), it is appar ent t hat a plot of ln (
1/2
t
1/2
) ver sus
E should give a st r aight line of slope RT/n
a
F. In addit ion, t he
4
E
for t he ir r ever sible

( )
( )
0
1 2 1 2
1 2
2
ln ln
a a
n n
RT RT k f
E t
F F
D
= +

...(10)
case shift s linear ly wit h ln C
0
and wit h t he cur r ent densit y I.
Values of
a
n
and
0
f
k can be det er mined t hr ough t he use of equat ion (10), which
is convenient t o wor k. Chr onopot ent iomet r y has cer t ain advant ages over polar ogr aphy
for t his t ype of wor k. The r eason being t hat t he diffusion pr ocess involved is much
simpler. Elect rodes ot her t han mer cur y can also be used and t he r eact ion can be st udied
in bot h dir ect ions by r ever sing t he cur r ent .
It is also t o be not ed t hat when kinet ic complicat ion pr ecede t he char ge t r ansfer
pr ocess, It
1/2
is not dir ect ly pr opor t ional t o concent r at ion.
Two component syst ems have also been st udied
by cur r ent -r ever sal chr onopot ent iomet r y and can
be t r eat ed quant it at ively under assumpt ion t hat
all species have equal diffusion coefficient s.
A var iat ion of cur r ent r ever sal chr onopot en-
t iomet r y is cycle chr onopot ent iomet r y in which
cur r ent is r ever sed r epeat edly at pot ent ials t aken
at t he t r ansit ion t imes of var ious waves. Sever al
ca s es , i n cl u di n g di ffu s i on con t r ol l ed s i n gl e
component syst em, elect r on t r ansfer followed by a
chemical r eact ion, and mult i-component syst ems
and st epwise r eact ion have been examined by
var ious wor ker s in t he past .
10.8 EXPERIMENTAL METHODS
10.8.1 Apparatus
1. Current supplies : In or der t o use high
cur r ent s cont inuously, it is convenient t o
use a var iable high-volt age power supply of good qualit y. Elese for const ant
cu r r en t s u ppl y ma y
ea sily be const r uct ed
fr om s ever a l 45-vol t
bat t er ies and a ser ies of
r esist or s a r r a nged in
s u ch a wa y t h a t
cu r r en t s fr om a few
milliamper es t o a few
micr oamper es may be
obt ained [10]. In or der
t o minimize t he heat ing
effect s if t he r esist or s
a r e of a fa i r l y h i gh
volt age. The const ant
cu r r en t ca n be
measur ed by inser t ing
a st andar d r esist or (R
s
)
a s shown in t he Fig.
10.20 in t he cir cuit and
measur ing t he volt age
dr op acr oss t his r esist or wit h a pot ent iomet er dur ing elect r olysis.
Const ant cur r ent sour ces of high qualit y can also be const r uct ed fr om oper at ional
amplifier s [17] by placing t he cell in t he feedback loop of an amplifier , t he
REF. AUX.
Fig. 10.19 : Chronopot ent iomet ric
cell wit h mer cur y-pool wor king
elect rode
E
.
V
o
l
t
s
v
s
.
S
.
C
.
E
.
Ti me
Fig. 10.20 : Met hods of t ransit ion-t ime measurement ;
ir r ever sible or dist or t ed cur ve
out put of which is a known pot ent ial t hr ough a known r esist or . A const ant
cur r ent will pass t hr ough t he cell, if t he pot ent ial is const ant . The main advant age
of t his t ype of cir cuit is for t hose met hods which make use of var iable cur r ent s
such as, power of t ime chr onopot ent iomet r y [14].
A gr eat var iet y of r ecor der s (st andar d st r ip-char t ) ar e usually adequat e when
t he char t dr ive is const ant wit h t ime and t he pen speed is at least 1 sec. full
scale.
An oscilloscope of appr opr iat e t ype can also be used for measur ement of t r ansit ion
t imes.
10.8.2 Cells and Electrodes
Or dinar y cells wit h t hr ee elect r odes ar e used for chr onopot ent iomet r y. The wor king
elect r ode, t he auxiliar y elect r ode and t he r efer ence elect r ode [B] Fig. 10.19. Gr aphit e
elect r odes ar e also useful. This is because t heir anodic r ange is gr eat er t han t hat for
eit her plat inum or gold. Thr ee t ypes of mer cur y elect r odes have found gener al use for
chr onopt ent iomet r y. For example, Mer cur y pool, hanging dr op, and t he dr opping mer cur y
elect r ode. In or der t o obt ain r epr oducible elect r ode ar ea, t he mer cur y pool should be of
unifor m cr oss sect ion. The hanging mer cur y dr op elect r ode has gr eat er ut ilit y due t o it s
convenience, r epr oducible ar ea (about 0.2 per cent ), and t he saving t hat r esult s in t he
quant it y of mer cur y consumed.
Hanging mer cur y dr op elect r ode can also be for med by t he expulsion of a small
quant it y of mer cur y fr om a micr o-syr inge fit t ed wit h a micr omet er . These devices ar e
also commer cially available.
In or der t o synchr onize t he measur ement of dr op for mat ion, using some means, t he
dr opping mer cur y elect r ode can also be used.
10.9 THE TECHNIQUES
10.9.1 Measurement of Transition Times
The accur acy of chr onopot ent iomet r ic met hods depends on t he exact ness wit h which
t r ansit ion t imes can be measur ed. Fig. 10.8 shows a t ypical r ever sible chr onopot ent iogr am
wit hout much dist or t ion. To, measur e t r ansit ion t ime, t he simplest met hod is t o dr aw
Fig. 10.9, t he t angent lines CF and AD and locat e t he point Z. Her e t he pot ent ial t ime
cur ve depar t s fr om a st r aight line. The t r ansit ion t ime is t hen t akes fr om Z t o AD. In
an accur at e syst em t he pot ent ial at which Z is locat ed will be ver y close t o const ant . In
such syst ems pr ecise r esult s can be obt ained simply by measur ing at some const ant
pot ent ial near by but not necessar ily at , Z. The met hod of finding Z, is t o be pr efer r ed
if n values and even mor e impor t ant , if diffusion coefficient ar e of int er est . The met hod
appear s t o be super ior as r egar ds simplicit y and accur acy.
If t he pot ent ial-t ime cur ve is dist or t ed or as t he wor king elect r ode as well. Micr o
r efer ence and auxiliar y elect r ode ar e made t o cont act t he dr op above. A mer cur y elect r ode
of special design can also be used. The st andar d chr onopot ent iomet r ic r elat ionship apply
t o t his appar at us.
Some int er est ing wor k can also be r epor t ed in which a t hin layer of solut ion is f
confined next t o t he wor king elect r ode sur face [6]. Thin layer chr onopot ent iomet r y also
has advant ages like :
1. Chr onopot ent iogr ams ar e oft en less dist or t ed t han t he cor r esponding semi
infinit e-diffusion case.
2. Kinet ic st udies, par t icular ly of slower r eact ions, can be car r ied out . This is due
since t he pr oduct of elect r ode r eact ion ar e held near t he elect r ode and ar e t hus
available for fur t her st udy.
3. St udies of adsor bed r eact ant s can be made since in many cases an appr eciable
fr act ion of a species in t he cell may be r emoved by adsor pt ion.
10.10 APPLICATIONS
10.10.1 Concentration Measurements
Chr onopot ent iomet r y is not as lar ge as compar ed t o polar ogr aphy, Chr onopot ent iomet r ic
under opt imum condit ions is capable of measur ing concent r at ions wit h an accur acy of
0.5 t o 1% [8]. Wor k wit h elect r odes ot her t han mer cur y can be car r ied out wit h super ior
r esult s t o polar ogr aphy. Specially wit h r ot at ing, elect r ode. It could be a mat t er of choice
in chr onopot ent iomet r y for wor king at anodic pot ent ials, alt hough cyclic volt ammet r y
and r ot at ing disk elect r ode ar e ext ensively used.
10.10.2 Electrode Kinetics
Var ious met hods for measur ing t r ansit ion t imes of ir r ever sible chr onopot ent iomet r ic
waves have been compar ed and comment s r epor t ed [18] ir r ever sible Fig. 10.20. Pr act ically
it is desir able t o const r uct t wo t angent lines necessar y t o locat e point A. The t r ansit ion
t ime is t hen t aken fr om A t o t he t angent line for t he beginning por t ion of t he cur ve. The
met hod of locat ing Z, as alr eady given is pr efer able. Her e being t aken fr om Z t o
ext ension of t he st ar t ing por t ion of t he pot ent ial t ime cur ve. Too lar ge values of ar e
obt ained when t he chr onopot ent iogr am is ver y dist or t ed.
10.10.3 Electrode Pretreatment
A fr esh sur face is easily obt ainable while using DME or t he hanging dr op, and t his t he
main advant age of t hese elect r ode r at her t han using solid elect r odes like plat inum. The
noble met al sur faces ar e liable t o be oxidized. In such cases pr et r eat ment of elect r odes
is necessar y [2].
10.10.4 Differential and A.C. Chronopotentiometry
A met hod of det er mining t r ansit ion t imes, differ ent iat ion of pot ent ial t ime cur ve has
been suggest ed [9]. Differ ent iat ion is accomplished in r ever sible pr ocesses since t he
magnit ude of t he sinusoidal component of t he pot ent ial is pr opor t ional t o dE/ dt. Cur ve,
if t hey ar e of dE/ dt t ype, show a maximum at t he inflect ion of t he pot ent ial t ime cur ve
or change sign if of t he d
2
E/dt
2
t ype.
10.10.5 Thin-Layer Chronopotentiometry
Chr onopot ent iogr ams can, however , be t aken on single dr ops [10] wit h a value of only
0.05 ml. The cell used consist s of a plat inum plat e wit h a small depr ession t o hold t he
dr op in place. This plat e ser ves best r esult s wer e obt ained wit h an algebr aic met hod of
calculat ing t he t r ansit ion t imes. Wit h t he aid of a digit al comput er , a least squar e
a n a l ys i s of ch r on opot en t i omet r i c cu r ve wa s a l s o a ccompl i s h ed. However ,
chr onopot ent iomet r y is quit e impor t ant for t he st udy of ir r ever sible r eact ions [13].
The fact r emain t hat chr onopot ent iomet r y has not been ext ensively used t o measur e
t he kinet ic par amet er s like k and for ir r ever sible r eact ion may be due t o bet t er and
mor e r apid t echniques.
10.10.6 Chemical Kinetics
One of t he major applicat ions of chr onopot ent iomet r y t o dat e has been t he st udy of
chemical r eact ions eit her pr eceding or following elect r on t r ansfer r eact ions.
Chr onopot ent iomet r y can be applied t o chemical kinet ics in a way analogous t o any
ot her concent r at ion measur ing t echnique. The main advant ages of chr onopot ent iomet r y
involves invest igat ion of chemical r eact ions closely coupled wit h elect r on t r ansfer
r eact ions.
React ions which pr ecede t he elect r ode t r ansfer include bot h t he addit ion or loss of
hydr ogen or hydr oxide ion and t he dissociat ion of met al complexes. Mar k and Anson
[12] made quit e some invest igat ion in t he ar ea.
React ions which follow elect r on t r ansfer r eact ion can also be st udied. Cur r ent r ever sal
chonopot ent iomet r y is quit e helpful for such a wor k.
10.11 ADSORPTION
Adsor bed molecules ar e in lower fr ee-ener gy st at e t han t hose in solut ion and t hus mor e
difficult t o r educe or oxidize [5]. Anot her r easonable possibilit y is t hen t o assume t hat
t he adsor bed layer under goes elect r olysis only aft er t he usual t r ansit ion t ime for t he
diffusing species.
The fact is t hat , while t he adsor bed layer is r eact ing t owar d t he end of t he elect r olysis,
mor e soluble species diffuse upt o t he elect r ode t hus r educing t he cur r ent efficiency.
Recent ly, r adiot r acer met hods and t hin-layer chr onopot ent iomet r y have been used t o
invest igat e adsor pt ion of var ious subst ances specially t hat of iodine [15].
10.12 APPLICATIONS
One of t he most int er est ing has been t he wor k on fused salt , wher e sever al ot her
st andar d met hod, such as polar ogr aphy cannot be applied.
Th i ck n es s of t h i n fi l ms on va r i ou s met a l s h a s a l s o been s t u di ed by
chr onopot ent iomet r ic met hods [38], [39]. The met hod is similar t o t hat used t o st udy
elect r ode oxidat ion. Calculat ion of t hickness could be calculat ed by t he for mula
T = 10
5
M i/An Fd ...(2)
wher e, T is t he t hickness in angst r oms, M is t he gr am for mula weight of t he compound,
d is t he densit y of t he compound, and A is t he specimen ar ea. Ot her symbols have t he
st andar d meaning.
References
1. Bar d, A.J . Anal Chem. 33, 11 (1961).
2. Bar d, A.J . Elect r oanalyt ical Chemist r y, Dept . of Chemist r y, Univ. of Texas Aust in,
Texas.Vol I. p. 178 and 183.
3. Ber zins T. and Delahay, P.J . Am. Chem. Soc., 75 4205 (1953).
4. But t er J .A. and Ar mst r ong. Tr ams. Far aday Soc., 30 1173 (1943). and Anal. Pr oc. Royal
Soc., London A 139, 406 (1933).
5. Brdi cka R., Collect ion Czech. Commun. 12, 522 (1947).
6. Chr ist en C.K. and Ason, F.C. Anal. Chem. 36, 723 (1964).
7. Delahay P. and Ber zins T. J . Am. Chem. Soc., 75, 2486 (1953).
8. Davis, D.G. Anal. Chem. 33, 1839 (1961).
9. Iwamot o, R.T. Anal. Chem. 31, 1062 (1959).
10. Iwamot o, R.T. and Adams R.N. and H. Lot t , Anal. Chem. Act a. 20, 84 (1959).
11. Kar aoglan off. Z. Elect r ochem. 12.5 (1906).
12. Mar k H.B. and Ason, F.C., Anal. Chem. 35, 722 (1963).
13. Moor head E.D., and Fur man N.H. Anal. Chem. 32, 1507 (1960).
14. Mur r ay R.W. and Reilley C.N.J . Elect r oanal. Chem. 3, 64 (1962).
15. Ost er Young R.A. and Anson F.C., Anal. Chem. 36, 975 (1964).
16. Reilley, C.N. Manot ov G. Anal. Chem. 27, 4786 (1955).
17. Reilley, C.N.J . Chem. Edu. 39, A 853 (1962).
18. Russel R.C.D. and Pet er son, J .N.J Elect r oanal. Chem. 5, 467 (1963).
19. Sand, M.J .S. Phil. Mag. 1, 45 (1901).
20. Bar ker G.C. J enkins I.L. Analyst 77, 685 (1952).
21. Bar ker G.C. Pr ogr ess in Polar ogr aphy (P. Zuman and I.M. Kolt hoff) Vol. 2. p. 411
int er science N. 7 (1962).
22. Kambar a Bul. Chem. S.C., J apan 27, 523, 529 (1954).
23. Kalouscek, M. Chem. List y 40, 149 (1946) Colln. Czech. Chem. Commun. 13, 105 (1948).
24. Kout ecky J . Chem. List y 49, 1454 (1955) Collect ion Czechoslov. Chem. Communs. 21, 433
(1956).
25. Wer ber J . Chem. List y 52, 1888 (1958) Collect ion Czechoslov. Chem. Communs. 24, 1770
(1959).
26. Gilber t G.A., Ri DEAL E.K. : Tans. Far aday Soc., 47, 369, (1951)
27. Lingane, Elect r oanalyt ical Chemist r y Int er science, N.Y. 2nd Ed. 1958 pp. 351415.
28. Lingane J .J . : J . Am. Chem. Soc., 67 1916 (1945).
29. Mar k H.B., Smit h E.M., Reilley C.N. : J . Elect r oanal. Chem. 3, 98, (1962).
30. Meit es L : Anal. Chem. 27, 1114 (1955).
31. Lingane. J .J . Elect r oanalyt ical Chemist r y, Index Science, New Yor k 2nd. ed. (1958), pp.
315415.
32. Br eyer , B. Gut man F. and Hacobian S., Aust . J . Scient . Res. A/3, 558 (1950).
33. Br eyer , B. and Bauyer H.H., Alt er nat ing Cur r ent Polar ogr aphy and Tensammet r y, in
Chemical Analysis (P.J . Elving and I.M. Kolt hoff, eds.), Vol. 13, Wiley (Int erscience), New
Yor k, (1963).
34. Reilley C.N. and St umm W.; in Pr ogr ess in Polar ogr aphy (P. Zuman, ed., wit h t he
collabor at ion of I. M. Kolt hoff), Vol. I. Chap. 5, W. Int . Sci. N.Y. (1962).
35. Gr aham, D.C., J . Elect r ochem. Soc., 98, 370C (1952).
36. Kambar a T., and Tachi, I. Bull. Chem. Soc., J apan 25, 135 (1952).
37. Fr umkin, A.N., Z. Physik. Chem., 164, 121 (1933).
38. Evans U.R., and Bannist er , L.C., Pr oc. Royal Soc. (London), A125, 370 (1929).
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1170 (1939).
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CHAPTER 11
ADVANCES IN D.C. POLAROGRAPHY
11.1 DEVELOPMENTS IN D.C. POLAROGRAPHY
The d.c. polar ogr aphy is defined t o mean cur r ent -volt age r elat ionships (volt ammet r y) at
const ant pot ent ial when a dr opping elect r ode (D.M.E.) is used. This is t he classical d.c.
polar ogr aphy, or iginat ed by Pr ofessor J ar oslav Heyr ovsly in about 1922. In usual pr act ice,
t he volt age of t he D.M.E. wit h r espect t o a r efer ence elect r ode, usually calomel, is
scanned linear ly and t he r esult ing cur r ent is r ecor ded as a funct ion of volt age. The
condit ion of const ant pot ent ial is adequat ely sat isfied if t he r at e of volt age scan is
enough so t hat t he change of volt age dur ing t he life of each D.M.E. dr op is less t han
about 10 mV. D.C. polar ogr aphy is par t icular ly useful for inor ganic and for or ganic
chemical analysis of minor and of t r ace level const it uent s in aqueous and in non-aqueous
solvent s. It has also cont r ibut ed t o t heor et ical elect r ochemist r y.
In d.c. polar ogr aphy wit h a pot ent iost at , i.e., at cont r olled pot ent ial t her e ar e cer t ain
advant ages like : iR does not significant ly affect t he D.M.E. so t hat t he r egular
polar ogr ams ar e undist or t ed and t he effect ive scan r at e r emains const ant , a necessar y
condit ion for quant it at ive t ime-derivat ive polarography. Also convenient pH-t ype reference
elect r ode may be used when E
1/2
infor mat ion is unnecessar y. The quasi-r efer ence elect r ode
may be used.
Equat ions have been der ived for simple, r ever sible diffusion-cont r olled pr ocesses
which quant it at ively compar ed r elat ive sensit ivit y and r esolut ion of r egular and of fir st ,
second, and t hir d der ivat ive d.c. polar ogr ams. On t his basis, t he r esolut ion of d.c.
polar ogr aphy can be compar ed wit h t hat of ot her met hods.
Convent ional d.c. r egular and der ivat ive polar ogr ams can be r apidly obt ained if a
D.M.E. having a cust omar y flow r at e but a dr op t ime of 0.5 sec or less (i.e., diffusion
cont r olled) is used wit h fast cir cuit s and scan r at es. The specific r esist ance is low
enough so t hat t he t ip need not be close t o t he D.M.E. Relat ionships bet ween concent rat ion
and diffusion-cur r ent and concent r at ions and fir st der ivat ive peak height ar e linear for
cell concent r at ions fr om 5 10
6
t o 1 10
4
. By polar ogr aphy in an or ganic solvent s,
t her e is also t he possibilit y of det er mining species t hat ar e unst able in wat er .
11.1.1 Principle of Potentiostatic (Controlled-Potential) Electrolysis
As lat e as in 1942, Kickling [8] developed a met hod for aut omat ic elect r onic cont r ol of
t he pot ent ial of a wor king elect r ode wit h r espect t o t hat of a r efer ence elect or de, i.e.,
a pot ent iost al and many applicat ions of t his pr inciple have since been descr ibed. In
cont r olled-pot ent ial d.c. polar ogr aphy, t he command volt age is t he sum of t he init ial and
t he scan volt ages. In t he pot ent iost at t he command volt age is compar ed wit h t he act ual
value of t he volt age of t he D.M.E. wit h r espect t o t hat of t he r efer ence elect r ode, and
t he differ ence bet ween t hese, t he er r or volt age, in t he input signal at t he summing point
of t he pot ent iost at . The out put volt age of t he pot ent iost at is applied bet ween t he count er
elect r ode and gr ound. The D.M.E. is held at vir t ual gr ound pot ent ial wit h a cur r ent
amplifier . In t he polar ogr aphy, t he locat ion of t he pot ent ial differ ence t hat cor r esponds
t o t he command volt age is t hus t he pot ent ial of t he equipot ent ial sur face t hat passes
t hr ough t he t ip of t he r efer ence elect r ode wit h r espect t o t he pot enit al of t he D.M.E. For
being st able, t he pot ent iost at should cont r ol t he volt age bet ween t he wor king and
r efer ence elect r ode t o wit hin a few millivolt s of t he command volt age.
11.2 TIME-DERIVATIVE D.C. POLAROGRAPHY
The quant it at ive t ime-der ivat ive d.c. polar ogr aphy r equir es const ant and r epr oducible
scan r at es, comput at ion of aver age cell cur r ent , and comput at ion and r ecor ding of t ime
der ivat ives of aver age value of cell cur r ent . These condit ions ar e easily obt ained wit h
simple elect ronic circuit s.
I n nt h der ivat ive d.c. polar ogr aphy, t he object is t o r ecor d a signal t hat is dir ect ly
pr opor t ional t o d
n
i (dE)
n
as a funct ion of E (volt age). The nt h der ivat ive is obt ained by
n fir st der ivat ive cir cuit s
in cascade. Thus only t he
inst r ument at ion used t o
obt a i n t h e n eces s a r y
con di t i on s for fi r s t
der ivat ive polar ogr aphy,
n eeds a t t en t i on . F or
h i gh er der i va t i ves ,
degr adat ion of signal t o
n oi s e r a t i o h a s been
cir cumvent ed by use of
fast scan r at es. This will
be discussed lat er . The
ou t pu t of t h e pol a r o-
gr aph is calibr at ed, for
example, for fir st and for
s econ d der i va t i ve d. c.
pol a r ogr a ph y r es pec-
t ively, in A min
1
and
in A min
27
. Since t he
ma gn it u de t h r ou gh ou t
a n nt h der ivat ive wave is dir ect ly pr opor t ional t o t he nt h power of dE/ dt, it is essent ial
t hat dE/ dt be of a known, const ant value. A wide r ange of highly r epr oducible values of
dE/ dt having ver y low noise levels ar e obt ained by means of an elect r onic scan gener at ing
E, volts
E
= 77mV
P
E
R
C
E
N
T
M
A
X
I
M
U
M
V
A
L
U
E
d
T
d
i
Fig. 11.1 : Relat ive r esolut ion of r egular , fir st der ivat ive and
second der ivat ive polar ogr ams
P
E
R
C
E
N
T
M
A
X
I
M
U
M
V
A
L
U
E
T
E
,
volts
E
= 118mV
P
E
R
C
E
N
T
M
A
X
I
M
U
M
V
A
L
U
E
E, volts
E
= 72mV
d
T
d
t 2
2
cir cuit t hat consist s of an oper at ional amplifier cur r ent -int egr at ing syst em fed by a
const ant cur r ent of appr opr iat e sign and magnit ude [10]. In t hese cir cuit s, an unst abilized
oper at ional amplifier is used. The const ant cur r ent is der ived fr om a volt age-r efer ence
zener diode.
The basis of t he analog met hod of comput ing t he t ime der ivat ive of a volt age signal
is t he fundament al pr oper t y of a capacit or and t hat Q = CE (1), wher e Q is t he char ge,
st ar ed in a capacit or of capacit ies C and E is t he volt age developed acr oss t he capacit or .
Real capacit or s ar e r eadily available whose pr oper t ies, at fr equencies of int er est in
der ivat ive polar ogr aphy, ver y closely appoximat e t hose if an ideal capacit or . Consequent ly,
if t he signal volt age E, is impr essed acr oss a capacit or C, t he cur r ent passing t hr ough
t he capacit or i
C
, is dir ect ly pr opor t ional t o dE/ dt as shown in t he equat ion :
dQ/ dt = CdE/ dt ...(1)
Simp le (I d ea l) Op er a t ion a l Amp lifier Der iva t ive Comp u t er : Some improvement
over t he per for mance at t ainable above
wit h only a passive RC net wor k is
possible by use of t he above given
amplifier . The common connect ion of
C and R is connect ed t o t he summing
point of t he amplifier and t he fr ee
t er mina l of R is connect ed t o t he
out put t er minal of t he amplifier . The
input signa l E, is connect ed fr om
gr ound t o t he fr ee t er minal C and t he
out put , E
0
, is t he volt age fr om gr ound
t o t he out put t er minal of t he amplifier .
The out put volt age of t he amplifier ,
E
0
is :
E
0
= RC
d
dt
E ...(2)
wh i ch s h ows t h a t E
0
is t he t r ue
der ivat ive of t he input signal, E. The
a dva n t a ges of t h e s i mpl e, i dea l ,
oper a t i on a l a mpl i fi er der i va t i ve
comput er ar e as follows : Ther e is no
t ime lag because all of t he input signal
is impressed across C. The value of
RC may be high in or der t o obt ain
high sensit ivit y wit hout t he int r oduct ion of t ime log. Anot her advant age is t hat useful
load cur r ent may be dr awn fr om t he amplifier wit hout affect ing t he accur acy of t he
der ivat ive comput at ion.
Addit ion a l Requ ir emen t s for Opt imu m Resolu t ion a n d Sen sit ivit y : For optimum
r esolut ion, t he r ecor ded der ivat ive wave must be of t heor et ical for m, wit hout dist or t ion
Fi g. 11.2 : Qualit at ive compar ison of r esolut ion
by r egular and der ivat ive polar ogr aphy.
Advances in D.C. Polarography 137
0.50
In
+++
Cd
++
0.5 a
0.1 a/min.
0.55 0.60 0.65 0.70
E volts vs S.C.E.
0
CONDITIONS :
O.R.N.L. model Q-1988-ES
polarography
1 10 IN and 2 10
Cd in 0.1 KCI
I.P. is 0.45 volts vs S.C.E.
5 microamp. current range
Sargent 2 to 5 sec. Capillary
Scan rate is 0.02 v/min., 0.04
v./ inch
Regular : undamped
Derivative : quad. parallel-T,
RC current ave. filter
1-3-61
4 ++ 4
++
M M
M
due t o iR losses or t o t ime lag
br oadening. The r ecor ded wave
for ms must be dict at ed by t he
r educt ion pr ocesses at D.M.E.,
and be undist or t ed by cir cuit r y
per for ma n ce. Th i s h a s been
achieved at scan r at es up t o 300
mV min
17
, but even above t his,
wher e some t ime lag dist or t ion
occur s, der ivat ive polar ogr ams
a r e s t i l l h i gh l y r epr odu ci bl e
because t he cir cuit s ar e linear
s ys t ems . Th e ma gn i t u des of
t hese effect s and t he scan r at e
below which t hese magnit udes
a r e n egl i gi bl e a r e r ea di l y
pr edict ed fr om t he known t ime
l a gs of t h e s ys t ems . F or a
r ever s i bl e wa ve, a s en s i t i ve
cr it er ion is whet her t he r ecor ded
volt age at which t ha peak occur s
is independent of t he dir ect ion
of scan.
S h o r t Dr o p Ti m e o f
D.M.Es : It has been point ed out t hat a shor t dr op t ime D.M.E. is needed in or der t o
at t ain opt imum r esolut ion (at fast scan r at es) and opt imum sensit ivit y. It is also indicat ed
t hat shor t dr op t ime ar e less affect ed by vibr at ion and ar e less noisy in aqueous and in
or ganic solvent s t han t he usual 2 t o 5 sec D.M.E.s.
Si gn a l t o Noi s e Ra t i o : In pr act ice, t he sensit ivit y is limit ed t o t he signal t o noise
r at io (SN), of t he cell cur r ent r at her t han by t he magnit ude of far adaic cur r ent , i.e., or
t he pr esence of a r esidual cur r ent , i
r es
, whose magnit ude [7] at low concent r at ions of
depolar izer is lar ger t han iF[7] i.e., r at her t han t he r at io of i
F
t o i
r es
. This has been
explained by a number of equat ions [9]. In case of nt h der ivat ive polar ogr aph, t he t er m
in equat ions ar e each r eplaced by t heir nt h der ivat ive.
The pr imar y fact or t hat limit s t he sensit ivit y of polar ogr aphy is t he noise (imper fect
r epr oducibilit y) of t he cur r ent at a D.M.E. The S/N and gener al usefulness of t he D.M.E.
is equal t o or bet t er t han t hat of ot her kinds of polar ized elect r odes. In par t icular , t he
best S/ N was obt ained wit h small or ifice and wit h smaller ver t ical or ifice D.M.E.s. It
is ant icipat ed t hat t he S/ N of der ivat ive d.c. polar ogr aphy will be highest wit h shor t
dr op t ime D.M.E.s of t hese designs at fast scan r at es wit h t he new fast d.c. polar ogr aph.
The r epr oducibilit y of fir st der ivat ive peak height s depends upon t he r epr oducibilit y
of t he scan r at e and also upon t he r epr oducibilit y of t he r egular aver age cur r ent wave
since t he lat t er is t he input signal t o t he der ivat ive comput er . In or der t o get best
Fig. 11.3 : Det er minat ion of n by measur ement of
der ivat ive polar ogr am.
0.45
E volts vs S.C.E.
0
0.49 0.53 0.59 0.63
E IN
+++
0.04 a/min.
H
W
H
2
dt
dt
ave
CONDITIONS :
O.R.N.L. model Q-1988-ES
polarography
Quadruple parallel-T, RC l ave.
filter
Sargent 2 to 5 sec. capillary
Initial potential is 0.45 volts
vs. S.C.E.
Current range is 2
microamperes
Scan rate is 0.01 volts per min.
110
4
IN
++
in 0.1 KCI
30 Jan. 1961
M M
n = 90.5/
(25C)
W
(mV)
n = 90.5/30.6 = 2.96
r epr oducibilit y r esult s, t he solut ion should be well spar ged. The r epr oducibilit y of r egular ,
wave height s and of fir st der ivat ive peak height s is essent ially t he same.
11.2.1 Direct Proportionality of First Derivative Peak Heights to i
d
Theor et ically, for a simple r ever sible diffusion cont r olled pr ocess, wit h const ant D.M.E.
char act er ist ics, t emper at ur e and scan r at e, t he fir st der ivat ive peak height s should be
dir ect ly pr opor t ional t o id. This r elat ionship has been ver ified for Tl
+
, Cd
++
, Pb
++
, et c.
The r esult s show t hat t he height s of t he der ivat ive peaks have t he same r elat ionship
t o concent r at ion as do t he cor r esponding r egular wave height s.
11.2.2 Relative Signal Levels in Regular and in First, Second, and Third
Derivative D.C. Polarography
The r elat ive at t ainable sensit ivit ies of r egular and of fir st , second and t hir d der ivat ive
d.c. polar ogr aphy depends on t he at t ainable S/ N in each case. The degr ee of noise
depends upon t he specific har dwar e t hat is used and is best evaluat ed exper iment ally.
It is possible t o calculat e t he r elat ive signal levels fr om t he equat ions for a simple,
r ever sible, diffusion cont r olled pr ocesses. This calculat ion ser ves as a guide t o t he r elat ive
sensit ively limit s under ideal condit ions. New fast d.c. polar ogr aphs have been designed
t o r ecor d r egular and fir st , second and t hir d der ivat ive d.c. polar ogr ams.
The r at io of t he height s in A min
1
of t he peak of t he fir st der ivat ive d.c. polar ogr am
t o t he diffusion cur r ent A of t he cor r esponding r egular polar ogr am is :
4
nF dE
RT dt
...(3)
wher e dE/ dt is t he scan rat e in V min
1
and t he ot her symbols have t he same significance.
The r at io of t he height in A min
2
of eit her peak of a second der ivat ive d.c. polar ogr am
t o t he diffusion cur r ent in A of t he cor r esponding r egular polar ogr am is :
2 2
2
1 0 3 9
n F dE
. RT dt
| | | |
| |
\ . \ .
...(4)
The r at io of t he height in A min
3
of t he middle peak of a t hir d der ivat ive d.c.
polar ogr am t o diffusion cur r ent in A of t he cor r esponding r egular polar ogr am is :
3 3
3
8
n F dE
RT dt
| | | |
| |
\ . \ .
...(5)
It is of int er est t o compar e calculat ions made fr om t he above equat ions [14]. The
impor t ance of at t aining condit ions allowing t he use of fast scan r at es is obvious fr om t he
above equat ion.
11.2.3 Criterion for Relative Resolving Power of Various Methods of
Polarography
The quest ion ar ises of whet her t he concent r at ion of all t hese species can be det er mined
polar ogr aphically or t he concent r at ion of one of t he species wit hout er r or due t o t he
r educt ion or ot her wise. This may happen whenever sever al species r educe at successive
volt age wit hin t he volt age r ange cover ed. It is well known t hat t he E
1/2
s of t he waves
can somet imes be shift ed r elat ive t o each ot her by cont r olling pH or by complex for mat ion
of by ot her changes in t he medium and t hat int er fer ence may be pr event ed by r emoving
a species by solvent ext r act ion. This may somet ime solve a par t icular over lap pr oblem.
If t her e is no int er act ion bet ween t he pr imar y species or bet ween t hese and t he
product s of elect rolysis, t he polarogram of t he mixt ure is equal t o t he sum of a polarograms
of t he suppor t ing elect r ot ype and polar ogr ams of each species t hat would be obt ained
if each wer e pr esent separ at ely in t he suppor t ing elect r olyt e :
i
cell
(E) = i
r es
(E) +
1
F
i (E) +
2
F
i (E) +
i
F
1
...(6)
The net polar ogr am
= polar ogr am of suppor t ing elect r olyt e + polar ogr am of species 1
+ polar ogr am of species 2 + ... ...(6)
Condit ions under which r egular and der ivat ive d.c. polar ogr ams of t heor et ical for m
can be r ecor ded wit h polar ogr aphs. See r ef. [14] for fur t her det ails.
11.2.4 Geometrical Overlapping for Successive Waves
In t he case of fir st der ivat ive d.c. polar ogr aphy a fir st der ivat ive wave has a maximum
value at E
1/2
. In case wher e t he t wo fir st der ivat ive waves have a close E
1/2
s, t he posit ion
of one or bot h of t he maximum values in t he net fir st der ivat ive pr ogr ams ar e not
necessar ily at t he cor r esponding E
1/2
values. In sever e over lapping, t he net pr ogr amme
may have only one br oad peak. This is a gemoet r ical effect . Taking for example if t he
const it uent der ivat ive polar ogr am due t o species 2 is incr easing r apidly at t he E
1/2
or
species 1, t he net der ivat ive polar ogr am can cont inue t o incr ease beyond t he E
1/2
for
special. This means t hat measur ement s of geomet r ical over lapped der ivat ive polar ogr ams
should be made at chosen const ant volt ages (usually at t he E
1/2
) and not summit volt ages
of t he net wave. This consequence of geomet r y is not unique t o polar ogr aphy. This is
even impor t ant in absor pt ion spect r oscopy [13] and in gas chr omat ogr aphy [13].
RELATIVE RESOLUTION OF REGULAR AND OF FIRST, SECOND AND
THIRD DERIVATIVE D.C. POLAROGRAPHY
The equat ions for a simple, r ever sible, diffusion cont r olled pr ocess can be r efer r ed t o
[21]. The Fig. 11.4 ar e plot t ed for t he following condit ions :
id is equal for t wo successive polar ogr ams and n is 2 for bot h polar ogr ams. In each
case t he per cent age of t he maximum value is plot t ed as a funct ion E. The separ at ion
of E
1/2
s t hat r esult in t he second polar ogr am cont r ibut ing 1% t o t he height of t he fir st
is shows in each case. This separ at ion is explained as follows : r egular polar ogr am E/
2 = 118 mV; fir st der ivat ive polar ogr am, E
1/2
= 77 mV; second der ivat ive polar ogr am,
E
1/2
= 72 mV. The r esolut ion of fir st der ivat ive d.c. polar ogr aphy is consider ably bet t er
t ha n t ha t of r egula r d.c. pola r ogr a phy. The r esolut ion of second der iva t ive d.c.
polar ogr aphy is somewhat bet t er t han t hat of fir st der ivat ive d.c. polar ogr aphy. The Fig.
11.5 shows t he impr oved r esolut ion of t he fir st der ivat ive d.c. polar ogr aphy over t hat of
r egular d.c. polar ogr aphy.
0.45
E
0
vol ts vs S. C. E.
0.49 E
+++
In
E
++
Cd
0.65
16 Feb. 1961
0. 1 a/ mi n.
di
dt
ave
4.
110 In and 2110 Cd
in 0.1 0.1 KCl
5.
(Indicated by plotted
points)
NET DERIVATIVE POLAROGRAM :
SUM OF CONSTITUENT DERIVATIVE
POLAROGRAMS
4 +++ 4 ++
M M
M
CONSTITUENT
DERIVATIVE
POLAROGRAM :
1. 0.1 M KCl
2. 110 IN in
0.1 KCl
3. 210 Cd in
0.1 KCl
4 +++
4 ++
M
M
M
M
CONDITIONS :
O.R.N.L. model Q-1988-ES polarograph
Quadruple parallel-T, RC current ave.
filter
Sargent 2 to 5 second capillary Initial
potential 0.45 volts vs S.C.E
Scan rate 0.02 volts per minute
Supporting electrolyte is 0.1 KCI
Current range is 5 microamperes full scale
M
2
3
1
1
Fi g. 11.4 : Compar ison of net der ivat ive polar ogr am wit h sum of const it ut ent
der ivat ive polar ogr ams.
The polar ogr ams of In
3+
and Cd
2+
ar e shown in t he Fig. 11.6. For mor e det ails
r elevant lit er at ur e may be consult ed.
Rela t ive r esolut ion of sinusoida l a .c., squa r e wa ve, a nd fir st der iva t ive d.c.
polar ogr aphy.
The evaluat ion of n by measur ement of a fir st der ivat ive d.c. polar ogr am is illust r at ed
in Fig. 11.7.
Br eyer and Bauer [11] r epor t ed t hat t he widt h of t he sinusoidal a.c. polar ogr aphic
wave at half-height in millivolt s is given by
9 0 5 .
n
...(7)
This is for simple diffusion cont r olled pr ocess t hat ar e consider ed r ever sible at t he
sinusoidal a.c. volt age fr equency t hat is used.
Bar ker [2] r epor t ed for a simple r ever sible wave, t hat at 25C, t he widt h of t he
squar e wave polar ogr am at half it s maximum height in millivolt s is
9 0 4 .
n
...(8)
Also, for a peak t o peak amplit ude of t he squar e wave volt age t hat is much less t han
RT/ nF (condit ion being opt imum).
Ther e is, however , no differ ence in t he r elat ive r esolving power of t hese met hods of
polar ogr aphy in case t he wor king condit ions ar e opt imum for sinusoidal a.c., squar e
wave, and fir st der ivat ive d.c. polar ogr aphy.
11.2.5 Mathematical Resolution of Overlapped First Derivative d.c. Polarograms
In pr act ice, t her e will be many cases wher e successive const it uent fir st der ivat ive d.c.
polar ogr ams over lap t o t he ext ent t hat t he peaks in t he net polar ogr am will be incr eased
by t he over lap even t hough t he r esolut ion of fir st der ivat ive polar ogr aphy exceeds t hat
of r egular polar ogr aphy. If t he r ecor ded polar ogr ams ar e of t heor et ical for m, t he amount
of over lap is not being incr eased by t he polar ogr aphic cir cuit r y and depends only upon
t he r elat ive n, F E
1/2
, and concent r at ion values.
The following condit ions ar e r equir ed in or der t o use mat hemat ical analysis t o r esolve
over lapped fir st der ivat ive d.c. polar ogr ams.
1. The D.M.E. char act er ist ics must be const ant for t he dur at ion of t he measur ement .
2. The E
1/2
s must be r epr oducible and independent of concent r at ion.
3. The magnit ude of a der ivat ive polar ogr am at any fixed pot ent ial must be dir ect ly
pr opor t ion t o concent r at ion over t he concent r at ion r ange involved as pr edict ed
by t he equat ion [4]. The net der ivat ive polar ogr ams must be equal t o t he sum
of t he const it uent der ivat ive polar ogr ams as pr edict ed in t he equat ion under
r efer ence [14].
Four exper iment al polar ogr am showing t he addit ivit y of polar ogr am of individual
pr ocesses ar e r epr oduced as shown in Fig. 11.9. Polar ogr am No. 1, is a fir st der ivat ive
d.c. polar ogr am of t he suppor t ing elect r olyt e polar ogr am No. 2 is a fir st der ivat ive d.c.
polar ogr am of 1 10
4
M ln
3+
in t hat suppor t ing elect r olyt e. Polar ogr am No. 3 is a fir st
der ivat ive d.c. polar ogr am of 2 10
4
MCd
2+
in t hat suppor t ing elect r olyt e. Polar ogr am
No. 4 is a fir st der ivat ive d.c. polar ogr am of a solut ion cont aining bot h
1 10
4
M ln
3+
and 2 10
4
MCd
2+
...(9)
in t hat suppor t ing elect r olyt e, t he plot t ed point s have been obt ained by gr aphically
summing polar ogr ams No. 1, 2 and 3. It is seen t hat t her e is a good agr eement bet ween
t he exper iment al net polar ogr am, No. 4, and t he act ual sum of t he const it uent
polar ogr ams, t he plot t ed point s.
It is t o be not ed t hat in t he above figur e t he fir st peak of t he net fir st der ivat ive d.c.
polar ogr am does not occur at t he E
1/2
for t he fir st species. This is a geomet r ical effect
and not a shift in E
1/2
in solut ion cont aining bot h species. This illust r at es t he impor t ance
of measur ing all of a ser ies of net polar ogr am at t he t wo chosen fixed pot ent ials r at her
t han at sumit pot ent ials in t he net polar ogr ams.
11.2.6 Mathematical Resolution of Regular Polarography Compared to First
Derivative d.c. Polarography
The effect s of n, E
1/2
and r elat ive concent r at ions on t he degr ee of r esolut ion of t wo
polar ogr aphic waves have been discussed by Mller [19]. Also it was point ed out t hat
iR losses would degr ade t he r esolut ion. He also concluded t hat , in t he absence of iR
dist or t ion, t he separ at ion of t he E
1/2
s would have t o be at least 180/n mV in or der t o
measur e t he t wo wave height s independent ly. Even when t wo waves ar e so sever ely
over lapped t hat t he net polar ogr am looks like a single wave, t he mat hemat ical met hod
can be applied t o calculat e t he height of each of t he t wo equivalent waves making up
t he net wave.
The accur acy wit h which t wo over lapped r egular polar ogr ams can be r esolved
mat hemat ically depends on t ha pr ecision wit h which t he ser ies of measur ement s can be
made at t he fixed pot ent ial E.
11.2.7 D.C. Polarography in Non-aqueous Solvents and Particularly in Solvent
Extracts
Polar ogr aphic invest igat ions and analyses have been made in gr eat number of or ganic
solvent s, solvent mixt ur es and wat er -or ganic solvent mixt ur es. In t he case of non-aqueous
or ganic solvent s one of t he difficult ies is t hat t he specific r esist ance of such solut ions,
even aft er suppor t ing elect r olyt e is added, can be high enough t o r esult in lar ge iR
volt age in t he solut ion. These can be pr event ed fr om affect ing t he for ms of t he r ecor ded
polar ogr ams if a cont r olled-pot ent ial polar ogr aph is used pr oper ly. The iR
bulk
losses ar e
not seen by t he pot ent iost at input of t he t ip of t he r efer ence elect r ode is locat ed out side
t he cur r ent pat hs in t he solut ion, and in cases wher e iR inner is of significant magnit ude.
In t his case only a small por t ion of t hese losses is seen by t he pot ent iost at input of t he
t ip of t he r efer ence elect r ode is wit hin about 0.1 of t he r adius of t he D.M.E. dr op fr om
t he sur face of t he D.M.E. dr op. Cont r olled-pot ent ial d.c. polar ogr aphy should, t her efor e,
have special advant ages for polar ogr aphic wor k in non-aqueous solvent s. Some species
ar e insoluble in wat er but under go useful elect r ochemical r eact ions in non-aqueous
solvent s or in solvent mixt ur es. In some cases, cer t ain ions cannot be det er mined in
wat er polar ogr aphically because of specific solvent effect s or int er fer ence fr om hydr ogen
wave or by cat alyt ic hydr ogen waves. The combinat ion of polar ogr aphy and a liquid
chr omat ogr aphic column by Kemula [9] is pr omising for gas-liquid chr omat ogr aphy for
t he analysis of complex mixt ur es of or ganic compounds. This is because it is difficult and
in some cases impossible t o find a st at ionar y phase on which all t he component s of a
mixt ur e can be separ at ed.
El e ct r och e mi ca l Re q u i r e me n t s for P ol a r ogr a p h y i n Non -a q u e ou s Sol ve n t s ,
Sp e ci a lly i n Solve n t -e xt r a ct s : In t he case of polar ogr aphy, it is advant ageous t o have
t he pr esence of an excess of ionized suppor t ing elect r olyt e [6]. The high dielect r ic const ant ,
alt hough favour s t he for mat ion of ions and t ends t o incr ease t he solubilit y of a suppor t ing
elect r olyt e. This is not a sufficient condit ion t o ensur e t hat an elect r ochemical r eact ion
can be car r ied out . This fact is well known in t he elect r odeposit ion of met als fr om
or ganic solut ions [1].
Cont r olled-pot ent ial d.c. polar ogr aphy of met al complexes in solvent ext r act s.
The feasibilit y and usefulness of such complexed met als in solvent ext r act s has been
invest igat ed polar ogr aphically [4].
The met hod offer s cer t ain advant ages over polar ogr aphy in aqueous media.
1. The subst ance t o be det er mined can be concent r at ed sever al t old dur ing t he
ext r act ion st ep, t hus incr easing t he sensit ivit y of t he met hod and mat r ix element s
t hat int er fer e ar e r emoved.
2. A separ at e st r ipping st ep is not r equir ed. Also, t he possibilit y exist s of per for ming
polar ogr aphic analysis in an or ganic solvent wit h species t hat ar e not st able in
aqueous solut ion.
11.3 THEORY, PRINCIPLES AND APPLICATIONS
(a) Cycli c a n d P u lse Tech n i qu es : A belief r eview of a number of t echniques which
ar e r egar ded as offshoot s of st at ionar y-elect r ode volt ammet r y ar e being descr ibed
in t his sect ion.
I n os ci l l ogr a ph i c or
cat hode-r ay polar ogr aphy [7],
a r apid linear volt age sweep is
applied t o a dr opping elect r ode
near t he end of t he dr op life.
The r esult ing cur r ent pot ent ial
cu r ve i s di s pl a yed on t h e
scr een of an oscilloscope. Her e
t h e vol t a ge a ppl i ed t o t h e
elect r odes is a mplified a nd
con n ect ed t o t h e ver t i ca l
deflect ing plat es.
However , in t his applica-
t ion t he oscilloscope mer ely
r epl a ces t h e ga l va n omet er
a n d br i n g n o fu n da men t a l
change in t he polar ogr aphic
inst r ument at ion and because
of t his t he t er m oscillogr aphic
polar ogr aphy usually does not
include t he st udy of cur r ent
t ime cur ves.
A r at her high sensit ivit y is at t ained as a cause of t he lar ge r at e of change of pot ent ial
t hat is needed t o minimize var iat ions of dr op ar cs and deviat ions fr om linear diffusion
equat ions, but t his, in t ur n, gives r ise t o r at her lar ge char ging cur r ent s t o t he equat ion
(11.8).
i
e
/ i
p
= 0.023v
1/2
n
3/2
C
0
...(1)
wher e i.e., is t he char ging cur r ent , by assuming t ypical values for x and D
0
. Wit h v =
0.003 v/sec, n = 1, and C
0
= 0.01 mM. The char ging cur r ent is near ly 15% of t he peak
cur r ent and it would be even lar ger for an ir r ever sible pr ocess.
11.3.1 Single Sweep Methods
The shape of a cur r ent volt age cur ve depends on t he nat ur e of t he depolar izing volt age.
St ar t ing wit h a simple linear volt age sweep, applied t o t he elect r ode (lat e in t he life of
t he dr op) when t he gr owt hr at e of t he dr op-sur face var ies only slight ly wit h t ime (see
Fig. 11.5). The scr een wit h a long aft er glow is advant ageous in t his met hod.
(a) Ch a r gi n g Cu r r e n t : In case only when pur e suppor t ing elect r olyt e is pr esent in
t he exper iment al solut ion, t he cur ve obt ained shows t he char ging cur r ent ending
in an elect r olyt ic cur r ent due t o r educt ion of t he cat ion of t he suppor t ing
elect r olyt e at a negat ive pot ent ials, see Fig. 11.6. The for mula
g
E
t
k
t
1
t
Fi g. 11.5 : Compar ison of t he t ime dependence of t he
change in sur face ar ea of t he dr op q (upper curve) and of
t he volt age sweep E (lower curve) applied t o t he elect rode;
t
k
quiet per iod, t
1
dr op t ime
Fig. 11.6 : Current -pot ent ial curves for t he support ing elect rolyt e 1 N KOH :
left : single sweep, r ight : mult i-sweep
i
c
=
dQ
dt
...(2)
is gener ally used for t he char ging cur r ent , wher e Q is t he t ot al char ge on t he
elect rode at t ime t (Q can be expr essed as pr oduct of t he elect r ode ar ea q and
of t he specific char ge : (Q = q).
Hence i
c
=
dQ d dq
q
dt dt dt
= +
...(3)
ar r anging t he equat ion t akes t he for m :
i
c
=
d dE dq
q
dE dt dt
+
...(4)
wher e E denot es t he elect r ode pot ent ial.
The pot ent ial, in classical polar ogr aphy may be r egar ded as const ant dur ing t he life
of a single dr op. The fir st t er m is t hen zer o and t he following equat ion for t he char ging
cur r ent is t hus obt ained :
i
c
= EC '
2
3
dq
dt
=
0.85EC ' m
2/2
t
1/3
...(5)
The sur face of t he elect r ode, in oscillogr aphic met hods may be consider ed const ant
dur ing a single sweep. The second t er m in equat ion 3 may t hen be neglect ed, and one
can obt ain,
i
c
=
d dE
q
dE dt
...(6)
for t he char ging cur r ent .
The expr ession d/dE = d (CE)/dE = Cd, specific capacit y. It is t he capacit y of 1 cm
2
of t he elect r ode sur face at a given pot ent ial. It is called differ ent ial capacit y so as t o
dist inguish it wit h t he int egr al capacit y C, which aslo appear s in polar ogr aphic char ging
cur r ent . The t hir d coefficient in equat ion (6) is a const ant and indicat es t he r at e of
change of t he applied volt age v. Finally t he equat ion for t he char ging cur r ent r eads as :
i
c
= C
d
qv ...(7)
In pr inciple, it t hen follows t hat t he char ging cur r ent shows t he dependence of
di ffer en t i a l ca pa ci t y on
pot ent ial. The value of t he
differ ent ia l ca pa cit y is a n
i mpor t a n t pa r a met er
char act er izing t he elect r ode
double-layer specially is cases
wh en s u r fa ce-a ct i ve
subst ances ar e adsor bed. The
enables us t o follow r apidly
t he a dsor pt ion of sur fa ce-
a ct i ve s u bs t a n ces a t t h e
elect r ode over a wide r ange
of pot ent ials. The adsor pt ion
of t h e s u bs t a n ce u s u a l l y
occu r s wi t h i n a defi n i t e
pot en t i a l r egi on . Th i s
ch a n ges t h e di ffer en t i a l
capacit y of t he elect r ode and
consequent ly t he cha r ging
cur r ent . A Shar p maximum
Fig. 11.7 is char act er ize due t o t he inst ant aneous incr ease in differ ent ial capacit y
accompanying t he r ear r angemet of elect r ode double layer is t he pot ent ial at which t he
subst ance adsor bs or desor bs.
The for egoing equat ion (6) also holds for t his peak for t he char ging cur r ent . The
char ging cur r ent r ises as a linear funct ion of t he incr easing slope v of t he volt age sweep.
Many subst ances specially, or ganic exhibit capacit y phenomena. Hence oscillogr aphic
polar ogr aphy opens addit ional possibilit ies for analysis as compar ed t o classical
polar ogr aphy.
11.3.2 Electrolytic Current
Re ve r s i b le Ele ct r od e P r oce s s e s : The pr esence of a depolar izer in t he solut ion causes
an incr ease in t he elect r olyt ic cur r ent wit h r ising pot ent ial. The depolar izer is gr adually
Fi g. 11.7 : Char ging cur r ent for 0.5 M Na
2
SO
4
in t he
presence of oct yle alcohol. Mult i-sweep met hod. The current
peaks indicat e adsorpt ion and desorpt ion of t he surface film.
+i
i = 0
i
E
exhaust ed by elect r olyt e pr ocess at t he elect r ode sur face. Fr esh depolar izer is supplied
by diffusion and t he diffusion layer ext ends int o t he solut ion. The r at e of t he elect r ode
pr ocess incr eases wit h r ising elect r ode pot ent ial, but t he t r anspor t of depolar izer is
simult aneously r et ar ded. Consequent ly, t he cur r ent incr eases up t o a cer t ain maximum
value fr om which it t hen decr eases. Randles [8] and Sevik [9] independent ly solved
pr oblem for a r ever sible elect r ode pr ocess. The equat ion of t he cur r ent is gover ned by
linear diffusion of t he subst ance t owar ds an elect r ode, t he pot ent ial of which is changing.
The cur r ent pot ent ial cur ve can be expr essed by a t abulat ed funct ion passing t hr ough
a maximum. This maximum or peak cur r ent is an impor t ant value in oscillogr aphic
polar ogr aphy. It s significance cor r esponds t o t hat of bot h t he wave-height and t he half-
wave pot ent ial for classical polar ogr aphic cur r ent -volt age cur ve. The maximum cur r ent
is given by t he for mula :
i
max
= k
1
qn
3/2
cD
1/2
v
1/2
(A) ...(8)
wher e k
1
is a combined const ant depending on t he elect r ode pr ocess; q, t he elect r ode
ar ea (in cm
2
), which is consider e const ant dur ing t he volt age sweep, n t he number of
elect r odes, c t he depolar izer concent r at ion in moles/cm
3
, D it s diffusion coefficient (in
cm
2
. sec
1
) and v t he r at e of change of elect r ode pot ent ial (dE/ dt, in V sec).
Accor ding t o pr evious wor ker s, t he r at io of t he maximum cur r ent t o t he cur r ent on
t he falling par t of t he cur ves is given by
1 2 max
n
i
k
i
=
...(9)
in r ever sible, and in ir r ever sible elect r ode pr ocess by
( )
1 2
a
max
n
i
k '
i
=
...(10)
The const ant s k and k depend solely on pot ent ial. Fr om t he r at io i
max
/i an empir ical
met hod for det er mining t he number of elect r on for a r ever sible elect r ode pr ocess could
be used. The condit ion being t hat t he dict at ion of elect r olysis does not exceed sever al
seconds and t he differ ence bet ween linear and spher ical diffusion is not significant .
Rever sible elect r ode pr ocesses ar e char act er ized by st eep cur ve and shar p peaks
(Fig. 11.8) r ight cur ve. The pot ent ial cor r esponding t o t hese peaks is independent of
concent r at ion and by 29/n mV (at 25C) mor e negat ive t hen E/2 is r educt ions of mor e
posit ive in oxidat ions.
I r r e ve r si b le Ele ct r od e P r oce sse s : Delahay [3] was t he pioneer t o der ive t he
cor r esponding mat hemat ical funct ion. Accor ding t o which t he expr ession for t he peak
height i
max
is st at ed as follows :
i
max
= k
2
qn (n
a
)
1/2
cD
1/2
v
1/2
(A) ...(11)
This for mula is similar in for m t o t he above equat ion (7) except t hat t he t er m n (n)
r eplaces n
3/2
. Her e, is t he t r ansfer coefficient (0 < <1) and n
a
t he number of elect r ons
exchanged in t he slowest st ep of t he elect r ode pr ocess (0 < n
a
n). The value of t he
const ant k
2
is 2.99 at 10
5
at 25C. The pr oduct n
a
decides t he shape of t he
ir r ever sible cur ve Fig. 11.6
Th e h et er ogen eou s r a t e
con s t a n t
0
e
k for t h e
el ect r ode pr oces s i s
r esponsible for t he posit ion
of t h e cu r ve on t h e
pot ent ial axis. Since is
less t han 1 and n
a
is oft en
smaller t han n, t he peak
for an ir r ever sible pr ocess
is lower t han t hat for a
r ever sible pr ocess. It loses
it s a cut e for m Fig. 11.8
(l eft cu r ve) bu t i t s
pot ent ial does not change
wit h concent r a t ion. The
whole cur ve is dr awn out and is shift ed t o higher pot ent ials i.e., t o mor e negat ive ones
in r educt ion and in oxidat ion t o mor e posit ive ones wit h decr easing r at e const ant
0
e
k
The char act er of t he elect r ode pr ocess can be r eadily assessed fr om t he appear ance of
t he oscillogr aphic cur ve. Accor ding t o t he char act er of t he elect r ode pr ocess Mat suda
and Ayabe [6] pr ovide a gener al t heor et ical analysis of t he oscillogr aphic cur r ent -pot ent ial
cur ves for simple elect r ode pr ocesses wit h a single pot ent ial-det er mining st ep under t he
condit ions of linear diffusion. These aut hor s dist inguished t hr ee cases, accor ding t o t he
char act er of t he elect r ode pr ocess and also mat hemat ical equat ions wer e pr esent ed :
1. Rever sible pr ocesses wit h a het er ogeneous r at e const ant
0
e
k lager t han 0.3
( ) nv cm. sec
1
at 25C;
2. a quasi-r ever sible pr ocess wit h
0
e
k r anging fr om 0.3 ( ) nv t o 2.10
5
( ) nv cm.
sec
1
; and
3. Ir r ever sible pr ocess for which
0
e
k is less t han
2.10
5
( ) nv cm. sec
1
.
It t her efor e follows fr om t hese equat ions t hat in a quasi-r ever sible pr ocesses t he
peak incr eases non-linear ly wit h v
1/2
in cont r ast t o t he ot her t wo t ypes wher e t his
dependence is linear .
The cla ssifica t ion given shows t ha t t he t er m r ever sibilit y depends on t he
exper iment al condit ion. On incr easing v, t he number of pr ocesses t hat can be descr ibed
as r ever sible decr eases. The same effect is obt ained by eit her decr easing t he dr op t ime
or employing a st r eaming mer cur y elect r ode inst ead of t he dr opping mer cur y elect r ode
in classical polar ogr aphy.
Fi g. 11.8 : Oscillogr aphic cur ve (linear volt age sweep) : left
ir r ever sible t hr ee-elect r on r educt ion (Cr O
2
2
in 1 N KOH); right
r ever sible t hr ee elect r on r educt ion (Bi
3+
in 1 N HCl)
a
b
c
d
e
f
E
An oscillogr aphic cur ve appear s wit h t wo peaks
on t he scr een, if t he depolar izer is r educed in a t wo-
st ep elect r ode pr ocess (Fig. 11.9). It was demonst r at ed
by pr evious wor ker s t hat bot h peaks behave as if t hey
belonged t o t wo independent pr ocesses, r egar dless of
t he r at es of elect r ode pr ocesses for t he t wo st eps. The
t wo pea ks, wh en su fficien t ly a pa r t , n o mu t u a l
int er act ive of t he peaks occur and t hey ar e dir ect ly
pr opor t ional t o t he concent r at ion and t o t he squar e-
r oot of t he r at e of var iat ion of pot ent ial v.
11.3.3 Kinetic Currents
Oscillogr aphic cur ves have a char act er ist ic shape.
These cur ves have t he shape of convent ional cur r ent
volt age cur ve Fig. 11.10. The height of t he cur ve is
independent of v. The same r elat ion holds as for
polar ogr aphic kinet ic cur r ent s. The oscillogr aphic
cur ve for t he Br dicka [1] pr ot ein r eact ion show a
st riking similarit y t o t he classical polar ogr aphic cur ve.
Obviously t he cur r ent is gover ned by t he dependence
of t he cat alyt ic r eact ion on pot ent ial.
11.3.4 Types and Forms of Voltage Sweeps
By compar ing t he pot ent ial of t he peaks for r ising
a n d fa l l i n g s weeps , con cl u s i on s r ega r di n g t h e
r ever sibilit y of t he pr ocess can be dr awn. Anodic
cur r ent s for t he oxidat ion of subst ances in solut ion
a n d for t h e dis s olu t ion of a ma lga ms a r e mor e
convenient ly st udied wit h polar izat ion fr om negat ive t o posit ive pot ent ials. (Fig. 11.9
(b). The quiescent per iod of sweep is ut ilized for r educing t he depolar izer fr om t he
solut ion at const ant negat ive volt age, par t icular ly for pr epar ing t he amalgam by
deposit ing t he met al on mer cur y. The cat hodic and anodic maxima for per fect ly r ever sible
pr ocesses ar e 58/n mV apar t . In or der t o st udy r ever sibilit y, an equilat er al t r iangular
volt age sweep is par t icular ly advant ageous (Fig. 11.9 (c)). The depolar izer , which is
r educed in t he fir st phase is immediat ely r eoxidized in t he next phase and vice-ver sa.
The r esult ings cur r ent volt age cur ve has t wo br anches :
(i) cat hodic and a r ever se
(ii) anodic one (Fig. 11.10). The r ever sibilit y of t he peaks is indicat ed by t he r elat ive
posit ions of t he r educt ion and oxidat ion peaks.
11.4 MULTI-SWEEP METHODS
An oscilloscope wit h a nor mal cat hode r ay like wit hout aft er glow is used for t he mult i-
sweep met hod. A st able cur ve appear ing on t he scr een of t he oscilloscope can be easily
Fi g. 11.9 : Var ious t ypes of
volt age sweeps applied t o t he
elect r odes in oscillogr a phic
polarography
measur ed by alt er nat ing sawt oot h. Volt age sweep is
applied t o t he elect r ode eit her lat e in t he life of t he dr op
or dur ing t he whole per iod of it s gr owt h. This syst em
r esembles t he single-sweep met hod. The t r iangular
volt age sweeps can also be applied under t he same
condit ions. The met hod can be ut ilized in analyt ical
chemist r y.
In cases, wher e t he alt er nat ing volt age sweep is
applied t o t he elect r odes dur ing t he gr owt h of t he dr op,
t he cur r ent incr eases as a linear funct ion of t he dr op
sur face-ar ea and a ser ies of incr easing cur ves can be
observed on t he screen. These curves as already described
ar e chiefly used in qualit at ive invest igat ions due t o t he
difficult y in evaluat ion.
Wit h t r iangular volt age sweeps t he oxidat ion and
r educt ion per iods ar e of equal dur at ion and hence bot h
br a nches of t he cur r ent -volt a ge cur ve a r e equa lly
developed. As r epor t ed by pr evious aut hor s in t he cour se of sever al init ial cycles of t he
t r iangular volt age sweep t he cat hodic cur r ent decr eases somewhat and t he anodic cur r ent
incr eases at t he const ant elect r ode sur face unt il an equilibr ium bet ween t he cyclic
elect r ode pr ocesses and diffusion is at t ained. Delahay [39] int r oduced a r elay phase
aft er each sweep of t he saw-t oot h volt age. Dur ing t his per iod t he condit ion in t he
elect r ode int er face ar e r est or ed.
11.5 APPARATUS FOR APPLIED VOLTAGE OSCILLOGRAPHIC POLAROGRAPHY
Mat heson and Nichols [26] developed t he fir st oscillogr aphic assembly for st udying t he
polar izat ion of t he dr opping mer cur y elect r ode wit h volt age sweeps. They t est ed t he
polar izat ion by sine-wave and sawt oot h volt age sweeps by single sweeps on r apidly
falling dr ops in t he analysis of solut ions cont aining sever al cat ions. The lar ge char ging
cur r ent pr esent ed a dist ur bing fact or in pr act ical applicat ions. In addit ion t o dist or t ion
owing t o t he pot ent ial dr op (iR), t he char act er ist ic peaks gr adually decr ease ans become
r ounded. This is because an incr easing t he r esist ance, t he exper iment al condit ions
appr oach t hose for applied cur r ent oscillogr aphy.
An oscillogr aphic appar at us for st udying polar izat ion cur ves wit h a volt age st ep has
been const r uct ed by Vogel [31] as alr eady indicat ed.
The mult isweep inst r ument s wit h saw-t oot h impulses ar e used mor e ext ensively. By
decr easing t he fr equency sufficient ly t his met hod passes int o single-sweep oscillogr aphy.
This t ype of appar at us was descr ibed by Delahay [3]. Valent a [10] const r uct ed a univer sal
oscillogr aph giving volt age sweeps of all t he t ypes. This was used for st udying elect r ode
pr ocesses.
11.6 CONTROLLED CURRENT OSCILLOGRAPHIC POLAROGRAPHY
The basic cir cuit is t he same in t he met hod for elect r olysis wit h single cur r ent impulse
and alt er nat ing cur r ent oscillogr aphy. A high volt age, i.e., sever al hundr ed volt s is
Fi g. 11.10 : Reduct ion of Tl
+
in
1 M Na
2
SO
4
by an equilat er al-
t r iangular volt age sweep
applied t o t he polar ogr aphic cell t hr ough a lar ge r esist ance R fr om 10 t o 100 megohms
under t hese condit ions t he r esist ance in t he cell and t he elect r omot ive for ce of polar izat ion
ar e negligible in compar ison wit h ot her quant it ies in t he cir cuit . The cur ent int ensit y
given by t he volt age sour ce and by t he r esist ance does not depend on t he pr ocess
occur r ing at t he elect r odes. These pr ocesses manifest t hemselves by var iat ions in t he
elect r ode pot ent ials. In polar ogr aphy wher e t he pot ent ial of one of t he elect r ode r emains
const ant , only t he polar izable elect r ode changes it s pot ent ial.
The pot ent ial differ ence bet ween t he elect r odes r esult ing fr om t he passage of cur r ent
is amplified and applied t o t he hor izont al plat es of t he oscilloscope. The t ime base is
connect ed t o t he ot her pair of deflect ing plat es. The r esult ing pot ent ial t ime cur ve on
t he scr een shows t he var iat ion in
pot en t i a l of t h e pol a r i za bl e
elect r ode for a given cur r ent as a
fu n ct i on of t i me. Du e t o t h i s
dependence, t he met hod is t er med
chr onopot ent iomet r y. The met hod
i s fu l l y des cr i bed i n pr evi ou s
chapt er .
Al t e r n a t i n g Cu r r e n t
Os ci l l ogr a p h i c P ol a r ogr a p h y :
Th e met h od wa s fi r s t of a l l
int r oduced by Her ovsky as ear ly
a s 1941 [25]. The t echnique is
a na logous t o pola r iza t ion wit h
a l t er n a t i n g vol t a ge. Th e t i me
depen den ce of t h e a l t er n a t i n g
cur r ent used may ver y t r iangular
a n d s qu a r e wa ve a l t er n a t i n g
cur r ent s have been t est ed.
(a) P ot e n t i a l -Ti me Cu r ve s : The cur r ent for following fundament al E t cur ves is
shown in t he Fig. 11.11. In or der t o pr event t he consumpt ion of cur r ent only
dur ing alt er nat e dissolut ion and deposit ion of mer cur y at t he polar izable
elect r ode, a dir ect cur r ent is super imposed on t he alt er nat ing cur r ent . This
allows polar izat ion of t he elect r ode up t o t he pot ent ial for deposit ion of cat ions
of t he suppor t ing elect r olyt e. In case t he dir ect and alt er nat ing volt ages ar e of
t he same or der (10
2
V) and similar ly t he r esist ances in t he cir cuit (10
5
t o 10
6
),
t he condit ions for t he cont r olled cur r ent ar e maint ained. Wit h r egar d t o t he
dir ect ion of t he cur r ent t wo br anches on t he cur ve can be dist inguished : t he
ascending cat hodic br anch and t he descending anodic br anch. In one half-per iod
t he elect r ode funct ions as a cat hode and in t he next half per iod as an anodie.
The t ime-base Z is synchr onized wit h t he polar izing cur r ent so t hat s st at ionar y
fig. is obt ained on t he scr een (Fig. 11.12).
A
Rs
B
E O
Z
Fi g. 11.11 : Cir cuit for t r acing pot ent ial-t ime cur ves
dur ing polar izat ion by alt er nat ing cur r ent : Asour ce
of a.c. volt age; Bsour ce of d.c. volt age; R
s
r esist ance;
Eelect r olysis cell; Ooscillogr aph; Zt ime base
(b) Ch a r gi n g Cu r r e n t s : The suppor t ing
el ect r ol yt e i s n ot el ect r ol ys ed a t t h e
elect r ode and no depolar izer is pr esent in
t he solut ion, t he r esult ing cur ve depict s
t he char ging cur r ent . The condit ion being
t he amplit ude of t he cur r ent is quit e small.
In a fir st appr oximat ion it may be r egar ded
t hat t he elect r ode capacit y dur ing a single
cycle a s con st a n t a n d in depen den t of
pot ent ial : consequent ly it may be wr it t en
for t he char ging cur r ent of t he elect r ode
as capacit or :
i
c
=
dQ dE
C
dt dt
| |
=
|
\ .
...(12)
11.7 PULSE POLAROGRAPHY
In pulse polar ogr aphy [1,2] a single squar e-wave volt age impulse having a dur at ion of
about 40 m sec is applied t o each dr op at a pr edet er mined inst ant aft er it s bir t h, and
t he amplit ude of t he successive pulse ar e incr eased linear ly wit h t ime. The char ging
cur r ent decays r apidly aft er t he init ial change of volt age. Since t he dur at ion of t he pulse
is much longer t han in squar e wave polar ogr aphy a much longer t ime can be allowed
for t he char ging cur r ent t o decay. The r esist ance of t he cell is much less impor t ant , so
t hat consider ably mor e dilut e suppor t ing elect r olyt es can be employed. The r elat ively
slowly decar ying far adaic cur r ent t hat cont inues t o flow dur ing t he second 20 m sec of
t he pulse is r ecor ded against t he pulse amplit ude. The r esult ing cur ve has t he same
shape as an or dinar y polar ogr aphic wave, and t he limit of det ect ion is impr oved t o a
level t hat is pr obably of t he or der of 10
5
mM. Not ewor t hy fact is t hat t he limit of
det ect ion must be ver y near ly t he same for ir r ever sible pr ocesses as for r ever sible ones.
Der ivat ive pulse polar ogr aphy may be called as a second kind of pulse polar ogr aphy
[32]. It yields cur ve which ar e essent ially t he der ivat ives of t hose obt ained by t he
t echnique alr eady descr ibed. A single squar e wave volt age pulse having a dur at ion of
about 40 m sec is again applied t o each successive dr op at a pr edet er mined inst ant aft er
t he fall of it s pr edecessor , but t he pulses have a const ant amplit ude of about 50 mv and
ar e super imposed on a r elat ively slow linear n pot ent ial sweep. Dur ing t he fir st half of
t he pulse t he char ging cur r ent decays. Dur ing t he second half t he incr ease of cur r ent
is r ecor ded. The r esult ing incr ease of far adaic cur r ent pr oduced by a fixed change of
pot ent ial is plot t ed against t he pot ent ial. Thus a peak is obt ained at t he inflect ion point
of t he dic or pulse polar ogr am. The height of t he peak is pr opor t ional t o t he slope
di/ dE of t he polar ogr am which is descr ibed by t he eqn. [13].
E
rr/4
E
rf /4
= 3.76/n millivolt s ...(13)
This is smaller for ir r ever sible waves for which = n
a
t han for r ever sible ones for
which = n, and consequent ly t he sensit ivit y and limit of delect ion ar e poor er for
Fi g. 11.12 : Pot ent ial t ime cur ve
obt ained by polar izing t he elect r ode
wit h a sinusoidal a.c. cur r ent Zn
2+
in
1 M KOH
ir r ever sible waves. For a subst ance t hat under goes a r ever sible t wo-elect r on r educt ion
t he limit of det ect ion is of t he or der of 10
6
mM, r oughly an or der of magnit ude lower
t han in or dinar y pulse polar ogr aphy. On t he ot her hand, incr easing-amplit ude pulse
polar ogr aphy is bet t er suit ed t o wor k wit h ir r ever sible waves because t he height of t he
peak obt ained in t he der ivat ive t echnique is affect ed by any change in t he exper iment al
condit ions t hat r esult s in a var iat ion of n
a
.
The char act er ist ics of all t hese t echniques ar e br iefly summar ized for convenient
r efer ence in Fig. 11.13.
11.8 STRIPPING ANALYSIS
Ther e ar e t wo kinds of st r ipping analysis. Anodic st r ipping is used t o det er mine met al
ions t hat ar e r educed t o met hallic st at e dur ing t he pr eliminar y elect r olysis. This is
based on anodic cur r ent s obt ained when t he met als ar e r eoxidized.
CYCLIC AND PULSE TECHNIQUE
E
5 sec
2 sec
T
0
.
5
2
V
Instant of
drop fall
0
.
5
2
V
0.02 sec
E
1 2 3
0.0010.1 sec
E
E
1
2
3
Response
obtained
Signal
applied
Technique
Single-sweep
oscillographic
polarography
Multisweep oscillographic
polarography
(a) (b)
E
T
5 sec.
0.001 1 sec.
Instant of
drop fall
0
.
5
2
V
T
E
B
E
A
+ne
ne
3
1
3
E
Reversible couple
E E
Cessation of
reduction of A
Oxidation of B
Reduction
of C
1
2
2
1
Cessation of
catholic process
Reoxidation
of reduced form
Irreversible couple
Cyclic triangular-wave
oscillographic polarography
Triangular-wave oscillographic
polarography
(c) (d)
Cat hodic st r ipping is used t o det er mine halides, t hiols et c., which give anodic waves
at met allic elect r odes. The condit ion being t hat t he half-r eact ion yields an insoluble salt
t hat adher es t o t he elect r ode sur face. A cat hodic cur r ent is obt ained fr om t he r educt ion
of t he salt which accumulat es t her e. Cat hodic st r ipping has also been used t o evaluat e
t he t hickness of t ar nish films on such met als as ir on, copper , and silver [35]. Not only
t his but bot h cat hodic and anodic st r ipping have been used t o invest igat e t he adsor pt ion
of elect r oact ive subst ances ont o iner t elect r odes.
Act ually in convent ional volt ammet r ic analysis t he measur ement of a limit ing or
peak cur r ent which depends on t he r at e at which t he subst ance being det er mined
r eaches t he indicat or elect r ode, and t hat also includes a r esidual cur r ent . As t he
concent r at ion of t his subst ance decr eases, t he r at e at which it r eaches t he elect r ode
sur face also decr eases, but t he r esidual cur r ent r emains t he same. The r esidual cur r ent
becomes a lar ger and lar ger fr act ion of t he t ot al cur r ent measur ed. The limit of det ect ion
is r eached when t he t wo become indist inguishable.
If t he subst ance being det er mined is deposit ed ont o t he indicat or elect r ode at t he
plat eau of t he wave, pr olonged elect r olysis at such pot ent ials will cause it s r educt ion or
oxidat ion pr oduct t o accumulat e at t he elect r ode sur face. As t he accumulat ion pr oceeds,
t he supply of deposit ed mat er ial at t he elect r ode sur face may become ver y much lar ger
t han t hat of t he subst ance being det er mined was init ially pr esent . In case t he deposit ed
Alternating-current
oscillographic polarography
Oscillopolarography
0.001 0.2
sec.
1001000
microamp
B
C
T
A D
C
D
B
A F
T
E
T
A
B
C
Supporting
electrolyte
alone
Cathodic
transition
Anodic
transition
Reversible couple
Supporting
electrolyte
alone
Cathodic
transition
Anodic
transition
C
E
B
A
F
D
Reversible couple
E
Supporting
electrolyte
alone
Cathodic
transition
Anodic
transition
Irreversible couple
E
Irreversible couple
dE
dT
Technique
Signal
applied
Response
obtained
(e) (f)
subst ance can be r e-oxidized or r educed it will yield a cor r espondingly lar ger limit ing
or peak cur r ent . Bot h t he sensit ivit y and t he limit of det ect ion ar e consider ably impr oved.
This is t he pr inciple of t he t echniques called st r ipping analysis.
The applicat ion of t he analysis has been much ext ensively used and st udied and is
mainly devot ed t o anodic st r ipping in t he det er minat ion of met al ions.
St r ipping elect r odes, including hanging mer cur y dr op elect r odes, mer cur y pools, and
solid elect r odes of var ious, mat er ials ar e quit e suit able t han dr opping mer cur y elect r ode,
(g) (h)
Fi g. 11.13 : Summar y of t he signals applied and t he r esponses obt ained in
a number of cyclic and pulse t echniques
Alternating-current polarography Square-wave polarography
E
0.02 sec.
E = 20 mV
a.c.
dE
dt
d.c.
= 0.1 V./min
~0.004 sec. dE
dt
d.c.
= 0.1 V./min
~30mV.
Delay line
~2 sec.
interval of
measurement
Instant of
drop fall
i (rms)
a.c.
E
d.c. C
D
B
A
G
r
i
i
Cocay of
charging
current
Variation of current
during square-wave cycle
Square wave polarogram
2.5 sec./drop
E
d.c.
wher e st r ipping analysis t akes t he for m of oscillopolar ogr aphy. St r ipping analysis have
been per for med in many differ ent ways. It can be discussed in t wo differ ent ways ; (i)
t hose in which t he pr eliminar y deposit ion is quant it at ive, and (ii) t hose in which it is
not .
The simplest t echnique is t hat in which t he quant it at ive deposit ion is followed by
quant it at ive st r ipping of t he deposit ed mat er ial. Cur ve a of Fig. (11.14) shows t he
cur r ent -pot ent ial cur ve obt ained wit h a lar ge st ir r ed mecr ur y pool elect r ode in a solut ion
cont aining zinc (II). If t he pot ent ial of t he elect r ode is maint ained at a value on t he
plat eau of t he cat hodic wave, zine ions will be r educed as r apidly as t hey r each t he
elect r ode sur face. Consequent ly quant it at ive r educt ion t o zinc amalgam will r esult on
allowing sufficient t ime. Cur ve b shows t he cur r ent pot ent ial cur ve for amalgam elect r ode
t hus obt ained.
60
0
60
120
180
240
0.3 0.7 1.1 1.5 1.9
C
u
r
r
e
n
t
i
n
m
i
l
l
i
a
m
p
e
r
e
s
E , volt s vs. S.C.E.
w. e .
Fig. 11.14 : Cur r ent -pot ent ial cur ves obt ained wit h a lar ge st ir r ed mer cur y
pool elect r ode for (a) t he r educt ion of 0.6 mM zine (II) fr om 2 F ammonia
1 F ammonia cit r at e, and ( ) t he r e-oxidat ion of t he amalgam pr epar ed by
quant it at ive deposit ion of t he zine in 50 ml of t his solut ion int o 25 ml of
mur cur y at 1.45 V vs SCE
At any pot ent ial on t he plat eau of t he anodic wave, zinc at oms ar e r apidly r e-
oxidized. The quant it y of zinc pr esent in t he or iginal solut ion can be deduced fr om a
measur ement of t he quant it y of elect r icit y consumed in t he quant it at ive r e-oxidat ion.
Quant it at ive deposit ion is feasible even wit h a small elect r ode of t he volume of t he
solut ion is small. Roger s [5] designed a cell in which a small amount like 0.02 ml of
solut ion could be elect r olyzed at a plat inum wor king elect r ode. This is employed for t he
det erminat ion of silver by anodic st ripping. Inst ead of measuring t he quant it y of elect ricit y
consumed in t he st r ipping pr ocess at a pot ent ial on t he plat eau of t he anodic wave, t he
cur r ent -pot ent ial cur ve may be r ecor ded aft er t he deposit ion is complet e (Fig. 11.15).
As a mat t er of fact , it is bet t er and mor e convenient t o use an elect r ode of small ar ea
in a subst ant ial volume of solut ion. Quant it at ive deposit ion r equir es an inor dinat e lengt h
0
1
2
+1.0 +0.5 0
Direction of
polarization
C
u
r
r
e
n
t
,
m
i
c
r
o
a
m
p
e
r
e
s
E, volt vs. S.C.E
5.3 10
5
MCd
Cd
Pb
0.02
Micro
Amp.
0
C
u
r
r
e
n
t
1.0 0 0.5
Volt vs. S.C.E
Fi g. 11.15 : Cur r ent -pot ent ial cur ves for t he Fi g. 11.16 : Anodic st r ipping volt ammogr am
anodic st r ipping of 5.6 mg of silver fr om a obt ained wit h a small mer cur y pool elect r ode
plat inum elect r ode int o dilut e nit r ic or in a st ir r ed solut ion cont aining Cd II
sulphur ic acid and for t he suppor t ing
elect r olyt e alone
of t ime, and hence it is pr efer able t o deposit only some r epr oducible fr act ion of t he
st ar t ing mat er ial. To maint ain t his t he elect r ode at a pot ent ial on t he plat eau of t he
cat hode wave for a measur ed lengt h of t ime while st ir r ing t he solut ion at const ant r at e.
This must be accur at ely r epr oduced in successive exper iment s. St ir r ing is necessar y
even wit h a st at ionar y elect r ode like hanging mer cur y dr op-st ir r ing should be st opped,
solut ion allowed t o become quiet befor e measur ement s ar e t aken. The quant it y of met al
deposit ed is pr opor t ional t o t he concent r at ion of met al ion in t he sit uat ion and also t o
t he deposit ion t ime if it is not t oo gr eat .
It is not difficult t o analyze mixur e if t he deposit ion can be car r ied out at such a
pot ent ial t hat t he subst ance being det er mined is t he only one deposit ed. In case sever al
subst ances ar e deposit ed t oget her , t he for mat ion of an alloy or solid solut ion would
make it impossible t o st r ip any of t hem quant it at ively wit hout int er fer ence fr om t he
ot her s. The t echnique has been applied t o t he det er minat ion of nickel [3] by anodic
st r ipping fr om a plat inum elect r ode int o a t hiocyanat e solut ion, and t o det er mine halides
[6] by cat hodic st r ipping aft er anodic deposit ion on t o a silver or st at ionar y mer cur y
elect r ode. Car bon-past e and waximpr egnat ed gr aphit e elect r odes have also been employed
[4].
A
B
C
D
0 0. 4 0. 8 1. 2
A
n
o
d
i
c
c
u
r
r
e
n
t
Fi g. 11.17 : Anodic st r ipping volt ammogr ams obt ained wit h hanging mer cur y
dr op elect r odes in 0.1. pot assium chlor ide aft er deposit ion for 2 min. : (A) t he
r esidual-cur r ent cur ve, (B) wit h 0.5 mM zinc(II), (C) wit h 0.5 mM zinc(II) and 0.5
mM nickel(II), (D) wit h 0.5 mM nickel(II). The scan r at e was 6.7 mV/sec. The
peak near0.1 V on curve C is at t ribut ed t o t he oxidat ion of a nickel-zinc compound
Mer cur y elect r odes have t wo advant ages over solid ones for t he det er minat ion of
met als by anodic st r ipping. One is t hat amalgams do not cr eat e t he pr oblems ar ising
fr om t he var iable act ivit y of ver y t hin layer s of solid met als. This per mit s t he
measur ement of t he height of an anodic peak int ead of t he ar ea under it . The ot her is
t hat , if a mixed amalgam is sufficient ly dilut e, it s differ ent const it uent s can be r eoxidized
independent ly and a separ at e peak being obt ained for each. This per mit s mixt ur es t o be
analyzed much mor e easily t han wit h solid elect r ode. See Fig. 11.16.
A ver y impor t ant char act er ist ic of st r ipping pr ocedur es is t hat if all of t he couples
involved ar e r ever sible, t he anodic peaks on t he st r ipping cur ve occur in opposit e or der
fr om t he cat hodic peaks on t he volt ammogr am of t he solut ion being analyzed. In t he
cadmium peak pr ecedes t he lead peak, alt hough t he cat hodic peak of lead ion would
pr ecede t hat of cadmium ion. Wit h such couples st r ipping analysis pr ovides an easy
solut ion t o t he wave or der pr oblems. If one or bot h of t he couples is ir r ever sible, no such
gener alizat ion can be made. For example in dilut e chlor ide media t hat half-peak pot ent ial
of zinc ion is less negat ive t han t hat of cobalt ous ion, but on t he cont r ar y, t he cobalt
couple is so ir r ever sible t hat cobalt does not give an anodic peak. Finally, t he zinc peak
occur s fir st on t he anodic volt ammogr am as well as on t he cat hodic ones. Cur ves like
t hose shown in Fig. 11.17 r eveal t he exist ence of such compounds in many amalgam
cont aining t wo deposit ed met als. Compound for mat ion wit h mer cy may also occur t hose
cont aining only one. The slowness of t hese r eact ions is ver y helpful in polar ogr aphic
pur poses. This is because if t hey wer e fast t he half-wave pot ent ial of a met al ion would
be alt er ed by t he pr esence of anot her whenever t he t wo deposit ed met als r eact ed in t he
mer cur y phase.
The pr act ical applicat ions of st r ipping analysis includes t he det er minat ions of met als
and halides in r eagent gr ade chemicals, of met als and halides in nat ur al wat er , of lead
in ur ine, and of copper in st eels. For fur t her det ails a r eview by Shain (6) should be
consult ed.
References
1. Campbell and U.B. Thomas, Tr ams Elect r ochem. Soc., 76, 303 (1939).
2. Er ans, U.R. Bannist er , L.C., Pr oc. Royal. Soc. London, A 125 (370) (1929), U.R. Evans
and H.A. Hiley, Nat ur e, 139, 283 (1937).
3. Nicholson M.M., J . Am. Chem. Soc., 29.7 (1957).
4. Per one S.P., Anal. Chem. 35, 2091 (1963); E.S. J acobs, ibid, 35, 2112 (1963).
5. Roger s, L.B. and S.S. Lor d, J r . R.C., O Neill, Anal. Chem., 24, 209 (1952).
6. Shain, I. and Per one S.P., Anal. Chem. 33, 325 (1961).
7. Abner Br enner , J . Elect r ochem. Soc., 1956, 103, 652.
8. Bar ker , G.C., Anal. Chem. Act a, 1958, 18, 118.
9. Bar t let , J .C., and Smit h D.M., Can. J ., Chem. 1960, 38, 2057.
10. Belew, W.L., Applicat ions of Cont r olled Pot ent ial...Specific Resist ance Solut ions, M.S.,
Thesis, Dept . of Chem. Univ of Tennesse, Dec. 1963.
11. Br eyer B. and Bauer , H.H. Alt er nat ing Cur r ent Polar ogr aphy and Tensammet r y
(Int er science New Yor k 1963) p. 50.
12. Br ener , Abner , J . Elect r ochem. Soc. 1956, 103, 652.
13. Char lot , G., Bandoz J . Lambing and B. Tr emillan, Elect r ochemical React ions (Elsevier ,
Amst er dam, N.Y. 1962) p. 125.
14. Cooke, W.D., Kelley M.T. and Fischer , D.J ., Anal. Chem. 1961, 33, 1209.
15. Hickling A. Elect r ochem. Act a, 1961, 5 161.
16. Kemula, W. and Kublik, Z., Advances in Analyt ical Chemist r y and Inst r ument at ion, cd.
Reilley C.N. (Inc. N.Y.) 1963, Vol. 2, pp. 123-177.
17. Kelley, M.T., and Fischer , D.J . and J ones H.C., Anal. Chem. 1960, 32, 1262.
18. Kor t um G. and Bockr is OM. Text Book of Elect r ochemist r y (Elsevier New Yor k, Vol. II)
1951, pp. 364-365.
19. Muller , O.H., J . Chem. Edu. 1941, 18, 320.
20. Vandenbelt , J .M., and Henr ich. C., Appl. Spect r oscopy 1953, , 171.
21. Hills. G.J ., Proceedings of Third Int ernat ional Congress, Sout hampt ion, Vol. 1 Macmillan,
London. Ref. p. 115.
22. Br dicka R., : Z, Elect r ochem. 48, 278, 686 (1942).
23. Delahay, P. : J . Phys. and Colloid Chem. 53, 1279 (1949).
24. Delahay, P. : J . Am. Chem. Soc., 75, 1190 (1953).
25. Heyr ovsky, J . Chem. List y 35, 155 (1941).
26. Mat heson, L.A., Nichols N : Tr ans. Elect r ochem., Soc. 73 93 (1938).
27. Mat suda, H., Ayabe Y : Z., Elect r ochem. 59, 494 (1955).
28. Randles, J .E.B., Tr ans. Far aday Soc., 44, 344 (1948).
29. Randles, J .E.B., Analyst 72, S. 301 (1947).
30. Valent a, P., Thesis Polar ogr aph Inst it ut e Pr abha (1955).
31. Vogel J ., Pr oc. 1st Int er nal Polar ogr aph Congr ess Vol. III, p. 731 (1952).
32. Bar ker , G.C., and Gar dner A.W., Z. Anal. Chem. 173, 79 (1960).
33. Boduy, V. 1., Kot lova, I.V. and U.S. Lyapikor , Zavodskaya lab, 28, 1042 (1963).
34. Meit es Louis Polar ogr aphic Technique P. 570. J ohn Wiley & Sons New Yor k.
35. Mar icle, D.L. Anal. Chem., 35 683, (1963).
CHAPTER 12
VOLTAMMETRIC METHODS
12.1 VOLTAMMETRY
Four elect r ochemical t echniques-volt ammet r y (i.e., dir ect -cur r ent , alt er nat ing-cur r ent ,
fa st -sca n, a nd pulse pola r ogr a phy a long wit h volt a mmet r y a t solid elect r odes),
coult omet r y (const ant cur r ent and const ant pot ent ial), pot ent iomet r ic t it r at ion (includes
Differential Pulse Polarogrphy
Fast Scan Polarogrphy
A.C. Polarography
Coulometry(Constant I)
VoltammetrySolid Electrode
D.C. Plarography
Amperometry
Potentiometry
Coulometry(Constant E)
10 ng/ml 100 ng/ml 1 g/ml 10 g/ml 100 g/ml
Fi g. 12.1 : Range of pr act ical usefulness of elect r oanalyt ical t echniques.
t he use of ion-specific elect r odes), and amper omet ic t it r at ion ar e most commonly
employed. Each of t hese elect r oanalyt ical t echniques and t heir pr act ical r ange of
usefulness is pr esent ed in Fig. 12.1.
Coulomet r ic met hods ar e absolut e and have been shown t o be par t icular ly useful
since being absolut e do not r equir e chemical st andar ds. Mor e r ecent ly, fast scan and
differ ent ial pulse polar ogr aphy have become ext r emely useful for t he measur ement s of
dr ugs in biological fluids. However , t he major limit at ion of t hese t wo highly sensit ive
polar ogr aphic t echniques is t he est ablishment of absolut e specificit y. To ensur e specificit y,
TLC s epa r a t i on i s oft en cou pl ed wi t h pol a r ogr a ph i c mea s u r emen t s . A l i qu i d
chr omat ogr aph can be coupled dir ect ly t o an elect r ochemical det ect or . A lar ge number
of phar maceut ical pr oblems can be sor t ed out by t his appr oach.
12.1.1 Coulometric Methods
Cont r olled pot ent ial coulomet r y has been applied ext ensively t o pr ecision det er minat ions
[2] and t o t he est ablishment of n values for elect r ode r eact ions. The t echnique has also
used for t he elucidat ion of elect r ode r eact ions [1,6]. The t echnique is ver y useful when
used in conjunct ion wit h a t hin-layer cell wher e complet e elect r olysis is r apid.
The t echnique involves t he det er minat ion of t he quant it y of mat er ial elect r olyzed
fr om t he amount of char ges passed t hr ough an elect r ochemical cell dur ing elect r olysis.
Far adays law r elat es t he measur ed char ge t o t he amount of mat er ial elect r olyzed.
=
Q
N
nF
...(1)
wher e, N is t he number of moles of subst ance being elect r olyzed, Q is t he t ot al char ge
passed (coulombs), n is t he number of elect r ons t r ansfer r ed per molecule, and F is t he
Far adays const ant .
In cont r olled-pot ent ial coulomet r y t he pot ent ial of a wor king elect r ode is applied at
a value such t hat complet e elect r olysis of t he desir ed species occur . The t ot al char ge
passed dur ing t he exhaust ive elect r olysis is obt ained by int egr at ing (elect r onically) t he
cur r ent . The complet ion of elect r olysis is indica t ed when t he cur r ent becomes
indist inguishable fr om t he r esidual cur r ent . The char ge due t o t he r esidual cur r ent
must be subst r act ed fr om t he t ot al measur ed char ge in or der t o obt ain t he far adic
char ge for t he elect r ode r eact ion of int er est . This r esidual char ge is est imat ed by
r epeat ing t he exper iment on suppor t ing elect r olyt e and int egr at ing t he cur r ent over
t he same t ime int er val. Ther e is no guar ant ee, however , t hat t he pr ocesses r esponsible
for t he r esidual cur r ent s ar e complet ely independent of t he pr esence of sample and/or
pr oduct . Maximizing t he magnit ude of t he cur r ent dur ing elect r olysis and minimizes t he
t ime r equir ed for t he complet e elect r olysis; besides t he gener al t echnique of volt ammet r y
t her e exist specific descr ipt ion r egar ding var ious fact or s which need at t ent ion. These
ar e as such innumer at ed below.
Th i n La ye r Volt a mme t r y (TLV) : This is a ver y slow t echnique and t his fact is
used t o a gr eat advant age in quant it at ive st udies of elect r ode r eact ions wit h small
het er ogeneous r at e const ant s. Hubbar d [4, 5] r eviewed and pioneer ed t his ar ea. TLV
is also applicable t o examinat ion of met al deposit ion and adsor pt ion.
Schmidt and co-wor ker s [8] car r ied out t his wor k. The t echnique has been helpful
is mechanism st udies of r edox cont r olled solut ion chemist r y.
The number of coulombs t o oxidize a subst ance R confined wit hin a t hin layer cell
is given by Far adays Law,
=
0
R
Q nF VC ...(2)
wher e
0
R
VC is t he init ial (t = 0) concent r at ion of R and V is t he volume of t he t hin layer
Voltammetric Methods 163
cavit y. If t he exper iment is car r ied out slowly enough, C
Ri
t will be unifor m acr oss t he
cell due t o r apid diffusional mixing in t hin solut ion films. The cur r ent at any t ime will
be given by
= =
, R t
dC dQ
i nFV
dt dt
...(3)
wher e nV (dCR, t/ dt) is t he number of equivalent s consumed per second can be r eadily
der ivat ized chemically t o yield elect r oact ive der ivat ives. The funct ional gr oups which
show excellent volt ammet r ic pr oper t ies include t he nit r o, nit r oso, quinone, azo, azoxy,
azomet hane, act ivat ed car bonyls, and act ivat ed double bonds [7]. For t he most par t ,
t he volt ammet r ic act ivit y of a compound can be deduced fr om an examinat ion of it s
funct ional gr oups. In case t he compound under invest igat ion is insoluble in aqueous
media, t hen or ganic solvent s such as alcohols, dioxane, acet onit r ile, dimet hyl sulphoxide
and dimet hyl for mamide must be employed. Occasionally, pur e non-aquous solvent s of
high dielect r ic const ant , such dimet hyl for mamide, act onit r ile, dimet hyl sulphoxide,
pyr idine, or glacial acet ic acid cont aining t et r a alkyl salt s may be r equir ed t o at t ain
highly negat ive pot ent ials (gr eat er t han1.8 V vs SCE) wit hout suppor t ing elect r olyt e
decomposit ion.
Volt a mmet r i c r esea r ch i s qu i t e ext en si ve i n p h a r ma ceu t i ca l comp ou n d s : The
volt ammet r ic analysis of dr ugs in phar maceut ical pr oduct s is by for t he most common
use of elect r ochemist r y for analyt ical-phar maceut ical pr oblems. (10
3
10
8
M), a ny one
met hod can r eadily be applied t o t he analysis of phar maceut icals in bulk and in dosage
for ms. Solid elect r ode volt ammet r y (which excludes polar ogr aphy) has an inher ent
det ect ion limit of appr oximat ely 10
4
10
5
M and is consequent ly limit ed t o t hese
applicat ions, small amplit ude polar ogr aphic t echniques (ac and pulse) can be applied t o
t he measur ement of impur it ies in bulk and dosage for ms, and t o t he essay of dr ugs and
met abolit es in biological fluids following high-dose administ r at ion wher e levels ar e at
least 10
6
M (1 g/mL sample). Only t he t echniques of fast -scan polar ogr aphy and
differ ent ial pulse polar ogr aphy wit h limit s of dect ion of appr oximat ely 100-200 and 10
20 ng/mL of biological fluids, r espect ively, ar e capable of measur ing dr ugs in biological
fluids following t her apeut ic administ r at ive on a r out ine basis.
The appeal of t he volt ammet r ic met hods of analysis for or ganic compounds is
at t r ibut able t o t heir simplicit y and r apidit y. An ext r emely lar ge number of or ganic
compounds ar e eit her dir ect ly r educible at t he DME or oxidizable at a solid elect r ode
or can be r eadily r educible at t he DME or oxidizable at a solid elect r ode.
12.1.2 Voltammetric Methods
Pot ent iomet r ic and coulomet r ic t it r at ion met hods ar e fair ly univer sal and can be applied
t o a wide var iet y of pr oblems, wher eas volt amet r ic met hods ar e dist inct ly limit ed t o
easily r educible or oxidizable compounds. On t he ot her hand, volt amet r ic met hods ar e
clear ly t he most useful for low-level quant it at ion and have a wide linear dynamic r ange
as given in Fig. 12.1 of t he chapt er . Her e, volt ammet r y is defined as elect r olysis at a
micr oelect r ode which is limit ed by t he mass t r ansfer r at e at which molecules move fr om
t he body of t he solut ion t o
t he elect r ode. The cur r ent
is followed as a funct ion of
t he pot ent ial applied using
t hr ee elect r ode cells of 1-
50 ml wor king volume. For
mos t r edu ct i on s t h e
wor k i n g el ect r ode i s a
dr opping mer cur y elect r ode
(DME ) or a h a n gi n g
mer cu r y dr op el ect r ode
(HMDE). Solid elect r ode
vol t a mmet r y wh i ch i s
t ypi ca l l y empl oyed for
(anodic oxidat ion) pr ocesses
can use a r ot at ing plat inum
el ect r ode (RP E), a wa x
i mpr egn a t ed gr a ph i t e
elect r ode (WIGE), a car bon
past e elect r ode (CPE), or a
gl a s s y ca r bon el ect r ode
(GCE).
Since t he volt ammet r ic
t echniques demonst r at e a
lar ge linear dynamic r ange.
A plot of i vs E (eq. 4) defines t he ideal t hin-layer volt ammogr am as shown in Fig.
12.2. It is t o be not ed t hat t he peak is symmet r ical about E
0
, and t hat t he cur r ent dr ops
t o zer o aft er t he pot ent ial passes t hr ough E
p
, and t hat i
p
is dir ect ly pr opor t ional t o scan
r at e
( )
( )
( )
( )
{ }
R
n F VC nF RT E E
i
RT nF RT E E
(

=
(
+

2 2 0 0
2
0
exp
1 exp
'
/
/ '
...(4)
The cur r ent is maximum at E = E
0,
, so
=
2 2 0
4
R
p
n F VC
i
RT
(v is t he scan r at e in V/s) ...(5)
The number of coulombs passed in fully t r aver sing t he peak is given by equat ion
Q = nF
0
R
VC , since t he conver sion of R t o O is complet e.
In case when t he scan dir ect ion is r ever sed, a r educt ion wave is obt ained (as shown
by dot t ed line) for t he r ever se r eact ion which is an exact mir r or image of t he oxidat ion
wave. This r esult is obt ained only for a fully r ever sible elect r ode r eact ion. When t he
Fi g. 12.2 : Thin-layer volt ammet r y for a r ever sible one-
elect r on oxidat ion.
E(+)
O
E
0
E
0
+100 mV E
0
100 mV
O + e R
R E O
ia
i
c
het er ogeneous r at e const ant is ver y slow, t he for war d and r ever se waves will lose t heir
symmet r y and t he peak pot ent ial will separ at e.
Thin layer cyclic volt ammet r y is also somet imes used in conjunct ion wit h an opt ically
t r anspar ent t hin-layer elect r ode t o obt ain spect r a, E
0,
, and n for r edox couples by t he
spect r o pot ent iost at ic t echniques and t hin layer coulomet r y. Cyclic volt ammet r y is
used init ially t o locat e t he r edox couple and give an est imat e of E
0,
.
St ir r ed -Solu t ion Volt a mmet r y : This t echnique ut ilizes current -volt age relat ionships
which ar e obt ained at a st at ionar y elect r ode immer sed is a st ir r ed solut ion. In t his
aspect it is ext r emely useful t o consider a t ypical cur r ent -volt age cur ve (volt ammogr am)
in t er ms of t he concept of concent r at ion-dist ance pr ofiles. Hence t he pot ent ial is
consider ed as t he cont r olled var iable r at her t han cur r ent .
The cur r ent r esult ing fr om an applied pot ent ial is det er mined by t he slope of t he
concent r at ion-dist ance pr ofile of t he r eact ant at t he elect r ode sur face. It can be fur t her
expr essed in t er ms of Ner nst diffusion layer concept .
In t he Fig. 12.3, a t ypical cur r ent volt age cur ve t hat would be obt ained for a
solut ion cont aining equal concent r at ion of O and R. The shape of t his cur ve can be
under st ood by consider ing t he slopes of t he concent r at ion-dist ance pr ofiles t hat ar e
depict ed for sever al r epr esent at ive pot ent ials. Dur ing oxidat ion cur r ent is det er mined
by t he slope of t he pr ofile for R, wher eas t he all concent r at ion pr ofiles ar e complet ely
r elaxed befor e t he next pulse is applied and ever y pulse imit at es a new chr oamber omet r ic
exper iment . The lengt h of t
d
r equir ed t o accomplish t his will depend on t he chemical
r ever sibilit y of t he syst em,
which would be short er for
r ever sible r eact ions and
l on ger for i r r ever s i bl e
r eact ion.
A fully (chemically and
elect r ochemically) r ever -
sible syst em is considered
a s a n exa mpl e. Th e
r ever sible syst em gives
t he r esponse t o a r amp
excit at ion as illust r at ed in
t he Fig. 12.3 a nd only
t hr ee pulses ar e chosen
for examinat ion.
Respon se t o pu lse A :
Her e t he pulse amplit ude
is insufficient t o init iat e
s i gn i fi ca n t fa r a di a c
r eact ion and t he sample
concent r at ion pr ofiles not
dis t u r bed. Th e cu r r en t
r esponse is t hen pr imar ily
Fi g. 12.3 : Volt ammogr am wit h r epr esent at ive concent r at ion-
dist ance pr ofiles for a solut ion cont aining equal concent r at ions of
O and R. D
O
= D
R
C
S
R
=C
S
O
C
S
R
C
S
O
= O
C
D
R
= C
D
O
O + e R
ic
POTENTIAL
E = E
0,
E
ref
C
S
O
C
S
R
= O
i
la
R O + e
i
lc
ia
C
u
r
r
e
n
t
due t o char ging and double-layer capacit ance t o t he new pot ent ial (E
i
+ E). The cur r ent
sampled just bet ween is negligible; for by t hat t ime t he double layer is fully char ged.
Re s p on s e t o P u ls e B : Now t he pulse amplit ude ext ends t o t he half-wave pot ent ial
for t he r eact ive species, concent r at ion gr adient s will for m and t he significant far adiac
cur r ent will be sampled. It is t o be not ed t hat t he double-layer char ging cur r ent will
have decayed away when t he sample is t aken. This t ime-domain discr iminat ion against
i
dl
is a pr incipal advant age of pulse volt ammet r y pr ofile for O is t he det er mining fact or
dur ing r educt ion. A limit ing cur r ent (i
e
) is r eached when t he sur face concent r at ion C
s
of t he cont r olling species becomes effect ively zer o.
12.2 LARGE-AMPLITUDE PULSE VOLTAMMETRY (LAPV)
The t echnique is t he nor mal pulse volt ammet r y wher e in t he excit at ion wave for m
consist s of successive pulses of gr adually changing amplit ude bet ween which a const ant
init ial pot ent ial is applied. The init ial pot ent ial is usually chosen in a r egion wher e
none of t he sample component s ar e elect r ochemically r eact ive. The cur r ent r esponses
may be measur ed eit her dur ing t he for war d st ep, aft er r et ur n t o t he init ial condit ion,
or bot h. Usually, t he cur r ent is sampled only at t he end of t he for war d st ep and t he
r emainder of t he r esponse wave for m is ignor ed. The sampled cur r ent is t hen plot t ed
against t he pulse height s (t hus volt ammet r y). Somet imes t he differ ence bet ween
successive sampled cur r ent is plot t ed as a funct ion of pot ent ial. This r esult s in a
r esponse having a der ivat ive shape. It is impor t ant t o r ecognize t hat all var iat ions of
LAPV ar e in essence a ser ies of pot ent ial pulse chr onoamper omet r y exper iment s.
The Fig. 12.4 illust r at es t he simplest example of LAPV of a st at ionar y elect r odes.
In t his case it can be assumed t hat t he t ime delayed bet ween pulses is such t hat t he
init ial condit ion is r est or ed. This implies t hat t he far adia cur r ent would t hus follow a
modified Cot t r ell equat ion :
i = nF AC
0
( | |
| |
+
( | |
\ . (
\ .
1 1
2
1
O
R
C D
t C
...(6)
wher e for a r ever sible syst ems X = 0.
( )
S
O
i
S
R
C nF
E E E
RT
C
| |
( = +
|

\ .
...(7)
In t he case of pulse B, (E
i
+ E) = E
1/2
.
So ( )
/
S S
O R
C C
= 1 and
( )
1
1
S S
O R
C C
+ + = 0.5 ...(8)
Re s p on s e t o p u ls e C : It is t he limit ing case of chr onoamper omet r y. The sur face
concent r at ion becomes effect ively zer o and t he r esponse will follow t he Cot t r ell equat ion.
On plot t ing t he sampled cur r ent ver sus t he applied pot ent ial a complet e pulse
volt ammogr am r esult s as shown in t he last figur e. When t he differ ence bet ween
successive samples is plot t ed (Fig. 12.4) a peaked r esponse is obt ained.
Fi g. 12.4 : Int r oduct ion t o st at ionar y elect r ode LAPV
E
t
d
t
p
(A)
E()
Time
Excitation Waveform
C
O
= C
0
O
C
O
= 0
PULSE A
no reaction
X
(B)
PULSE B
X X
at t = t
p
+ r
PULSE C
at t = t
p
+ r
System response to selected pulses
(C)
t
sample
t
p
sample
t
p
t
sample
t
p
t
p
+ r
Current Response to Selected Pulses
(D)
LAPV
E()
i
sampled
i
sampled
Derivative LAPV
E()
(E)
When LAPV is car r ied out wit h a DME, t he t echnique is lar ge amplit ude pulse
polar ogr aphy (LAPP). This is usually r efer r ed t o as nor mal pulse polar ogr aphy. One
pulse is applied per dr op at a fixed t ime lat e in t he life of t he dr op. The cur r ent is
sampled just befor e t he dr op is dislodged by mechanical means, a t ime at which t he
r at e of change of ar ea is smallest . Because t he pulse widt hs ar e usually in t he 50-ms
r egion, t he elect r ode is effect ively st at ionar y and of fixed ar ea dur ing each pulse. Since
each dr op is a new elect r ode, t he t ime bet ween pulses t
d
is made t o be t he dr op t ime.
The t iming cir cuit r y t hat is used t o gener at e t he pulses also funct ions t o t r igger an
elect r ochemical dr op knocker or a st at ic mer cur y dr op elect r ode.
Somet imes it is useful t o apply ident ical pulse t o sever al dr ops befor e incr easing
t he amplit ude. This allows for t ime aver aging and some impr ovement in t he signal-t o-
noise r at io. LAPP is analyt ically useful, being sensit ive t o 10
6
M in some cir cumst ances.
In an int er est ing var iat ion of LAPP or iginally descr ibed by Kalousek [9] t he pot ent ial
a ppl i ed t o DME i s a l t er n a t el y
swit ched fr om an init ial pot ent ial
(which is sufficient ly negat ive of t he
E
1/2
for a r educible species t o cause
a limit ing cat hodic cur r ent ) t o a
ser ies of pot ent ial pulses changing
in height fr om values mor e posit ive
t h a n E
1/2
t owa r d mor e nega t ive
values. The cur r ent is sampled lat e
in t he life of each pulse, as indicat ed
i n t h e F i g. 12. 5. At fi r s t t h e
r educt ion pr oduct for med at t he
init ial pot ent ial is oxidized dur ing
anodic wave Fig. 12.5. Aft er t he
pulse height s pass t hr ough E
1/2
and
r each pot ent ials for r educt ion, a
cat hodic cur r ent is r ecor ded. The
r ela t ive va lues of i
a
a n d i
c
will
depend on t he r ever sibilit y of t he
r ea ct ion a n d t h e s pecific pu ls e
wi dt h s a n d s a mpl i n g t i mes
employed.
I n yet a not her va r ia t ion t he
cur r ent is r ecor ded at t he init ial
pot ent ial following a ser ies of pulses
incr easing in amplit ude fr om t he
i n i t i a l pot en t i a l t owa r d mor e
n ega t i ve va l u es (i .e., t he sa me
exilat ion as shown in Fig. 12.4 (a).
When t he pulses r each sufficient ly
n ega t i ve pot en t i a l s t o ca u s e
Fi g. 12.5 : In one of many possible var iat ions of
LAPP t he cur r ent is sampled on a r ever se st ep just
pr ior t o dr op fall. (a) excit at ion, (b) r esponse
i
c
i
c
isampled
i
a
reverse reaction
forward reaction
O R
R O
E()
(B)
i
a
Ei
E()
O R
( A)
E
t
d
R O
Ti me
sampl e taken
her e
r educt ion of t he species, t he pr oduct of t he r educt ion is oxidized at E
i
, and t he sampled
anodic cur r ent is r ecor ded unless t he couple is t ot ally ir r ever sible. This is equivalent t o
a ser ies of pot ent ial pulse chr onoamper omet r y exper iment s wit h samples t aken on t he
r ever se st ep. Techniques of t his t ype have been used, at t imes, in r ever sibilit y st udies
and for ident ificat ion of unst able pr oduct s of elect r ode pr ocesses [3].
12.3 DIFFERENTIAL AND DERIVATIVE VOLTAMMETRY
This t echnique was or iginally devised by Semer ano and Riccoboni. Two indicat or
elect r odes at t he same pot ent ial in differ ent solut ions ar e used, and t he differ ence
bet ween t he cur r ent s flowing t hr ough t hem is r ecor ded as a funct ion of t heir common
pot ent ial. A simple cir cuit , t hat ser ves t he pur pose is shown in Fig. 12.6, wher e t he
magnit ude of pot ent ial dr op E
R
indicat ed by t he r ecor der is given by
E
R
= i
1
R
1
i
2
R
2
...(9)
ind. ref.
Cell 1
Cell 2
ind. ref.
Recorder
i
1
i
2
R
2
R
1
To polarizing circuit
Fi g. 12.6 : Schemat ic diagr am of a simple cir cuit for differ ent ial volt ammet r y
A solut ion of t he suppor t ing elect r ode alone could be placed in cell 2 and an ident ical
solut ion cont aining an elect r oact ive subst ance may be placed in cell 1. In case t he t wo
indicat or elect r odes ar e exact ly ident ical, t he var iat ion of i
2
wit h pot ent ial will be
exact ly t he same as t he var iat ion of t he r esidual cur r ent included in i
1
. Hence, if R
1
and
R
2
ar e equal, E
R
will be pr opor t ional t o t he cur r ent due t o t he elect r oact ive subst ance
alone. The r esult ing plot of E
R
against indicat or elect r ode pot ent ial will pr ovide an
aut omat ic cor r ect ion for t he r esidual cur r ent . This can be used t o compensat e for t he
final cur r ent t o impr ove t he shape of a cat hodic wave occur r ing at pot ent ials so negat ive
t hat it s plat eau is t oo shor t t o be measur ed on an or dinar y volt ammogr am.
Compensat ion can be achieved, not only for t he r esidual cur r ent , but also for t he
cur r ent on t he plat eau of t he pr ior wave. As an example a por t ion of t he cadmium-zinc
solut ion yielding t he polar ogr am is shown in Fig. 12.7 might be placed in cell 1 while
suppor t ing elect r olyt e in cell 2. The cir cuit is t hen adjust ed t o pr ovide a pot ent ial on
Fig. 12.7 : Schemat ic der ivat ive volt ammogr ams obt ained wit h (a) a single r educible
subst ance, illust r at ing t he measur ement of t he peak height , and (b) a mixt ur e of t wo
such subst ances giving over lapping peaks, showing t hat t he mor e difficult y r educible
subst ance is mor e r eadily det ect ed t han det er mined
b
max
di
dt
max
di
dt
a
d
i
/
d
t
Potential
t he plat eau of t he cadmium wave. A concent r at ed solut ion of cadmium ion might be
added t o cell 2 t o decr ease E
R
t o zer o. Differ ence bet ween t he concent r at ion of cadmium
ion in t he solut ion, bet ween t he ar eas of t wo st at ionar y or solid indicat or elect r odes,
or bet ween t he values of m for t wo dr opping elect r odes, or bet ween t he values of m for
t wo dr opping elect r odes can be compensat ed by suit able adjust ment of t he r at io R
1
/R
2
.
As such t he plot of E
m
against indicat or elect r ode pot ent ial would t hen show only t he
zinc wave.
The for egoing applicat ions (bot h) ar e t er med subt r act ive volt ammet r y.
Some difficult y is involved in differ ent ial polar ogr aphy, in which dr opping elect r odes
ar e used as t he indicat or elect r ode. Because unless t he cycles of dr op gr owt h and fall
ar e exact ly synchr onized t he differ ence of cur r ent will under go wide per iodic fluct uat ions
even t hough t he t wo elect r odes yield t he same aver age cur r ent . Kolt hoff and Lingane
called t his as beaded st r ing effect .
Der ivat ive volt ammet r y consist s of r ecor ding t he r at e of change, di/dt , of t he cur r ent
flowing t hr ough a volt ammet r ic cell against t he pot ent ial E of t he indicat or elect r ode,
which is var ied at a const ant r at e dE/ dt. The values of di/ dE is small at pot ent ials
pr eceding t he wave, incr eases t o a maximum at t he half-wave pot ent ial.
This happens when t he wave obeys eit her of t he equat ions :
( )
( ) | |
005915 .
log /
d e
d E
d i id i n
=
...(10)
E
d.e
= E
1/ 2

00542 .
n
log
i
id i
...(11)
It t hen decr ease again t o a ver y small value on t he plat eau. The maximum deflect ion
of t he galvanomet er or r ecor der occur s at t he half-wave pot ent ial. It is pr opor t ional t o
t he diffusion cur r ent (and hence t o t he concent r at ion of t he elect r oact ive subst ance
r esponsible for t he maximum) and incr eases as t he r at e of polar izat ion incr ease. It is
lar ger for a r ever sible wave t han for an ir r ever sible one involving t he same over all
number of elect r ons, and it incr eases as n or n
a
incr eases.
For r ecor ding a der ivat ive volt ammogr am, t he simplest pr act ical t echnique consist s
of connect ing a condenser having a high capacit ance in ser ies wit h t he galvanomet er
or t he r esist or acr oss which t he r ecor der is connect ed.
On a der ivat ive polar ogr am t wo clear peaks which can easily be ident ified ar e
obt ained. Peak height s in der ivat ive polar ogr aphy have t o be measur ed by a base-line
t echnique. If t her e is only one wave on t he polar ogr am, t he der ivat ive cur ve has t he
t ypical shape as shown in Fig. 12.7 (a) and t he height of t he peak can be measur ed,
t hough wit h uncer t aint y.
References
1. Bar d, A.J . and Sont hanam K.S.V. in Elect r oanalyt ical Chemist r y, Vol. 4, Mar cel Dekkar ,
New Yor k, 1970.
2. Har r an, J .E., Elect r oanalyt ical Chemist r y, Vol. 8 (A.J . Bar d, ed.) Mar cel Dekkar , New
Yor k, 1975.
3. Heinman William R. Dept . of Chemist r y Univer sit y of Cincinnat i, Cincinnat i and Ohio,
Kissinger Pet er T., Dept ., of Chemist r y Pur due Univer sit y Inc. West Lafayet t e Indiana.
4. Hubbar d A.T., and Anson F.O., in Elect r oanalyt ical Chemist r y, Vol. 4. (A.J . Bar d, ed.)
Mar cel Dekkar , New Yor k, 1970.
5. Hubbar d A.J . CRC Cr it , Rev. Anal Chem. 3 : 201 (1973).
6. J anat a, J . and Mark H.B., J r. Elect roanalyt ical Chemist ry, Vol. 3. (A.J . Bard, ed.) Marcel
Dekkar , New Yor k, (1969).
7. Punger , E., Feher Z. and Nagy, G., Act a Chem. Hung. 70 : 207 (197) and Abst r . 23 : 747
(1972).
8. Schmidt E., Elect r ochim. Act a, 8, 23 (1963).
9. Kalousek M. Collect ion Czechoslov. Chem. Communs., 13, 105 (1948).
CHAPTER 13
CONTROLLED POTENTIAL
ELECTROLYSIS
13.1 ELECTRO-ORGANIC SYNTHESIS AND THE TECHNIQUE
Ther e has been a vigor ous expansion of t he classical ar eas of or ganic elect r oanalysis
and it s applicat ions t o physical or ganic chemist r y [9] as well as elect r osynt hesis and
r elat ed mechanisms. Besides t hese many new fields have opened dur ing t his per iod. In
br ief may be included as r esear ch and applicat ions of or ganic elect r ochemist r y in fuel
and solar cells [5], high ener gy bat t er ies, cor r osion inhibit or s, elect r odeposit ion of met als
and paint , or ganic semiconduct or s, or ganic phot o elect r ic mat er ials, et c. Recent ly int er est
is developing in t he applicat ion of t hese t echniques t o t he st udy of biological pr ocesses
phar macy and phar macology and also t he new br anch-Bioelect r ochemist r y. Recent
st udies also involve t he fabr icat ion and t est ing of chemically modified and ion select ive
elect r odes which have at t r act ed unusual int er est in elect r ocat alysis, elect r o synt hesis,
phot osensit izat ion and elect r osensor s [3].
Thus, for t he pr oduct ion of a number of chemical, t he elect r ochemical r out es has an
edge over t he chemical met hods specially in r egar d t o ease of oper at ion, enhanced
pr oduct pur it y, pollut ion cont r ol and ease of oper at ion.
Besides a number of advant ages, t he t echnique has some limit at ions t oo. The main
dr aw back is t hat t he r eact ions ar e slow and t hus consume mor e t ime. The choice of
solvent s is also r est r ict ed along wit h t he limit ed choice of t he suppor t ing elect r olyt e.
The or ganic elect r ode r eact ions can be classified as descr ibed below. However , t hese
depend of t he nat ur e of final pr oduct s and it s for mal mode of for mat ion.
Some impor t ant t ypes of r eact ions ar e list ed below :
13.1.1 Pure Electron Transfer
Anodic and cat hodic elect r on t r ansfer is t he element ar y pr ocess under lying in all
elect r ochemical r eact ions. These finally r esult in t he for mat ion of r adical ions fr om
neut r al molecules (Eq. 1 and 2).
R E
R E'
+
+ e
...(1)
R Nu
+
e
R Nu'
...(2)
and neut r al r adicals fr om char ged species (Eq. 2 and 3).
R E
R E' + e
...(3)
R Nu
+
+ e
R Nu' ...(4)
In major it y of cases, r adical ions and neut r al r adicals ar e consumed as t hey ar e
for med in ver y fast chemical follow up r eact ions giving r ise t o a wide var iet y of pr oduct s.
13.1.2 Conversion of Functional Groups
This t ype of r eact ion is similar t o it s chemical count er par t in which a funct ional gr oup
is r educed or oxidized t o anot her one for example, as given equat ions (5), (6 and 7)
R NO
2
4H
e
+
+
+
R NHOH
2
2H
e
+
+
R NH
2
...(5)
R COOH
4
4H
e
+
+
+
R CH
2
OH ...(6)
...(7)
The oxidat ion of pyr idine met hanols t o pyr idine car boxylic acids has (eqn. 7) been
car r ied cut in nickel oxide elect r ode [11].
13.1.3 Substitution Reactions
A gener al expr ession for anodic subst it ut ion r eact ions is given in (Eq. 8).
Her e E is oft en hydr ogen at om, which can also be anot her at om or gr oup e.g., t-
but yl, OCH
3
, Cr COO
R E + Nu
R Nu + E
+
+ 2e
...(8)
A gener al equat ion (9) confor ms t o t he cat hodic subst it ut ion e.g.,
R Nu + E
+
+ 2e
R E + Nu
...(9)
Her e E
+
, in most cases, is H
+
or an equivalent pr ot on donor . It can also be a neut r al
molecule, such as CO
2
or met hylbr omide, wher eas Nu is a leaving gr oup of some kind
e.g., halogen, RSO, RSO
2
, N
+
R
3
, et c.
13.1.4 Addition Reactions
In an anodic addit ion, t wo nucleophilic molecules ar e added acr oss a double bond (eq.
10) or in a syst em of double bonds wit h loss of t wo elect r ons.
Nu Nu
| | ...(10)
R
2
C = CR
2
+ 2Nu
R
2
C CR
2
+ 2e
Similar ly, in a cat hodic addit ion r eact ion t wo elect r ophilic molecules add acr oss a
double bond (eq. 11) or in a syst em of double bonds wit h addit ion of t wo elect r ons.
E E
| | ...(11)
R
2
C = CR
2
+ 2E
+
+ 2e
R
2
C CR
2
The most impor t ant r eact ion is cat hodic hydr ogenat ion wher e E
+
is a pr ot on donor
(eq. 11). For t his r eact ion t he aut hor s [5] have t r ied elect r ocat alyt ic hydr ogenat ion of
amino benzoic acids at plat inum cat hode in 2N per chlor ic acid media giving r ise t o
bicyclic lact ams and est er (eq. 12).
+ 6 e + 6 H
+
N H
2
COOH
H O
2
N H
O
...(12)
13.1.5 Elimination Reactions
Anodic and cat hodic eliminat ion is simply t he r ever se of cat hodic (eq. 11) and anodic (eq.
10) addit ion r espect ively.
13.1.6 Coupling Reactions
Two simple ver sions of for mal anodic coupling exist , namely coupling-eliminat ion
(eq. 13) and coupling addit ion (eq. 14) :
2R E R R + 2E
+
+ 2e
...(13)
2Nu + 2 C = C
Nu C C C C Nu + 2e
...(14)
The for mer t ype is best r epr esent ed by t he hist or ical Kolbe React ion (16)
2R COO
R R + 2CO
2
+ 2e
...(16)
The cat hodic count er par t s of eq. (13, 14) ar e indicat ed in (eqs. 17 and 18)
2R Nu + 2e
R R + 2Nu
...(17)
2E + 2 C = C + 2e
+
E C C C C E ...(18)
React ion (18) is of gr eat impor t ance in cases wher e E
+
is a pr ot on. The gener al
designat ion for t his mode of coupling is elect r o hydr odimer izat ion. The best known case
being t he flag ship and gr ant swinger of elect r oor ganic chemist r y all over t he wor ld,
Monsant os pr ocess (eq. 19) for making adiponit r ile dir ect ly fr om acr ylonit r ile.
2CH
2
= CH CN + 2H
+
+ 2e
NC (CH
2
)
4
CN ...(19)
13.1.7 Cyclization (Intramolecular and Intermolecular) [2, 11, 12]
Oxidat ive int r amolecular cyclizat ion of 2-nit r o aniline affor ding benzofur oan (eq. 20) in
t he pr esence of elect r ogener at ed iodonium ions, which behave as cat alyt ic oxidizing
agent , and at t he same t ime as an elect r on car r ier .
N O
2
N H
2
I
+
N
+
N
O
O
...(20)
Controlled Potential Electrolysis 175
13.2 ELECTROCHEMICAL ACTIVITY IN HETEROCYCLIC SYSTEMS
Het er ocyclic compounds occupy a unique posit ion in t he field of or ganic chemist r y.
Elect r ochemical st udies of nit r ogen cont aining het er ocycles ar e almost as old as t he
field of elect r ochemist r y it self. The nit r ogen cont aining het er ocyclic compounds have
been of much int er est for elect r ochemist r y as not all but many of t hem, in one way or
t he ot her ar e r elat ed t o any biochemical pat hway, ener gy t r ansfer syst em, or medicinal
significance.
The elect r olyt ic r eact ion pat hways of N-het er ocyclic r eact ions may be enumer at ed in
gener al cat egor ies as shown below :
Elect r olyt ic Reduct ion Het er ocyclic Syst ems:
(i) Hydr ogenat ion
(ii) Dimer izat ion
(iii) Hydr odimer izat ion
(iv) Halogen eliminat ion
Elect r olyt e Oxidat ion Het er ocyclic Syst ems:
(i) Coupling
(ii) Fr agment at ion
(iii) Anodic subst it ut ion
The elect r olyt ic r eact ions in which a het er ocyclic syst em is for med, may be classified
in differ ent ways accor ding t o t he t ype of bond for mat ion. These ar e descr ibed below :
1. Ring closur e r eact ions
2. Ring cont r act ion r eact ions
3. Ring expansion r eact ions
13.2.1 Ring Closure Reactions
Suit ably subst it ut ed molecules can under go int r a- and/or int er -molecular elect r ophilic
and/or nucleophilic r eact ion ut ilizing ot her wise unst able elect r ogener at ed funct ional
gr oups, giving r ise t o het er ocyclic compounds [3, 4, 5, 6]. Thus, in t hese syst ems t he r ole
of cur r ent is t o br ing one or bot h t he r eact ion cent er s t o a suit able oxidat ion st at e. In
a r ing closur e syst ems t her e is eit her .
(a) At t ack of an elect r olyt ically for med nucleophile (e.g., alcohol, hydr oxylamine,
amine hydr oazine, on an elect r ophilic cent er e.g.,) car bonyl, cyano, nit r o and
nit r oso der ivat ive gr oups, commonly t er med as r educt ive cyclizat ion sect ions.
The r educt ion of compounds suit ably subst it ut ed wit h r educible funct ional gr oups
can be advant ageously used for het er ocyclic r ing syst ems. The guiding pr inciple
for such a r eact ion is t o for m a nucleophilic cent er in t he molecule by cat hodic
r educt ion of a funct ional gr oup and t hen t o get t his t o r eact wit h an elect r ophilic
cent er (suit ably which may also be for med in an elect r ochemical pr ocess or be
pr esent in t he st ar t ing mat er ial) posit ioned for r ing closur e [3, 4]. Reduct ive
cyclizat ion r eact ion of amino benzoic acids have been chosen as model examples
by t he aut hor s [5]. Ther e give r ise t o bicyclic lact ans and est er . Thus, t he
elect r ocat alyt ic hydr ogenat ion and subsequent int r amolecular cyclizat ion of
4-amino benzoic acid affor ded 2-azo bicyclic [2, 2, 2] oct an-3-one (eqn. 12).
The polar izat ion st udy of a syst em (oxidat ion or r educt ion) is achieved by t hr ee
elect rode syst em consist ing of working elect rode auxiliary elect rode, and reference elect rode
as shown in Fig. 13.4. The polar izat ion cur ves ar e dr awn bet ween elect r ode pot ent ial
E ver sus cur r ent densit y i (t he cur r ent passed per unit sur face ar ea of t he wor king
elect r ode) or log cur r ent densit y, in t he absence and pr esence of depolar izer t o find a
suit able r ange of cur r ent densit y applicable t o t he syst em under st udy.
Nor mally pot ent iost at ic and galvanost at ic t echniques pr oduce ident ical polar izat ion
cur ves wit h only one except ion t he sigmoid char act er ist ic which can only r epr oduce in
pot ent iost at ic cont rol, see Fig. 13.4. In t his figure, t he full line represent s t he pot ent iost at ic
met hod, while t he dot t ed line r epr esent s t he galvanost at ic met hod).
In or der t o under st and t he pr act ical ut ilit y of polar izat ion cur ves, in elect r osynt hesis,
a syst emat ic appr oach of t his concept can be ver y well explained by t aking a gener al
example of elect r olyt ic r educt ion as shown in Fig. 13.5.
In Fig. 13.5, cur ve 1 r epr esent s t he polar izat ion cur ve obt ained in t he absence of
depolar izer . The small cur r ent flowing bet ween a and b may be due t o t he pr esence of
a small amount of r educible mat er ial pr esent in t he solut ion or , t o diffusion of hydr ogen
away fr om t he cat hode. Visible hydr ogen evolut ion commences in t he vicinit y of b,
which gives t he so-called bubble over volt age pot ent ial. Beyond t his t he gas is evolved
fr eely wit h lit t le fur t her polar izat ion.
If a depolar izer is pr esent (cur ve II), t he r educt ion of depolar izer will occur in
pr efer ence t o hydr ogen evolut ion. If t his r educt ion is r elat ively slow, t he cat hode pot ent ial
will r ise fr om a t o b' as shown in cur ve II. Bet ween a and b' t he r educt ion efficiency
is 100%, but at t he pot ent ial b', which is close t o b, appr eciable hydr ogen evolut ion will
commence and t he cur r ent efficiency will fall. For a r apid r educt ion pr ocess, t he cat hode
pot ent ial r ises slowly (cur ve III) unt il limit ing cur r ent densit y is at t ained. Aft er t hat a
r apid incr ease of pot ent ial and hydr ogen liber at ion occur s.
Ta fe l Eq u a t i on : An elect r ode pr ocess can be descr ibed by eq. (23).
OX + Ze
R ...(23)
wher e OX r epr esent s par t icles which ar e near t he elect r ode and ar e subject t o r educt ion
by accept ing Z elect r ons. R denot es par t icles for med immediat ely aft er t he char ge-
t r ansfer st ep.
The r at e of elect r ochemical r eact ion (eq. 30) expr essed in t he unit s of cur r ent densit y
in t he for war d i r educt ion and r ever se i oxidat ion dir ect ions can be descr ibed by
means of gener al kinet ic equat ions (24, 25)
i
= zF K
1
C
OX
...(24)
i
= zF K
2
C
R
...(25)
At equilibr ium i.e., at t he r ever sible pot ent ial of t he syst em, E = E
r
i
=
i
= zF
0
1
K C
OX
= zF
0
2
K C
R
= i
0
...(26)
wher e i
0
is t he exchange cur r ent at t he elect r ochemical st age. The Ner nst equat ion (27)
holds good
E
r
= E
0
+
RT
zF
ln
OX
R
C
C
...(27)
wher e E
r
is t he pot ent ial differ ence acr oss t he int er face at equilibr ium, E
0
is t he st andar d
pot ent ial of t he r edox couple C
OX
/ C
R
.
When t he elect r ode pot ent ial depar t s fr om t he equilibr ium value in t he negat ive or
posit ive dir ect ion, assuming t he value E
r
r eact ion (23) will pr oceed pr edominant ly in one
dir ect ion at a r at e iE det er mined by t he equat ion (28)
iE = i i = zF (Ek
1
C
OX
EK
2
C
R
) ...(28)
and t he r elat ionship bet ween cur r ent (cur r ent densit y) and pot ent ial is r epr esent ed by
t he But ler -Volmer equat ion (35) for condit ions wher e concent r at ion at t he int er face and
t he bulk ar e t he same :
i = i i
s
= i
( )
( )

1 /
e
zF RT
e
e zF RT e
...(29)
wher e
e
= E
1
E
r
, is t he elect r ochemical over pot ent ial i, t he equilibr ium exchange
cur r ent densit y, i, t he net cur r ent . The dist r ibut ion coefficient char act er izing t he
fr act ion of t he double layer ener gy t hat effect s t he for war d r eact ion is known as t he
t r ansfer coefficient . Thus t he fr act ion of t he ener gy r equir ed for t he for war d r eact ion
is and t hat for t he backwar d r eact ion is (1 ).
The equat ion (29) can be simplified for making cer t ain appr oximat ions.
The equat ion : =
( ) 1
RT
zF
ln
( )
+
0
1
RT
i
zF
ln i
a
...(30)
can be t r ansfor med int o Tafels equat ion for t he anodic pr ocess
= a
a
+ b
a
log i ...(31)
a
v
tan v=b
5 4 3 2 1 0 +1
(E),
Fig. 13.6 : Det ermining Tafel const ant s aand b from a semilogarit hmic
plot of over pot ent ial against cur r ent densit y i at 0 or 0
Thus, t he over pot ent ial is linear ly dependent on t he logar it hm of t he cur r ent densit y
and obeys Tafels equat ion
= a + b log i ...(32)
The Tafel const ant s a and b depend on t he elect r ode mat er ial, t emper at ur e, t he
solut ion composit ion and cur r ent densit y and t hus gains fundament al significance.
The det er minat ion of r elat ionship bet ween cur r ent and pot ent ial assumes impor t ance
for elect r ochemical r edox r eact ion of or ganic compounds. The value of i
0
(excha nge
cur r ent ) and (t r ansfer coefficient ) for a single st ep elect r ochemical act can be found
gr aphically in Fig. 13.6, by plot t ing against log i in t hat r egion of over pot ent ials
((zF
n
) > RT) wher e eit her equat ion
=
ln ln
c
RT RT
i i
zF zF

...(33)
(st r ong cat hodic polar izat ion) or equat ion (st r ong anodic polar izat ion is sat isfied. The
slope b of t he is log i st r aight t ime in Fig. 13.6 is equal t o 2.3RT/ zF, and hence
= 2.3
b
RT
zF
...(34)
The exchange cur r ent i can be det er mined fr om t he value of over pot ent ial a, at log
i = 0, i.e., at unit cur r ent densit y
i
0
= 10
azF/2.3RT
= 10
a/ b
...(35)
The mor e gener al expr ession of equat ion (29) can be r ewr it t en as follows :
ln
0
ln
1
n
n
zF RT
zF i
i
RT
e
...(36)
= 0 = (V)
log
i
1e
zF /RT
Fi g. 13.7 : Gr aphical det er minat ion of t he exchange cur r ent densit y i
0
and t r ansfer
coefficient by subst it ut ing exper iment al dat a int o Eqn. (36).
References
1. Baizer , M.M., Or ganic Elect r ochemist r y, Mar cel Dekkar , New Yor k (1973).
2. Bar d, A.J ., and Lund H., Encyclopedia of Elect r ochemist r y of element s, Vol. 13,
Mar cel Dekkar , New Yor k (1979).
3. Daniel, C.S., Kuwana, T. and Roger , G.P., J . Elect r oanal. Chem., 98, 345 (1979).
4. Lacan, M.K., J akopac, V., Domani O. Rogic, and Tabokovic I., Synt h. Commun. 4, 219
(1974).
5. Lund, H., Adv. Het er ocyclic Chem., 12, 213 (1970).
6. Nat ar ajan, P., Tr ans SAEST, 17, 145 (1982).
7. Eber son, L. and Nyber g, K. in Advances in Physical Or ganic Chemist r y, Vol. 12, Aca.
Pr ess (London) 1976.
8. Selley, N.J . in Exper iment al Appr oach t o Elect r ochemist r y Ch. 6, Edwar d Ar nold,
London, 1977.
9. Weinber g, L.L., Techniques of Elect r oor ganic Synt hesis, Par t I & II, Wiley, New
Yor k, 1974.
10. Zuman, P., C.L. Per in, Or ganic Polar ogr aphy, J .W. & Sons, New Yor k (1969).
11. Zut shi R. Rast ogi and G. Dixit , Tr ans, SAEST 17, 295 (1982).
12. Zut shi K., Rast ogi R.J . Pr akt . Chem. 325 (1983), Ext . Abst r . 33r d ISE Meet ing, Lyon
(Fr ance) P. 704, Sept ember 6-10, 1982.
CHAPTER 14
CORROSION
PART A : PRINCIPLES AND CONTROL
14.1 CORROSION AND CONTROL
The det er ior at ion of a subst ance, usually t he conver sion of ir on, st eel and ot her alloys
and met als int o oxides, hydr at ed oxides, car bonat es, or ot her compounds due t o t he
act ion of air or wat er or bot h cause cor r osion. The minor component s pr esent in t he air
or wat er ar e impor t ant fact or s in t he r at e of cor r osion and pr oduce t he kind of cor r osion
pr oduct s. Nat ur al minor component s such as car bon dioxide in air and wat er cause
ser ious cor r osion, but cont aminat es int r oduced by all t ypes of air and wat er pollut ion
usually acceler at e cor r osion. Salt s, such as sea wat er , ar e ser ious causes of cor r osion.
Sulphur in fuels such as coal, oil, gasoline and nat ur al gases and ot her fuels ar e also
impor t ant sour ce of cor r osion, so t hat r emoval t r eat ment s ar e common except for coal,
alt hough t he mode of t r eat ment and t he met hods may be differ ent . Elect r ic cur r ent s
fr om power sour ces, or fr om differ ences in composit ion of mat er ials in gr ound or differ ent
par t s of met al object s ar e also acceler at or s of cor r osion.
Cor r osion Inhibit or sConvent ionally ar e a syner gist ic combinat ion of sodium nit r it e
bor ax and or ganic inhibit or s which ar e used, as t he case may be, t o pr event cor r osion
most commonly of fer r ous and non-fer r ous met al and alloy sur faces in low make up as
well as closed cooling and heat ing syst ems.
The efficiency of inhibit or s in t he cont r ol of cor r osion can be evaluat ed r eliably by
t he applicat ion of Tafel Int er cept met hod and Linear Polar isat ion Resist ance Techniques.
As per r ecent development s t hese t echniques have been successfully employed in t he
evaluat ion of ur eas, t hiour ea and semit hiocar bazide. Int er est ing r esult s have been
obt ained wit h t hiour ea as inhibit or . Resear ches have been going on fr om t ime t o t ime
t o over come t he losses due t o cor r osion and also t o impr ove t he qualit y of t he pr oduct
specially wit h r espect t o safet y.
Cor r osion ha s a lwa ys been consider ed a s one of t he impor t a nt subject s of
elect r ochemist r y and engineer ing for a long t ime as t he dest r uct ion caused t o mat er ials,
by t his pr ocess has been incr easing ever y year . In addit ion t o t his incr ease t her e has
been gr owing use of met als in moder n t echnology. Bot h t hese aspect s t oget her wit h t he
cor r osive envir onment , t he moder n civilizat ion has been gener at ing, for ces. The scient ist s
and engineer s ar e adopt ing met hods t o r educe t his cor r osion loss. Cor r osion pr event ive
t echniques and pr ot ect ion met hods have been evolved in r ecent year s which r equir e t he
immediat e at t ent ion of indust r ies.
Corrosion 187
Ant icor r osive paint ings, epoxy coat ings, galvanisat ion t echniques et c. have been t opics
of gr eat r elevance in t he pr esent day t echnology. Hot cor r osion of mat er ials has been
causing a gr eat concer n for immediat e solut ion t o t he pr oblem. Not only t his, a similar
pr oblem is faced in micr o cor r osion.
In t he pr esent t ext gener alised aspect s of cor r osion ar e pr esent ed so also t he
pr event ive met hods which pr esent some basic inst r ument al and elect r onic aspect s of
elect r ochemical t echniques specific t o cor r osion st udy and evaluat ion. St andar d elect r o-
analyt ical met hods have been discussed, ver y br iefly, st r essing t he devises used and t he
basic elect r ical cir cuit s in use.
Elect r ochemica l inst r ument a t ion ha s under gone a ma jor r evolut ion a ft er t he
int r oduct ion of oper at ional amplifier s. The measur ement , amplificat ion, cont r ol of cur r ent
or volt age have assumed new dimensions in accur acy. Int r oduct ion of t hese t echniques
have r esult ed in r apidit y of measur ement of cur r ent -volt age of EMF vs concent r at ion
plot s. The inst r ument at ion needed for t he measur ement of ionic concent r at ions has
become incr easingly sophist icat ed.
Equally r evolut ionar y has been t he int r oduct ion of digit al met hods and t he adver t
of micr opr ocessor s in measur ement met hods. This has r esult ed in int elligent inst r ument s
wit h pr ogr amming capabilit y and built -in sophist icat ed dat a analysis. Bot h r esear ch as
well as cor r osion t est ing labor at or ies have been benefit ed fr om t hese advancement s
t er ms. The ease of car r ying out t est s and dat a analysis and r eliabilit y of r esult s.
The first part discussion in t he present t ext is limit ed t o t he following aspect regarding
inst r ument at ion in cor r osion t est ing and r esear ch [2].
14.1.1 Ion Selective Electrodes
These oper at e on t he basis of membr ane equilibr ium [1]. When a membr ane separ at es
t wo solut ions and assuming it is r epr esent ing a t hin select ion of elect r ically conduct ing
mat er ial. As such it develops a pot ent ial whose magnit ude is cont r olled by t he
concent r at ion of t he ions. For t he membr ane, ideally a single ion specificit y is pr efer r ed.
Combining t he membr ane elect r ode wit h a non-polar izable r efer ence elect r ode; it should
be possible t o measur e cell emf. The most common membr ane viz. t he glass elect r ode
is r epr esent ed by :
Ag/AgCl/HCl (0.01 m)/glass/HA, NaA, NaCl/AgCl/Ag ...(1)
wher e Ag/AgCl is a r efer ence elect r ode being used as br idge elect r ode. In a t ypical pH
measur ement , t he commonly used r efer ence is a sat ur at ed colonel elect r ode :
Ag/AgCl (0.1 m)/ glass/H
+
Test solut ion KCl (sat d.) HgCl
2
/Hg (SCE) ...(2)
The cell pot ent ial may be r epr esent ed as
E = const . +
RT
ZF
ln a
n
+ (Solut ion) ...(3)
TABLE 14.1
Typica l pot en t ia ls of Ion -Select ive elect r odes [3] (25C)
Ion Output Potential Calibration Range Resistance
(mV) Range (m) (M)
Anions
F
200 t o + 200 1 10
10
0.20
Cl
0 t o + 200 1 5 10
5
30
Br
120 t o + 200 1 5 10
6
30
I
390 t o + 90 1 5 10
6
30
Cat ions
Cd
++
70 t o 280 1 10
8
1
Cu
++
+180 t o 20 1
Pb
++
+30 t o 160 1 10
10
1
Ca
++
+80 t o 60 25
K
+
+200 t o 200 1 10
7
250
Na
+
+100 t o 400 100
H
+
+414 t o 414 1 10
14
200
+
4
NH +150 t o 100 1 10
4
50
wher e t he EMF E depends on a const ant , namely t he st andar d elect r ode pot ent ial E
0
and a concent r at ion dependent t er m RT/ ZF. In aH
+
, (4). Thus t he cell pot ent ial is
dir ect ly pr opor t ional t o t he ionic concent r at ion. Typical out put pot ent ials of ion select ive
elect r odes wit h r espect t o Sat ur at ed Calomel Elect r ode (SCE) ar e given in (Table 14.1).
As indicat ed in t he t able, t hese ion select ive elect r odes have high int er nal r esist ance
and t hus r equir e for signal amplificat ionamplifier s wit h ver y high input impedance
(Zi). For a measur ement accur acy of 0.1%, t he enquir ed Zi is at least t hr ee or der s of
magnit ude higher t han t he elect r ode impedance. Thus for a glass elect r ode having
t ypical impedance of 2 10
8
ohms, t he amplifier should have Zi of 10
11
10
12
ohms.
E
R
p
=10 ohms
E =1Volt
6
cell
Cell
R
+
|Y loss|
R
load
Fi g. 14.1 : Effect of int er nal r esist ance of t he
measur ing device on t he accur acy of measur ement
Figur e 14.1 descr ibes t he equivalent cir cuit of an ion-select ive elect r ode based cell
having an impedance of R
p
and t he measur ement amplifier impedance of R
load
. The
r esult ing er r or volt age V
loss
manifest s as er r or which diminishes wit h incr ease in R
load
.
14.1.2 OPERATIONAL AMPLIFIERS
Oper at ional amplifier s ar e t he building
blocks of most amplifier s. These have
di ffer en t i a l i n pu t t er mi n a l s . Th e
oper at ional amplifier (OA) can be used
t o implement eit her inver t ing or non-
inver t ing amplifier s. An ideal OA has
an infinit e Z
i
, zer o out put impedance
(Z
0
), infinit e gain and zer o input bias
cur r ent (Fig. 14.2).
The OA of t he pur pose of inver t er
wit h gain ut ilizes a feedback cir cuit as
shown in Fig. 14.2. The cur r ent i
i n
flowing t hr ough R
i
is given by e
i
LR
i
.
Cur r ent flowing t hr ough R
f
is 0 e
0
/ R
f
.
Since no cur r ent flows int o t he input of OA (bias cur r ent zer o for ideal OA), i
in
= i
i
. Thus
e
0
= e
i
R
f
/ R
i
..(4)
i
in
i
f
R
f
+
Fi g. 14.3 : Cur r ent t o volt age conver t er for zer o r esist ance ammet er
Open loop gain of OA is t ypically 10
5
10
8
and t he feedback est ablishes st abilit y and
t he linear it y of t he amplifier . Cur r ent t o volt age conver t er s ar e usually implement ed by
dr opping t he cur r ent acr oss a r esist or and measur ing t he volt age dr opped acr oss it . OA
can be used t o implement a zer o r esist ance ammet er (Fig. 14.3). Since i
in
has t o flow
t hr ough t he feedback r esist or R
f
, t he volt age dr opped acr oss t he r esist or is
e
0
= i
in
. R
f
...(5)
Cur r ent t o volt age conver t er cir cuit s ar e used in pot ent iost at s, galvanost at s and
polar ogr aphy equivalent .
14.1.3 Potentiostat
The figur e given ahead shows t he basic pr inciple of a t ypical pot ent iost at ic cir cuit
highlight ing it s similar it y t o a t ypical OA based non-inver t ing amplifier . The pot ent ial
differ ence bet ween t he r efer ence elect r ode and t he wor king elect r ode is cont r olled by
OA.
The pot ent ial differ ences bet ween wor king a r efer ence elect r ode is cont r olled
independent ly of wor king and count er elect r ode polar izat ion r esist ance and elect r olyt e
r esist ance.
Corrosion 189
e
i
i
n
R
i
i
f
R
f
e
0
+
F i g . 14. 2 : Oper a t i on a l a mpl i fi er . I t s
ch a r a ct er i s t i cs a n d i n ver t i n g a mp l i fi er
configurat ion
14.1.4 Galvanostat
Galvanost at s ar e used in chr onopot ent io-
met r y, plat ing and ot her applicat ions wher e
t he cur r ent is r equir ed t o be cont r olled via
volt age cont r ol acr oss a fixed r esist ance
inser t ed bet ween r efer ence and wor king
elect r ode t er minals. A simple galvanost at
is given in schemat ic diagr am below :
14.1.5 Polarography
Pola r ogr a phy dea ls wit h obt a ining t he
cur r ent pot ent ial cur ve wit h a dr opping
mer cur y elect r ode (DME). It s use as an
analyt ical t ool, for under st anding mecha-
nisms of elect r ode r eact ions and for t he
st udy of complexes has st imulat ed development of it s t heor y and inst r ument at ion
polar ogr aphy has assumed a significant place in elect r ochemical t echniques aft er t he
int r oduct ion of AC polar ogr aphy (ACP), pulse polar ogr aphy (PP) and differ ent ial pulse
polar ogr aphy (DPP).
The det ails of all t hese t echniques have alr eady been descr ibed in t he for egoing
chapt er s on polar ogr aphy in t his t ext .
14.1.6 Pulse Plating Sources
However , infor mat ion on wave for ms and
equipment for pulse plat ing is descr ibed
br iefly.
Pulsed galvanost at ic plat ing can lead
t o met al deposit s of incr eased unifor mit y.
Th e r es i den ce t i me a t l ow a n d h i gh
pot ent ial may be chosen independent ly.
Inst r ument at ion for pulse plat ing depends
on t he power r ange as well as t he pulse
shape r equir ement . The figur e (shows t he
var ious wave for ms used in pulse plat ing).
The volt age t o cur r ent conver t er can be
used t o implement pulsed galvanost at ic
plat ing by employing a suit able wave for m
gen er a t or . Un i pol a r pu l s es ca n be
gener at ed by simple swit ching equipment
while popular pulses r equir e t he use of
complex swit ching schemes.
Fig. 14.4 : Use of operat ional amplifier t o make
galvanost at ic cir cuit s
Fi g. 14.5 : Var ious pulse plat ing wavefor ms.
R
C
Cell
d
V
ref
Cell = V
ref
/R
or1
Unipolar pulses
Bipolar pulses
Pulsed pulse reverse
Pulse-on-pulse
Duplex pulses
14.1.7 Micro Processor Based Instrumentation
Applica t ion of digit a l t ech -
n i qu es a n d t h e a dver t of
micr opr ocessor s ha s been a
major change in t he elect r o-
chemical inst r umen-t at ion. Use
of analog t o digit al conver t or
(ADC) and digit al t o analog
con ver t er (DAC) r es u lt s in
int er facing t he analog signals
t o t h e di gi t a l doma i n of
micr opr ocessor s. The t ask of
r a mp gener a t ion, set t ing of
scan limit s and super posit ion
of AC volt age is t aken over by
DAC a n d s oft wa r e. Si gn a l
pr ocessing is done by applying
s oph i s t i ca t ed ma t h ema t i ca l
algor it hms t o t he digit al dat a
off-l i n e. A t ypi ca l di gi t a l
pot ent iost at is shown in Fig.
14. 6, wh er ei n t h e bu i l di n g
blocks have been indicat ed.
14.1.8 Damage and Control
I n t r od u ct i on : Hydr ogen damage r esult ing fr om t he ent r y of hydr ogen int o st eel dur ing
pr oduct ion, fabr icat ion and ser vice condit ions is a major pr oblem. The mode of ent r y,
upt a ke a nd subsequent int er a ct ion of hydr ogen in st eels, t oget her wit h ot her
phenomenological aspect s of hydr ogen damage ar e r elevant t o pr esent day t echnology.
The effect s of hydr ogen on t he physical and mechanical pr oper t ies of st eels and
ot her alloys ar e r elevant t o many t echnological and engineer ing applicat ion.
As alr eady indicat ed hydr ogen damage is a major pr oblem in pr esent day t echnology,
as it places higher demands on t he per for mance of many st eels under act ual ser vice
condit ions. In fact hydr ogen embr it t lement and hydr ogen assist ed cr acking of st eels
limit t heir useful life and pose const r aint s in t he select ion of suit able st eels for cer t ain
useful component s. In one for m or t he ot her , hydr ogen pr oblems ar e encount er ed in (a)
nuclear power plant s, (b) t her mal power st at ions, (c) fer t ilizer plant s, (d) pet r oleum
r efiner ies, (e) aer ospace and (f) hydr ospace pr oject s so also in fusion r eact or t echnology.
14.1.9 Sources of Hydrogen and Modes of Entry
In gener al, st eels come in cont act wit h gaseous hydr ogen or hydr ogen pr oducing
envir onment . As such t he following sour ces may be r egar ded as t he main sour ces.
Corrosion 191
Fi g. 14.6 : Block schemat ic of a micr ocomput er
based pot ent iost at
DAC
To AUX
Voltage to current
converter
To AUX
Power booster
ADC
Analog
multiplexer
From WE
From REF
Digital computer
Current to voltage
Converter
Buffer
(i) Hydr ogen dissolved in molt en st eel dur ing pr oduct ion picked up subsequent ly
dur ing cast ing, heat t r eat ment and welding oper at ions.
(ii) Hydr ogen absor bed by st eel at elevat ed t emper at ur e an exposur e t o hydr ogen
cont aining envir onment .
(iii) Hydr ogen absor bed by t he st eel while in cont act wit h high pr essur e hydr ogen
gas.
(iv) Nascent hydr ogen absor bed by st eel dur ing pickling and elect r oplat ing.
(v) Hydr ogen and it s isot opes implant ed by high dose char ged par t icles or r adiat ion
in alloy st eels used as shields in fission and fusion devices.
(iv) Diffusion of hydr ogen in st eel occur s due t o t he gr adient in t he chemical pot ent ial
of dissolved hydr ogen. Ficks laws ar e obeyed and int er st it ial diffusion is t he
pr edominant pr ocess. Diffusion of hydr ogenat ion also be t he consequence of a
gr adient in elect r ic field (elect r on t r anspor t ) or a gr adient in t emper at ur e
(t her mot r anspor t ) or a gr adient in st r ess.
Duplex st ainless st eels have good r esist ance t o localized cor r osion and ar e widely
used in sever e cor r osive envir onment s like pet r oleum r efiner ies, pet r ochemical indust r ies,
mar ine at mospher e et c.
The high t emper at ur e, high pr essur e aqueous envir onment and t he pr esence of
r adiat ion pose a var iet y of cor r osion pr oblems for mat er ials used in Nuclear Power
Plant s. The cor r osion pr oblem of condenser s is common t o convent ional power plant s
including st ainless st eel pipes, int er nal component s and st eam gener at or s and off-shor e
sect or .
The degr adat ion of mat er ials t akes place when exposed t o high t emper at ur e.
Degr adat ion of mechanical pr oper t ies, loss of met al due t o cor r osion/oxidat ion, DC-
scaling or spalling of pr ot ect ive layer s, localized at t ack such as dent ing/heat spot s et c.
The high t emper at ur e cor r osion pr oblems ar e r elat ed t o t he air cr aft power plant s in
air cr aft indust r y.
Engines and gas t ur bines oper at e at elevat ed t emper at ur e t o r ealize maximum
efficiency. Such applicat ions r equir e mat er ials t o wit hst and damages due t o cr eep, fat igue,
cor r osion, er osionet .
Dur ing t he pr oduct ion of oil and gas fr om deep wells by combust ion, car bon dioxide
flooding et c., t her e is quit e a possibilit y of encount er ing hydr ocar bons associat ed wit h
undesir able fluids mainly, car bon dioxide and H.S. Bot h t hese fluids r esult in sever e
cor r osion in pr esence of even small amount s of wat er .
14.1.10 Mechanism of Corrosion of H
2
S CO
2
H
2
S is a colour less t r anspar ent gas wit h r ot t en egg odour . It s sp. gr . is 1.92, and 2.9
volumes gas ar e soluble in one volume of wat er at 20C. Nascent Hydr ogen is pr oduced
in t he elect r ochemical r eact ion of ir on.
Fe Fe
2+
+ 2e
...(7)
H
2
S S
2+
+ 2H
+
...(8)
Fe + H
2
S FeS + H
2
...(9)
2H
+
+ 2e
H + H H
2
...(10)
Nor mally bot h hydr ogen at oms combine t oget her at t he met al sur face t o for m
molecular hydr ogen.
Ther e ar e t wo dist inct phenomena which may occur due t o t he penet r at ion of hydr ogen
at om int o st eel lat t ice st r uct ur e.
(a) Sulphide st r ess cor r osion cr acking (hydr ogen embr it t lement )
(b) Hydr ogen induced cr acking.
(a) When H
2
S is int r oduced int o a syst em bot h sulphide ion and at omic hydr ogen
ar e pr esent in t he elect r olyt e. Sulphide ions r educe t he r at e of combinat ion of
hydr ogen at oms t o for m molecular hydr ogen, t hus cr eat ing a lar ge cone of at omic
hydr ogen on met al sur face. This r esult s in migr at ion of mor e at omic hydr ogen
t hr ough gain boundar ies of met al making t he met al br it t le. When t he met al is
under st r ess, due t o loss of duct ilit y, it fails wit hout being plast ically defor med,
r esult ing in sudden failur e.
(b) As alr eady explained, at omic hydr ogen is capable of penet r at ing any met al.
When t his at om migr at es int o st eel, it get s lodged in t he int er nal fissur es and
non-met allic inclusions. As mor e and mor e hydr ogen is t r apped, for mat ion of
molecular hydr ogen occur s. This molecular hydr ogen cannot diffuse out of st eel
and pr essur e in t he gas pocket incr eases. The equilibr ium pr essur e of at omic
hydr ogen wit h molecular hydr ogen is sever al hundr ed t housand pounds and is
capable of r epur ing any mat er ial.
14.2 MECHANISM OF CARBON DIOXIDE CORROSION
When CO
2
dissolves in mat t er it for ms car bonic acid which is cor r osive.
CO
2
+ H
2
O H
2
CO
3
...(11)
The sever it y of CO
2
cor r osion depends on CO
2
concent r at ion, it s par t ial pr essur e,
wat er cont ent , t emper at ur e, flow viscosit y, pr essur e et c. This t ype of cor r osion is gener ally
weight loss t ype, but in t he pr esence of CO
2
it can r esult in st r ess cor r osion. Pr essur e
incr eases t he solubilit y of CO
2
, while t emper at ur e decr eases t he same. In gas condensat e
wells, par t ial pr essur e of CO
2
is used as yar dst ick t o pr edict cor r osiveness. Less t han
3 psi par t ial pr essur e is non-cor r osive, 3 t o 30 psi may be cor r osive and mor e t han 30
psi is definit ely cor r osive.
Par t ial pr essur e (in psi) =
( )
2
t ot alpr essur e in psi % by vol of CO
100
Car bonic acid for med as above, r eact s wit h ir on t o for m ir on car bonat e.
Fe + H
2
CO
3
FeCO
3
+ H
2
...(12)
CO
2
and H
2
CO
3
act as cat alyst for evolut ion of hydr ogen. Anode zone is cor r oded while
cat hode zone r emains int act .
Ir on car bonat e for med as above, for ms a pr ot ect ive film against cor r osion, mainly
when t he t est is car r ied out under st at ic condit ions. Under dynamic condit ions or in pipe
under flow condit ions, t his layer is dest r oyed and fr esh cor r osion occur s. This exer cise
is cont inuously r epeat ed unt il t hick non-por ous pr ot ect ive film is made on t he sur face.
Nor mally CO
2
r esult s in unifor m cor r osion. But pit t ing or localised cor r osion can also
r esult under low flow or even at elevat ed t emper at ur e condit ions.
Corrosion 193
Inhibit ors : Acid Cor r osion Inhibit or s.
Gener ally, cor r osion of met als in acidic envir onment is caused by t he elect r ochemical
pr ocess which occur on t he met al sur face and/or at t he met al/solut ion int er face. Due t o
sever e envir onment r est r ict ions, or ganic chemicals ar e widely accept ed as bet t er acid
cor r osion inhibit or s.
The funct ion of t hese inhibit or s is br iefly descr ibed :
(i) Chemosor pt ion of or ganic molecule on met allic subst r at e wit h specific act ive
sit es like nit r ogen sulphur , oxygen, hydr oxyl gr oup or as unsat ur at ion in t he
molecule. This chemical adsor pt ion const it ut es a mono or mult inuclear layer on
t he met al sur face which is almost imper meable for ionic exchange.
(ii) Complexing of t he molecule wit h met al in which r emains in a solid lat t ice.
(iii) Neut r alizat ion of t he cor r odent .
(iv) Absor pt ion of t he cor r odent .
The or ganic cor r osion inhibit or s which have been pr oved successful t o a desir able
ext ent in pr event ing cor r osion of met als in acidic envir onment s can be cat egor ized in
t he following gr oups. These ar e :
(a) Acet ylene der ivat ives and aldehydes.
(b) Alkyl/ar yl ar r ives.
(c) Sulphur based amide der ivat ives.
(d) Long chain alkyl phenol et hoxylat es.
(e) Thiazoles/Pr iazoles.
(f) Quat er nar y ammonium compounds
(g) Or ganophosphor ous compounds, and
(h) Halogenat ed ar omat ics.
However , ideal cor r osion inhibit or s do r equir e cer t ain ideal condit ions. In or der t o
fulfill t hese r equir ement s t hey should exhibit t he following specificat ions.
They should be r eadily soluble which can easily be disper sed in acids and easy t o
monit or . At t he same t ime t hey should r emain st able in acids for sever al days and
should not float on bat h sur face. They should wit hst and t emper at ur e of use wit hout
decomposit ion. No insoluble compounds should be for med wit h met allic salt s. They
should fully pr event or at least significant ly r educe t he evolut ion of hydr ogen. They
should be easily r emovable fr om t he sur face by r aising and at t he same t ime hydr ogen
embr it t lement of met als should not be caused. No pit t ing cor r osion should t ake place as
well as t hey should not be har mful t o t he envir onment and should not cause unnecessar y
pollut ion.
Cor r osion inhibit ion st udies have been car r ied out fr om t ime t o t ime. Mor eover t he
subject of cor r osion wit h r egar d t o inhibit ion deals wit h engineer ing and allied t echnology.
The aut hor is specially t hankful t o t he aut hor s of t he book on met allic cor r osion
pr inciples and cont r ol published by New Age Int er nat ional Limit ed Publisher s, New
Delhi.
References
1. Kor yt a, J ., Ion select ive Elect r odes Cambr idge Univer sit y Pr ess, Cambr idge (1975).
2. Khosla, N.K., Met allur gical Engineer ing, Indian Inst it ut e of Technology, Bombay-400
076.
PART B : STABILITY OF METALS
14.3 THERMODYNAMICS AND THE STABILITY OF METALS
The r eal cr it er ion for deciding t he st abilit y of an ir on vessel is t he magnit ude of t he
r at e of it s dissolut ion. If it has a negligible r at e of cor r osion and sufficient st r engt h, it
is consider ed suit a ble for t he pur pose of const r uct ion or fa br ica t ion in a given
envir onment .
TABLE 14.2
Pr oduct s and Over all Ener get ics of Spont aneous Cor r osion React ions*
Hydrogen t ype, Oxygen t ype,
2
H
p
= 1.0 at m p
O2
= 0.21 at m
Metal S olid product Free-energy change at 25C,
cal g-mole
1
metal
Silver Ag
2
O + 27,000 1,080
Copper CuO + 24,800 37,450
Cu(OH)
2
+ 27,800 28,300
Cu
2
O + 9,500 18,600
Lead PbO (r ed) + 11,500 44,600
Nickel Ni(OH)
2
+ 7,800 48,500
Cadmium Cd(OH)
2
+ 600 55,600
Ir on Fe(OH)
3
+ 4,700 80,000
Fe(OH)
2
2,260 58,500
Fe
3
O
4
5,020 80,000
Zinc Zn(OH)
2
(?) 19,240 75,200
Chromium Cr (OH)
3
32,500 117,000
Aluminium Al(OH)
3
(?) 102,570 180,700
Magnesium Mg(OH)
2
84,000 140,000
*F. L. La Que and H. R. Copson, eds., Corrosion Resistance of Metals and Alloys, Reinhold
Publishing Cor p., New Yor k, 1963 (By cour t esy).
Supposing, even befor e calculat ing or measur ing t he cor r osion r at e; t he st abilit y of
st eel vessel is under quest ion as t o whet her t he Fe Fe
++
+ 2e de-elect r onat ion r eact ion
and t he elect r onat ion r eact ion, which t oget her const it ut e t he cor r osion pr ocess, pr oceed
spont aneously or not (equilibr ium t her modynamics).
Using t her modynamics such quest ions can be answer ed for example making use of
t he r elat ion bet ween fr ee ener gy change and equilibr ium pot ent ial in or der t o obt ain
fr ee ener gy changes for t he elect r onat ion and elect r onat ion r eact ions. The sum of t he
t wo fr ee-ener gy changes yields t he t ot al fr ee-ener gy change for t he cor r osion pr ocess
Corrosion 195
G = nFV ...(1)
If t his t ot al fr ee-ener gy change is negat ive, t hen t he cor r osion of t he met al will
pr oceed spont aneously. Calculat ed (Table 14.2) fr ee-ener gy changes for t he cor r osion
r eact ions of differ ent met als wit h hydr ogen evolut ion and oxygen r educt ion as t he
elect r onat ion r eact ions.
A shor t cut appr oach based on t he pot ent ial ver sus pH r epr esent at ion of equilibr ium
pot ent ials is also available. The appr oach is as follows:
Suppose t he M
n+
+ ne = M r eact ion does not involve pr ot on t r ansfer . It s equilibr ium
pot ent ial is t hen independent of pH and can t her efor e be r epr esent ed on t he pot ent ial
pH diagr am as a st r aight line par allel t o t he pH axis. Fig. 14.1.
Next , one consider s t he elect r on accept or A pr esent in t he solut ion which is in
con t a ct wi t h t h e met a l M a n d
calculat es t he equilibr ium pot ent ial
for it s r ea ct ion. Suppose it does
involves a prot on t ransfer as well, i.e.,
xA + mH
+
+ ne = yD + zH
2
O. Since
t his r eact ion involves bot h elect r on
t r a nsfer a nd pr ot on t r a nsfer , it s
equilibr ium pot ent ial will var y wit h
pH a nd ca n be r epr esent ed a s a
st r aight line sloping downwar d see
pot ent ial pH diagr am Fig. 14.8.
On ce on e h a s a pH pot en t ia l
diagr am wit h lines dr awn for t he
r eact ion M
n+
+ ne = M r eact ion and
for t he xA + mH
+
+ ne = yD + zH
2
O
r eact ion, all one has t o do is t o dr awn
line per pendicular t o t he pH axis at
t he par t icular value of pH cor r es-
ponding t o t hat of t he solut ion (see
last Fig). If t hat line int er sect s t he
M
n+
+ ne = M line at a mor e negat ive
value of pot ent ial t han t he xA + mH
+
+ ne = yD + zH
2
O line, t hen a simple
conclusion follows. The M
n+
+ ne = M
r eact ion will t end t o r un spont a-
neously in t he de-elect r onat ion dir ect ion and pr oduces M
n+
fr om M, i.e., dissolut ion, and
t he ot her r eact ion will t end t o pr oceed spont aneously as an elect r onat ion r eact ion (and
t hus absor b elect r ons supplied dur ing de-elect r onat ion) if a pat h is pr ovided for t he
elect r on flow fr om t he sink for t he de-elect r onat ion r eact ion t o t he sour ce for t he
elect r onat ion r eact ion. The met al M will be said t o cor r ode spont aneously.
On t his basis, it is clear fr om t he Fig. 14.8 ahead t hat , if t he solut ion in t he mild-
st eel r eact ion vessel cont ains Fe
++
ions at a concent r at ion of unit act ivit y and if t he pH
= 2, t he mat er ial of t he vessel must t end t o dissolve. [It is t o be not ed t hat , at higher
Pot ent ial
x
y
z
2
+n
e =
D
+
H
O
A
+m
H
+
M=M
n +
+ne
P
o
t
e
n
t
i
a
l
p H of
solut ion
pH
Fi g. 14.7 : The pot ent ialpH diagr am for t he given
syst em of t he met al-dissolut ion and elect r onat ion
react ion reveals t he t endency of t he met al t o corrode.
pH values, t he pot ent ial of ir on becomes pH dependent . This is because, wit h incr easing
OH
ion concent r at ion, t he Fe(OH)

2
species is for med and cont r ols t he pot ent ial. It s
concent r at ion is of cour se pH dependent , and t he excess fer r ous ions or iginally pr esent
ar e pr ecipit at ed]. It must , t her efor e, be r eject ed as an unsuit able mat er ial for holding
a pH = 2 solut ion.
Suppose, however , t hat t he solut ion in t he r eact ion vessel does not cont ain any
fer r ous ion. Then what is t he concent r at ion or act ivit y t hat must be inser t ed in t he
Ner nst expr ession for t he equilibr ium pot ent ial of t he Fe
++
+ 2e = Fe r eact ion? What
value should be used for C
Fe
++
in Fe, Fe
++
/
Fe
= ( ) ++
0
Fe
RT
E + l n C
2F Fe Fe
++
The value for C
Fe
+2
is obviously zer o, in which case Ner nst s equat ion for elect r ode
pot ent ial of t he Fe
++
+ 2e = Fe equilibr ium indicat es a value which would be highly
negat ive. Since t his pot ent ial
is negat ive wit h r espect t o t he
equilibr ium pot ent ial of any
possible elect r onat ion r eac-
t i on , t h e i r on wi l l s t a r t
dissolving and building Fe
++
concent r at ion in t he solut ion
layer which is in cont act wit h
t he elect r on sink ar ea of t he
ir on. If t his layer is st agnant
a nd t he Fe
++
ions a r e not
r emoved by a chemical r eac-
t ion, e.g., pr ecipit at ion, t he
Fe
++
concent r at ion will climb
up fr om zer o clear ly, t he Fe
++
ion concent r at ion adjacent t o
t he met al is det er mined by
t he amount of met al which
has dissolved, and how fast
t his diffuses away.
How mu ch i r on mu s t
dissolve t o at t ain a given Fe
++
concent r at ion? A fer r ous ion
concent r at ion of 10
6
mole lit er
1
cor r esponds t o t he dissolut ion of about 0.06 mg of ir on
per lit er of solut ion. Hence a concent r at ion of less t han 10
4
mole lit er
1
, e.g., 10
8
mole
lit er
1
, cor r esponds t o t he dissolut ion of ar ound a micr ogr am of ir on per lit er of solut ion
in cont act wit h t he met al. On t he ot her hand, a fer r ous ion concent r at ion of mor e t han
10
6
mole lit er
1
, e.g., 10
4
mole lit er
1
, r equir es t he dissolut ion of a few milligr am of ir on
per lit er of solut ion in cont act wit h it i.e., t he dissolut ion of a significant quant it y of
ir on.
Fig. 14.8 : The pot ent ialpH diagram for iron immersed
in a fer r ous-ion solut ion of unit act ivit y.
Corrosion 197
2H
+
2
e
H
+
2
Fe Fe
2+
+2e(Fe =1)
2+
0
0.441
E
(volts)
1 2 3
pH
I n vi ew of t h es e
consider at ion one can adopt
an ar bit r ar y, cr it er ion i.e.,
A fer r ousion concent r at ion
of 10
6
mol e l i t er
1
a n d
higher implies t he occu-
r en ce of con s i der a bl e
dissolut ion, i.e., cor r osion.
Put t ing t hese consider a -
t i on s i n ba ck gr ou n d, i f
con ven t ion a l in u s in g a
pot ent ialpH diagr am for
deciding whet her a met al
can possibly cor r ode or not ,
t o calculat e t he equilibr ium
pot ent ial for t he M
n+
+ ne =
M r eact ion for a met al ion
concent r at ion of 10
6
mole
lit er
1
.
A similar appr oach like
cor r os i on of mi l d s t eel
vessel not init ially cont ain-
ing Fe
++
ions can be used
t o inspect t he pot ent ialpH
diagr ams of ot her met als t o decide whet her t hey also t end t o cor r ode spont aneously or
not a solut ions of a given pH.
14.4 POTENTIALpH (OR POURBAIX) DIAPHRAGMS: USES AND ABUSES
It must not be imagined t hat t he ult imat e pr oduct of t he met al dissolut ion r eact ion is
always an ionic species, e.g., M M
n+
+ ne. Oft en it is a solid oxide or hydr oxide.
Fr om t he fr ee ener gy consider at ions, one can calculat e t he r ever sible pot ent ials for
a met al t hat is in equilibr ium wit h it s simple hydr at ed ions or wit h it s soluble pr oduct
of hydr olysis or wit h it s insoluble oxide. Such calculat ions give set of dat a (Table).
Pot ent ialpH diagr ams ar e useful in t his r espect t oo. Pot ent ial and pH condit ions
ar e indicat ed under which a solid pr oduct is t her modynamically st able. Fig. 14.9.
The r egions of t he pot ent ialpH diagr am in which oxide or hydr oxide for mat ion
r eceives t her modynamic appr oval ar ise as follows:
Consider ing t he case of ir on and assuming, t hat t he immediat e pr oduct of ir on
dissolut ions is fer r ous ions. The solut ion in cont act wit h ir on can dissolve fer r ous
ions only up t o t he limit which is given by applying t he law of mass act ion t o t he
r eact ion
Fe(OH)
2
+ 2H
+
= Fe
++
+ 2H
2
O ...(1)
Fi g. 14.9 : Example of pot ent ialpH diagr am for a syst em
wit h a solid phase as a dissolut ion pr oduct .
0 2 4 6 8 10 12 14
1.0
0
1.0
2.0
P
o
t
e
n
t
i
a
l
Fe
3+
FeO
2
4
O
xy
g
en
lin
e
H
y
dr
o
ge
n
lin
e
Fe
2
O
3
Fe(OH)
2
F
e
(
O
H
)
2
Fe
pH
Fe
2+
Accor ding t o t he Law of Mass Act ion, for a const ant concent r at ion of Fe(OH)
2
in
equilibr ium in a solid phase,
++
2 +
CF e
C H
= K = 10 + 13.29 ...(2)
or by CFe
++
= 2log C
H
+
+ 13.29
= 13.29 2pH ...(3)
If, as befor e, t he minimum concent r at ion of Fe
++
ions cor r esponding t o a piece
cor r oding ir on is ar bit r ar ily t aken as 10
6
mole lit er
1
, t hen
pH =
13.29+6
2
= 9.6
which means t hat above a pH of 9.6, Fe(OH)
2
is st able. Since t he Fe(OH)
2
/Fe
++
a
equilibr ium depends only on pH and not on pot ent ial i.e., it is a pur e pr ot on t r ansfer
r eact ion and does not involve elect r on t r ansfer . The Fe(OH)
2
/Fe
++
equilibr ium is shown
t he pot ent ial pH diagr am as a ver t ical line par allel t o t he pot ent ial axis (Fig. 14.10)
Above t he indicat ed pH value, t he concent r at ion of Fe
2+
ions is gover ned by t he
equat ion:
log CFe
++
= 2 log.C
H
+
+ 13.29 ...(4)
= 13.29 2 pH
hence, t he pot ent ial changes wit h incr easing pH wit h a slope of RT/F.
The quest ion of how t he cor r osion of a met al is affect ed by t he for mat ion of a solid
pr oduct of t he dissolut ion r eact ion is r at her complex. It is impor t ant however , t hat
wher eas t he pot ent ial pH diagr am indicat es t hat a par t icular hydr oxide, e.g., can be
for med only above a cer t ain pH value. It is exper iment ally obser ved t hat t he hydr oxide
is for med when t he elect r ode is immer sed in a solut ion wit h much lower pH value. This
appar ent cont r adict ion
ar ises (1) because t he
va l u e s of p H i n a
pot ent ialpH diagr am
a lwa ys r efer t o t he
s ol u t i on i n t h e
immediat e vicinit y of
t h e el ect r ode a n d
(2) because t he local
pH near an elect r ode
ca n i n cr ea s e wel l
above t he bulk pH of
t h e s ol u t i on i f t h e
elect r onat ion r eact ion
t a k es pl a ce a t t h e
el ect r ode con s u mes
Corrosion 199
Fi g. 14.10 : Example of pot ent ial pH diagr am for a syst em
wit h a solid phase as a dissolut ion pr oduct .
2.0
1.0
0
1. 0
0 2 4 6 8 10 11 12 14
Fe
3+
FeO
2
4
Fe O
3 2
F
e(O
H
)
2
F
e
(
O
H
) 2
O
x ygen lin e
H
y d
ro
g e
n
li n
e
hydr ogen ions (e.g., 2H
+
+ 2e H
2
) or gener at es hydr oxyl ion (e.g., O
2
+ H
2
O + 4e
4OH
).
Ther efor e, in conclusion, pot ent ialpH diagr ams can be used t o answer whet her a
par t icular cor r osion pr ocess is t her modynamically possible or not . A compact pict or ial
summar y is pr ovided in diagr ams indicat ing elect r on t r ansfer , pr ot on t r ansfer , and
elect r on and pr ot on t r ansfer r eact ions which ar e favour ed in t her modynamic gr ounds
when a met al is immer sed in a par t icular solut ion.
An example of lead is t aken in cont act wit h aer at ed wat er . The pot ent ialpH diagr am
shows t he equilibr ium pot ent ial for t he Pb
++
+ 2e = Pb r eact ion for a Pb
++
.
Concent r at ion of ~ 10
6
g lit er
1
t o be negat ive wit h r espect t o t he equilibr ium pot ent ial
for t he hydr ogen r educt ion r eact ion at a pH less t han about 5. This implies t he t endency
for lead t o cor r ode in an aer at ed aqueous envir onment . In fact t he r at e of cor r osion is
so negligible t hat lead is used in pipes for car r ying wat er .
14.5 ELECTRONATION REACTION IN CORROSION
A ver y impor t ant aspect of
t h e cor r os i on of met a l
concer ns t he elect r onat ion
r ea ct i on r equ i r ed t o
compl et e t h e cor r os i on
cir cuit by consuming t he
elect r ons t r ansfer r ed t o t he
met a l fr om t h e met a l -
di s s ol u t i on r ea ct i on . To
answer t he quest ion as t o
what is t he elect r onat ion
(cat hodic) r eact ion? Theor e-
t i ca l l y, i t ca n be a n y
r ea ct ion wit h a n equ ili-
br ium pot ent ial which is
mor e pos i t i ve t h a n t h e
equilibr ium pot ent ial of t he
met al-dissolut ion r eact ion.
In pr act ice, it is a r eact ion
of t he t ype : A + ne = D,
wher e A is an elect r on-
accept or species pr esent in
t he elect r olyt e which is in
cont act wit h t he cor r esponding met al. Consider ing t he aqueous elect r olyt es, t he elect r on
accept or s invar iably pr esent ar e H
3
O
+
ions and dissolved oxygen, and t he cor r esponding
elect r onat ion r eact ion being
2H
3
O
+
+ 2e 2H
2
O + H
2
[acid solut ions]
and O
2
+ 4H
+
+ 4e 2H
2
O [acid solut ions]
Fi g. 14.11 : The pot ent ialpH diagr am for lead.
0 2 4 6 8 10 14 12
pH
1.0
0
1.0
2.0
Pb
++ 0
6
0
0
6
?
Pb
6
PbO
6
?
?
6
Pb
3
O
4
H
yd
r
og
en
l in
e
O
x
yge
n
lin
e
PbO
2
P
o
t
e
n
t
i
a
l
or O
2
+ 2H
2
O + 4e 4OH
[alkaline solut ion]

The elect r olyt e may also cont ain species such as Fe
3+
ions or nit r ic acid, in which
case t her e can be addit ional elect r onat ion r eact ion of t he t ype:
Fe
3+
+ e Fe
2+
...(5)
or 3H
+
+
3
NO
+ 2e HNO
2
+ H
2
O ...(6)
The possibilit y wher e sever a l elect r ona t ion r ea ct ions a r e possible, i.e., t heir
equilibr ium pot ent ials ar e posit ive wit h r espect t o t he met al dissolut ion equilibr ium
pot ent ial. In such a case t he one which yields t he highest cor r osion cur r ent is
pr efer ent ially adopt ed. Ther e is no new pr inciple her e; when par allel r eact ions can
occur , t he cur r ent is cont r olled by t hat r eact ion which yields t he lar gest cur r ent
cor r esponding t o t he given pot ent ial. This point is ver y clear when t he incr ease in
cor r osion r at e of ir on in oxygenat ed solut ion. Compar ed wit h t hat in a deoxygenat ed one
i.e., t he r at e in t he lat t er case is decided by t he 2H
3
O
+
2e = 2H
2
O + H
2
elect r onat ion
r eact ion while in t he for mer case it is det er mined by oxygen r educt ion. The higher t he
pr essur e is of oxygen in gas phase, t he higher is cor r osion r at e. This is due t o t he
solubilit y of oxygen in t he elect r olyt e is pr opor t ional t o pr essur e.
TABLE 14.3
Effect of Oxygen P r essu r e on Cor r osion Ra t e of Ir on in
1
3
2
% Sodiu m Ch lor ide Solu t ion
Oxygen pressure, at m Corrosion rat e, mm
n1
0.2 2.2
1 9.3
10 86.4
61 300
Upon addit ion of dilut e nit r ic acid, t he cor r osion r at e is incr eased even mor e because
of t he occur r ence of r eact ion involving nit r ic acid.
14.6 THE CORROSION CURRENT AND CORROSION POTENTIAL
Consider ing a syst em consist ing of a met al cor r oding is an elect r olyt e, t he cor r osion
pr ocess involves a met al-dissolut ion de-elect r onat ion r eact ion at elect r on-sink ar eas on
t he met al and an elect r onat ion r eact ion at elect r on sour ce ar eas. This is applicable t o
a met als cor r oding by a Wagner Tr aud mechanism.
It has also been point ed out t hat t he cor r oding met al, is equivalent t o a shor t
cir cuit ed ener gy pr oducing all wit h t he following specificat ions : (1) The elect r on sink
(anodic) and elect r on sour ce (cat hodic) ar eas of t he equivalent ener gy-pr oducing cell ar e
chosen equal t o t he cor r esponding ar eas on t he cor r oding met al. Thus, t he t ot al met al-
Corrosion 201
Fi g. 14.12 : In het er ogeneous syst ems, t he
distances between source (e.g., metallic inclusions)
and sink point s ar e so small t hat a pr obe cannot
usually det ect any pot ent ial differ ence in t he
elect r olyt e bet ween t hem.
dissolut ion cur r ent I
M
and elect r onat ion cur r ent
0
S
I (not cur r ent densit ies) on t he
cor r oding met al ar e equal in magnit ude but opposit e in sign, just as t hey ar e in an
ener gy pr oducing cell.
I
M
=
0
S
I
...(7)
The r at e of cor r osion of t he met al is obviously given dir ect ly by t he r at e of met al
dissolut ion. Hence t he cor r osion cur r ent I
cor r
is equal t o t he met al-dissolut ion cur r ent I
M
:
I
corr
= I
M
=
0
S
I
...(8)
This is an impor t ant feat ur e of a cor r oding syst em. However , t her e is anot her feat ur e
of a cor r oding syst em. This ar ises fr om t he shor t -cir cuit condit ion of t he cor r osion cell
and of t he equivalent cell (Act ually, it can be r ecalled t hat t he elect r on sour ces and t he
sinks in t he cor r oding met al ar e int er nally shor t -cir cuit ed, and t he t wo elect r odes in t he
equivalent t o all ar e ext er nally shor t -cir cuit ed). Hence t he t ot al pot ent ial differ ence V
acr oss t he equivalent cell is zer o. But t his cell pot ent ial is composed of t he absolut e
pot ent ial differ ence acr oss t he int er faces at t he t wo elect r odes and t he pot ent ial dr op IR
in t he elect r olyt e :
V = 0 =
S
0

M
+ IR ...(9)
Since bot h elect r odes consist of t he same met al, no pot ent ial differ ence ar ises owing
t o met al-met al cont act .
Thus when IR = 0, t he pot ent ial
differ ence acr oss t he met al-elect r olyt e
int er face at t he elect r on-sour ce elect r ode
of t he shor t -cir cuit ed equivalent cell is
vir t ually equal t o t hat at t he elect r on-
sink elect r ode.
The validit y of t he assumpt ion IR =
0 i n t h e cor r odi n g met a l cou l d be
s u gges t ed t h a t i f t h e met a l i s
homogeneous and is cor r oding accor ding
t o Wagner -Tr aud mechanism, t he sink
and sour ce ar eas ar e separ at ed at any
one inst ant by a dist ance of t he or der of
a few angst r oms. Fur t her , t he sink and
sour ce ar eas ar e shift ing ar ound and
t her efor e smear ing out t he negligible
pot ent ia l differ ence in t he solut ion
adjacent t o t hese ar eas. Thus IR = 0 is
quit e t r ue.
The validit y of IR = 0 depends upon
t he separ at ion of sink and sour ce ar eas
a n d u pon t h e con du ct i vi t y of t h e
Corrodi ng
met al
El ectron
si nks
Area seen by
probe ines
si nks and sources
El ectrol yte
Gl ass wal l s
of probe
El ectron- source area
Impuri t i es
elect r olyt e, when t he met al has het er ogenet ies and is cor r oding by local cell act ion. This
happens in special cir cumst ances in which t he dist ance apar t of sink and sour ce ar eas
is t o be consider ed (of t he or der of cent imet er s). Under t hese sit uat ions, IR = 0 and
0
S
=
M
, implies a differ ence in t he met al elect r olyt e pot ent ial differ ence at elect r on
sour ce and sink ar eas. Gener ally, t he sink t o sour ce dist ance is of t he or der of micr ons
or even less i.e., t he conducing pat h in t he solut ion, hence IR becomes negligible. Thus,
t he
S
0
is vir t ually equal t o
M
, and any negligible differ ence t hat exist s occur s over
dist ances which ar e t oo small t o be r esolved by a pr obe used t o measur e t he pot ent ial
differ ence bet ween t he met al and t he solut ion.
This unifor m pot ent ial differ ence acr oss t he int er face bet ween a cor r oding met al and
it s elect r olyt e envir onment may be t er med t he cor r osion pot ent ial
cor r
. This is given
by t he expr ession:
corr
=
S
0
=
M
...(10)
It , t her efor e, follows t hat t he cor r osion pot ent ial on a het er ogeneous met al accor ding
t o local cell act ion is vir t ually equal t o t he mixed pot ent ial at an elect r ode on which
elect r onat ion and de-elect r onat ion r eact ions ar e occur ing on separ at ed sinks and sour ces
by space. This is ident ical t o a mixed pot ent ial when t he met al is cor r oding by a Wagner -
Tr aud mechanism.
14.7 THE BASIC ELECTRODICS OF CORROSION IN THE ABSENCE OF
OXIDE FILMS
Fir st ly, t he r at e of cor r osion, a quant it y of gr eat pr act ical significance is given by t he
cor r osion cur r ent I
corr
which is equal t o t he met al dissolut ion, de-elect r onat ion cur r ent
I
M
and t o t he negat ive of t he elect r onat ion (cat hodic) cur r ent
0
S
I at t he elect r on sour ce
ar eas, i.e.,
I
corr
= I
M
=
0
S
I ...(11)
The equat ion can be wr it t en as
I
corr
= I
M
= A
M
i
M
...(12)
Since t he met al dissolut ion cur r ent is equal t o t he pr oduct of t he cor r esponding
cur r ent densit y I
M
t imes t he sink ar ea A
M
and similar ly,
I
corr
=
0
S
I =
0
S
A
0
S
i
...(13)
Secondly, t her e is a unifor m pot ent ial differ ence, e.g., t he cor r osion pot ent ial
cor r
,
all over t he sur face of t he cor r oding met al. It is t his cor r osion pot ent ial which is associat ed
wit h bot h t he met al-dissolut ions and elect r onat ion cur r ent s, i.e.,
corr
= A
M
=
S
0
...(14)
In or der t o obt ain quant it at ive expr ession for t he cor r osion cur r ent and t he cor r osion
pot ent ial t he pr oper expr ession for t he met al dissolut ion and elect r onat ion cur r ent
densit ies have t o be subst it ut ed. In case when no oxide film is for med on t he sur face of
t he cor r oding met al and neit her of t he cur r ent densit ies is cont r olled by mass t r anspor t ,
Corrosion 203
it means t hat t her e is no concent r at ion over pot ent ial, t he But ler -Volmer expr ession for
t he de-elect r onat ion and elect r onat ion-cur r ent densit ies can be inser t ed. Thus,
I
corr
= I
M
= A
M
i
M
...(15)
Also, it could be wr it t en for t he r elat ion bet ween t he cor r osion cur r ent and t he
elect r onat ion cur r ent at t he elect r on sour ce ar ea as :
I
corr
=
0
S
I
...(16)
Aft er elabor at ing t he expr essions and solving t he equat ions it is made clear t hat t he
cor r osion cur r ent depends upon t he exchange cur r ent s (i.e. available ar eas and exchange
cur r ent densit ies).
The dependence of t he cor r osion cur r ent (t he r at e at which a met al dest r oys it self)
on t he exchange cur r ent s, Tafel slopes and equilibr ium pot ent ials of t he met al-dissolut ion
and elect r onat ion r eact ion is clear ly br ought out by solving t he mat hemat ical expr essions.
In gener al, t he mor e posit ive t he equilibr ium pot ent ial of t he elect r onat ion r eact ion is
wit h r espect t o t he equilibr ium pot ent ial for t he M
n+
+ ne = M r eact ion and t he lar ger
t he exchange cur r ent s (ar eas t imes exchange cur r ent densit ies) ar e, t he gr eat er is t he
r at e of cor r osion. The Tafel slopes also ent er in t he pict ur e. A such high slopes diminish
t he enhancing effect which t he exponent ial t er m has on t he r at e of t he cor r osive at t ack
on t he met al.
14.8 FACTORS AFFECTING THE RATE OF CORROSION AND
EVANS DIAGRAMS
Most of t he fact or s affect ing t he r at e of cor r osion can be under st ood fr om t he gr aphical
pr esent at ion of t he cur r ent -pot ent ial cur ves for t he met al dissolut ion and elect r onat ion
r eact ions.
Consider ing t he met al-dissolut ion r eact ion M
n+
+ ne = M, A cur ve could be const r uct ed
as in Fig. 14.13 for t he var iat ion of pot ent ial of an elect r ode. M wit h t he de-elect r onat ion
cur r ent cr ossing t he elect r ode-elect r olyt e int er face. Such a cur ve could be obt ained
eit her exper iment ally or fr om a knowledge of t he par amet er s which det er mine t he
over pot ent ial associat ed wit h t he de-elect r onat ion cur r ent densit y. For concent r at ion
over pot ent ial, t his par amet er is t he limit ing cur r ent densit y. And, for act ivat ion
over pot ent ial, t he par amet er s ar e t he exchange-cur r ent densit y and t he t r ansfer
coefficient s. If on t he same diagr am, one can super impose a cur ve for t he var iat ion of
t he pot ent ial of t he M elect r ode. Wit h t he cur r ent associat ed wit h t he elect r onat ion of
elect r on accept or pr esent in t he elect r olyt e. The cur r ent at which t he met al dissolut ion
and elect r onat ion ar e equal is, in fact , t he cor r osion cur r ent . Fig. 14.14. The pot ent ial
cor r esponding t o t he cor r osion cur r ent is t he cor r osion pot ent ial. Evans t ype of diagr ams
Fig. 14.15(a, b) could be obt ained if only t he magnit ude of t he de-elect r onat ion and
elect r onat ion cur r ent s ar e used in t he const r uct ion of ver sus I cur ves.
Corrosion 205
M M
n+
+ne
Metal dissolution current, I
P
o
t
e
n
t
i
a
l
,
e,M
Fi g. 14.13 : The pot ent ialcur r ent r elat ion for t he
met al-dissolut ion r eact ion.
xA+mH
+
+ne
yD+zH O
2
M M
n+
+ne
e,s
0
corr
e,M
I
s
0
I
M
I +I
Electronation
current
De-el ectronati on
current
Posi ti ve potenti al
Fi g. 14.14 : The pot ent ial-cur r ent r elat ion for t he t wo r eact ions occur r ing at a
cor r oding int er face. The cor r osion cur r ent and cor r osion pot ent ial ar e defined by
t he point on t he diagr am at which t he t wo cur r ent s I
M
and I
S
0
ar e equal.
Act ually, t he Evans diagr am obt ained depend upon t he cur r ent -pot ent ial cur ves for
t he met al dissolut ion and elect r onat ion r eact ions. Some of t he common diagr ams ar e,
shown in Figs. 14.1614.18.
In t hese diagr ams t he exchange cur r ent for t he met al dissolut ion r eact ion is much
gr eat er t han t hat for t he elect r onat ion, i.e. I >> I or in which I
0,S0
>> I
0,M
. Evans
diagr ams can also be used t o br ing out t he influence Tafel slopes. The influence of
equilibr ium pot ent ials can be seen in Fig. The effect of mass t r anspor t cont r ol int o
elect r onat ion cur r ent fr om Figs. 14.15(a, b); also 14.17(a & b) & 14.18 ahead. The effect
of an IR dr op in t he elect r olyt e bet ween t he elect r on-sink (anodic) and elect r on sour ce
(cat hodic) ar eas can also be r epr esent ed in an Evans diagr am Fig. which t hen shows t he
inequalit y of t he met al solut ion pot ent ial differ ence at t he t wo ar eas, i.e., t he anodic (or
de-elect r onat ion) and t he cat hodic (or elect r onat ion ar eas).
14.9 SOME COMMON EXAMPLES OF CORROSION
In t his sect ion some elect r odic pr inciples under lying some familiar inst ances of cor r osion
ar e being cit ed. In most cases, it is expect ed t hat t he unpr ot ect ed met al beneat h t he
br oken point spot (most ly in aut omobiles) which cor r odes. The exposed met al has a
bet t er access t o oxygen t han t he met al st ill cover ed wit h paint and is t her efor e t he
elect r on-sour ce ar ea. Act ually it is t he adjoining met al
under neat h t he paint coat ing which cor r odes. The sit uat ion
is much wor se since having a br eak in paint coat ings which
lea d t o spr ea ding of cor r oded a r ea r a t her t ha n t o a
r est r ict ion of cor r osion t o t he exposed spot Fig. 14.19.
Paint s and coat ings of var ious kinds, as such ar e only
par t ially useful in cor r osion pr event ion. Oft en cr acks or
pinholes ar e developed r esult ing in exposed spot s pr oviding
access t o oxygen giving r ise t o elect r onat ion r eact ion. This
r esult s in unseen cor r osion of sur r ounding ar eas.
Consequent ly, elect r onat ion r eact ion t akes place due
t o oxygen r educt ion and t his known as t he pr inciple of
differ ent ial aer at ion. To clar ify t he oxygen elect r onat ion
t ends t o occur at t he oxygen r ich ar ea and t he met al
dissolut ion t ends t o occur at t he oxygen poor ar ea. In such
ca ses t he oxygen r ich a r ea s a ct a s elect r on-sour ces
(cat hodes) and t he oxygen-st ar ved r egions as elect r on sinks
(anodes). Thus owing t o t he diffusion of oxygen on met al
sur face, a cor r osion cell is pr oduced in which elect r on sour ce
and sink ar eas ar e spat ially separ at ed.
Apa r t fr om cor r osion due t o differ ent ia l a er a t ion,
cor r osion of under gr ound met al st r uct ur es and pipelines
may also ar ise fr om st r ay cur r ent s.
The pr esence of a cur r ent car r ying cable in conduct ing
soil r esult s in st r ay cur r ent s passing t hr ough t he soil. These
st r ay cur r ent s may set up a pot ent ial differ ence bet ween
Met al
Corrosi on
M
n+
O
2
M
n+
Moi st
Atmosphere
Paint
F i g. 14.19 : As t he paint
coa t i n g i s da ma ged, t h e
corrosion couple is est ablished
wit h t he met al dissolving at
t he edges underneat h t he
coat ing, while t he exposed
pa r t is t h e pla ce for t h e
elect r onat ion of oxygen (and
t hus not t hat which disso-
lves).
t wo por t ions of a pipeline. Ther efor e, an elect r on-sour ce (cat hodic) and sink (anodic)
ar eas ar e developed and t hus t he pipelines t end t o cor r ode when t hey pass near elect r ic
lines.
14.10 CONTROL OF CORROSION CURRENT IN THE CORROSION PROCESS
On examining t he Evans diagr am, Fig. 14.15(a) it is obser ved t hat t he cor r osion cur r ent
is cont r olled by t he elect r onat ion (cat hodic) r eact ion and as such t he cor r osion pr ocess
is under elect r onat ion i.e., cat hodic cont r ol. This is when I
0M
>> I
0
,
0
. In anot her sit uat ion,
i.e., I
0
,
S 0
>> I
0,M
it could be indicat ed t hat de-elect r onat ion (anodic) cont r ol t akes place.
It is also possible t o have mixed cont r ol sit uat ion over t he cor r oding syst em when t he
cor r osion cur r ent is cont r olled by bot h t he de-elect r onat ion and elect r onat ion r eact ions.
It could also be called an ohmic cont r ol, wher e t he cor r osion cur r ent is det er mined by
t he IR dr op in t he elect r olyt e.
The cor r osion pr ocess can be looked upon as a consecut ive r eact ion consist ing t o t he
following four st eps say : (1) de-elect r onat ion, (2) elect r on flow in met al, (3) elect r onat ion,
and (4) ion flow in t he elect r olyt e. When a consecut ive r eact ion at t ains a st eady st at e,
t he net cur r ent s associat ed wit h t he var ious st eps ar e equal t o each ot her and also equal
t o over all cur r ent . Consider ing t he case of cor r oding met al, t he over all cur r ent is t he
cor r osion cur r ent and t her efor e:
I
corr
= I
M
= I
S0
= I = I
i
(wher e I
e
and I
i
ar e t he cur r ent s due t o elect r on. How in t he met al and ion flow in t he
elect r olyt e.)
Despit e t he equalit y of t he cur r ent s in t he var ious st eps, t he over all cur r ent in t he
consecut ive r eact ion may be cont r olled by one of t he four st eps. One is left wit h t he
possibilit y of t he t hr ee r at e cont r olling st eps. It is because t he elect r onic conduct ivit y of
t he met al will be high enough t o pr event elect r on flow in t he met al fr om cont r olling t he
cor r osion cur r ent . It is in t his way t hat t he cor r oding syst em becomes subject t o de-
elect r onat ion cont r ol or elect r onat ion cont r ol or cont r ol by ion flow in elect r olyt e (i.e.,
t he ohmic cont r ol).
In or der t o ident ify t he t ype of cont r ol over t he cor r osion cur r ent , one should know
t he r at e-det er mining st ep in a mult ist ep elect r odic r eact ion.
14.11 VARIOUS FACTORS IN DETERMINING CORROSION
Fir st and for emost , is t he fact t hat cor r osion depends a gr eat deal upon t he par t icular
met al involved. Sodium e.g., cor r odes vigor ously in aqueous solut ion and consider able
heat is evolved, spar ks ar e pr oduced and t he evolved hydr ogen explodes. On t he ot her
hand gold does not cor r ode at all and hence it s st abilit y is t he main r eason for it s used
as a monet ar y st andar d.
The st andar d equilibr ium pot ent ial for t he Na
+
+ e = Na r eact ion ext r emely negat ive
(2.71 V) wit h r espect t o t he equilibr ium pot ent ial of eit her t he hydr ogen evolut ion or
oxygen-r educt ion r eact ion.
Corrosion 209
For gold, t he st andar d equilibr ium pot ent ial for t he r eact ion Au
+++
+ 3e = Au r eading
is +1.50 V. This is mor e posit ive t han t he equilibr ium pot ent ial of eit her t he hydr ogen
evolut ion or oxygen r educt ion r eact ions. Hence, if t her e is unit act ivit y of ions in solut ion,
gold cannot cor r ode. When met als ar e ar r anged accor ding t o decr easing st andar d elect r ode
pot ent ials, a t able t hus yields what is called t he elect r ochemical ser ies. All met als wit h
E
0
values of negat ive wit h r espect t o hydr ogen, which has an E
0
of zer o, ar e known as
base met als and ar e expect ed t o cor r ode spont aneously. However , t he cor r osion r at e
is a quest ion of kinet ics and may pr ove t o be negligible e.g., lead. Met als wit h posit ive
E values ar e known as noble met als and ar e in cor r odible in deoxygenat ed solut ions
of pH = 0.
The influence of air and pH upon t he r at e of cor r osion of a met al is linked up wit h
t he fact t hat hydr ogen evolut ion and oxygen r educt ion ar e t he most common elect r onat ion
r eact ions in cor r osion. Whet her oxygen r educt ion or hydr ogen evolut ion becomes t he
pr edominant elect r onat ion r eact ion depends on sever al fact or s for inst ance.
1. The equilibr ium pot ent ial for oxygen r educt ion : O
2
+ 2H
2
O + 4e = 4 OH
is given
by
E
e
. O
2
/OH = 1.23 0.059 pH ...(17)
wher eas t hat for hydr ogen evolut ion
2H
+
+ 2e = H
2
is given by
+
2
e
E
= 0.059 pH ...(18)
t he for mer is always 1.2 V mor e posit ive t han t he lat t er Fig. 14.20 in a solut ion of t he
same pH.
Si n ce on e of t h e fa ct or s
det er mining t he cor r osion r at e is
t h e di ffer en ce bet ween t h e
equ i l i br i u m pot en t i a l s of t h e
el ect r on a t i on r ea ct i on a t t h e
elect r on-sour ce ar ea and of t he
met al dissolut ion r eact ion. It is
expect ed t h a t t h e oxygen
r educt ion r eact ion would always
be pr efer r ed, t he point being t hat
t her modynamics is on such a side.
2. Kinet ics gener ally favour s
t he hydr ogen-evolut ion r eact ion.
The exchange-cur r ent densit ies for
h yd r oge n e vol u t i on on t h e
cor r odible met als ar e gener ally
many or der of magnit ude higher
t h a n t h e e xch a n ge cu r r e n t
densit ies for oxygen r educt ion.
slope =
2.303RT
F
m
n
E=E+
2.303RT
nF
m
n
log
a
a
x
A
y
D
2.303RT
F
pH
pH
E
l
e
c
t
r
o
d
e
p
o
t
e
n
t
i
a
l
Fi g. 14.20 : The equilibr ium pot ent ial for a r eact ion
involving H
+
or OH
ions for any concent rat ion rat io of

accept or s and donor s depends linear ly on pH.
Taking t he case of ir on, t he i
0
for hydr ogen evolut ion is about 10
14
< amp
cm
2
. Thus in
highly acidic solut ions, hydr ogen evolut ion is t he pr efer r ed r eact ion.
3. The sit uat ion may be r ever sed as t he pH incr eases. The main r eact ion for t his
r ever sal is t hat t he exchange-cur r ent densit ies for hydr ogen evolut ion r eact ion depends
on t he hydr ogen ion concent r at ion. This is it so long as t he solut ion is sufficient ly
concent r at ed. As t he pH incr eases, t he hydr ogen ion concent r at ion decr eases and so
does t he exchange-cur r ent densit y for hydr ogen evolut ion.
It is t her efor e concluded t hat t he pr edominat ing elect r onat ion r eact ion depends
upon t he pH. Hydr ogen evolut ion gener ally has a subst ant ial r ole in highly acid r eact ions.
But in neut r al or alkaline solut ions, oxygen r educt ion plays a pr edominant par t in t he
r eact ion.
4. The oxygen molecules r equir ed for t he oxygen elect r onat ion r eact ion or iginat e
fr om dissolved air . The solubilit y of oxygen in wat er is of t he or der of 10
4
mole
lit er
1
. This is quit e a low concent r at ion and implies t hat t he limit ing cur r ent densit y
for oxygen r educt ion is of t he or der of 10
5
amp cm
2
in unagit at ed aqueous solut ions.
Hence when t he elect r onat ion of oxygen molecules is t he r eact ion associat ed wit h met al
dissolut ion in a cor r osion pr ocess. The t r anspor t of oxygen t o t he met al causes t he
maximum cor r osion r at e t o be t he value given by t he limit ing cur r ent densit y for oxygen
r educt ion. Consequent ly, in such a sit uat ion of oxygen-r educt ion cont r ol, agit at ion of t he
solut ion is which cor r osion is t aking place leads t o an incr ease of t he limit ing cur r ent
for oxygen r educt ion and t her efor e t o an incr ease of t he cor r osion r at e.
TABLE 14.4
Effect of
at At mospher ic Temper at ur es*
Hydrogen- Oxygen-
saturated acid saturated
Material Acid N (no oxygen) acid
Corrosion rat e, mm yr
1
Mild st eel Sulfur ic 1.2 31 358
Lead Hydr ochlor ic 1.1 17 163
Copper Hydr ochlor ic 1.1 17 1380
Tin Sulfuric 1.2 9 1100
Nickel Hydr ochlor ic 1.1 6 440
* F. L. La Que and H. R. Copson, eds., Corrosion Resistance of Metals and Alloys, Reinhold
Publishing Cor p., New Yor k, 1963.
illust r at es t he ext ent of t he effect t hat hydr ogen and oxygen elect r onat ion r eact ions
have on t he r at e of cor r osion of differ ent met als in differ ent acid media.
Corrosion 211
PART C : PASSIVATION
14.12 PASSIVATION : TRANSFORMATION FROM A CORRODING AND
UNSTABLE SURFACE TO A PASSIVE AND STABLE SURFACE
One of t he ways of pr ot ect ing a met al fr om cor r osion is when t he double-layer field is
alt er ed in such a way as t o diminish t he met al dissolut ion r eact ion which r esult s in
cor r osion. The fact is t hat t he unst able sur face of an act ively cor r oding met al can
somet imes, be made passive and st able by increasing t he pot ent ial in t he posit ive direct ion.
This of cour se depends on t he met al and t he solut ion condit ions.
When a met al is t o be t est ed for cor r osion, a piece of cor r odible met al, t he t est
elect r ode, is immer sed in an elect r olyt e along wit h t wo ot her elect r odes. One of t hese
is non polar izable r efer ence elect r ode and t he ot her , an auxiliar y elect r ode. An elect r onic
device Pot ent iost at is used for t he pur pose Fig. 14.21. The pot ent iost at measur es t he
pot ent ial V of t he t est elect r ode under st udy and compar es t his wit h t he select ed value
V* fr om t he pot ent ial sour ce (in t he pot ent iost at ). Act ually, t he, pot ent iost at cont r ols
t he r at e of char ge t r ansfer r eact ions at t he met al-solut ion int er face. By incr easing t he
de-elect r onat ion or elect r onat ion cur r ent , pushes t he elect r ode pot ent ial in t he posit ive
or negat ive dir ect ion t o t he pr e-select ed value.
The use of pot ent iost at facilit at es enables one t o hold t he pot ent ial of t he elect r ode
at chosen values and make measur ement s of t he st eady-st at e cur r ent densit y at each
value of t he pot ent ial. Differ ent met als exhibit differ ent passivat ion pot ent ials e.g., see
Table 14.5.
Potenti al
source
Potentiostat
V
+
I
V
Ref
electrode
Test Auxi l i ary
el ectrodes
Fi g. 14.21 : In a pot ent iost at ic cir cuit , an imposed pot ent ial differ ence V * dr ives t he
cur r ent fr om t he auxiliar y elect r ode t o t he t est elect r ode t ill t he pot ent ial differ ence V
becomes equal t o V *, so t hat t he t ot al input int o t he pot ent iost at falls t o zer o.
Corrosion 213
Once t he met al is passivat ed, t he cur r ent s which flow ar e negligible. Usually 100 t o
1000 t imes less t han t he dissolut ion cur r ent at t he maximum in t he cur r ent pot ent ial
r egion in which t he cor r osion cur r ent incr eases wit h incr easing pot ent ial. For all pur poses,
cor r osion has ceased and t he met al has been anodically pr ot ect ed. This is done by
pumping elect r ons away fr om t he met al inst ead of pumping elect r ons int o t he met al, as
in cat hodic pr ot ect ion.
TABLE 14.5
Ap p r oxima t e P a ssiva t ion P ot en t ia ls of Some
Met a
V, N-Hydrogen S ca
Gold +1.36
Plat inum +0.91
Ir on +0.58
Silver +0.40
Nickel +0.36
Chr omium 0.22
Tit anium 0.24
This met hod of st abilizing a met al is lar gely used in lar ge t anks used for st or ing oil
cont aining wat er and ar e acidic.
14.13 THE MECHANISM OF PASSIVATION
On consider ing t he enfor ced passivat ion of nickel in acid solut ion, it t ur ns out t hat t her e
comes a cr it ical pot ent ial at which a film of Ni (OH)
2
. Suddenly for ms on t he met al
sur face. This film for mat ion, cannot explain passivat ion because it occur s at pot ent ials
negat ive t o t he passivat ion pot ent ial. This film t hat is for med is called a pr epassive film.
It is, t her efor e, concluded t hat t he mechanism of enfor ced passivat ion of nickel in
acid solut ions consist s of t he for mat ion of a passive film at pot ent ials negat ive t o t he
passivat ion pot ent ial. This film is a necessar y condit ion of passivat ion, t hough not
sufficient . The passive film has t o become an elect r onic conduct or .
In cases of spont aneous passivat ion if a met al is cor r oding spont aneously at a r at e
less t han t he minimum cur r ent densit y, it will cor r ode and cor r ode.
But suppose t he dissolut ioncur r ent densit y is gr eat er (dur ing cor r osion) t han t he
minimum cur r ent densit y, t hen a film will for m by a dissolut ion pr ecipit at ion mechanism
and t hus t he met al will passivat e spont aneously. Explanat ion for well-known fact t hat
ir on cor r odes dr ast ically in dilut e nit r ic acid but becomes pr ot ect ed by a passive film in
concent r at ed nit r ic acid.
14.14 THE THERMODYNAMICS OF PASSIVATION
An impor t ant conclusion t hat is dr awn on discussing t he phenomenon of passivit y is
t hat t he sur face of a met al can under t he appr opr iat e envir onment al condit ions be
cover ed wit h oxide films. The pot ent ial
pH di a gr a ms Fi g. 14. 22 for met a l s
indicat e t he condit ions for t he st abilit y
of a met al immunit y fr om cor r osion, of
it s ions (cor r osion), and it s oxides t he
possibilit y of passivat ion.
An impor t ant point is t o be bor ne in
mind t o under st and oxide for while using
pot ent ialpH dia gr a ms t o under st a nd
oxide-film for mat ion on elect r odes. Also,
it is impor t ant t o not e t hat it is only t he
pH of t he solut ion which is adjacent t o
t he elect r ode which is r elevant and not
t he pH if t he bulk solut ion. Thus, e.g.
t he pH adjacent t o an elect r on-sour ce
elect r ode may be incr eased t o 9 by t he
r emoval of Hydr ogen ion (2H
+
+ 2e
H
2
O), wher eas t he bulk pH r emains 3.
As such t he pot ent ialpH diagr am must
be examined at a pH of 9 and not at a pH of 3.
The oxide for mat ion does not necessar ily imply passivat ion unless t he oxide, films
have t he r ight pr oper t ies i.e., t he elect r onic conduct ivit y. In such case only t hey can
ser ve as excellent inhibit or s of cor r osion. The films must also sat isfy ot her r equir ement s
t oo i.e., (i) The pr ot ect ive oxide films must be mechanically st able, (ii) t hey must not
flakeoff or cr ack. and (iii) t he films must be cont inuous. The cor r osion, cells can be set
up, if t hey ar e por ous or full of pinholes. The cat hodic r educt ion of oxygen could be one
r eact ion occur ing on t he oxide, and met al dissolut ion, in t he por es.
14.15 ROLE OF HYDROGEN IN CORROSION
(i) Diffusion into a metal
Sufficient emphasis has been laid as t he fact t hat t he inst abilit y of met al sur faces
ar ises fr om an elect r odic mechanism. In such a case an elect r onat ion r eact ion t eams up
wit h t he met al-dissolut ion r eact ion t o keep numer ous micr o cor r osion cells r unning.
Thus elect r odic char ge t r ansfer r eact ions at t he sur face have far r eaching implicat ions
for t he st r engt h of bulk met als.
Consider ing a cor r oding met al wher e t he hydr ogen evolut ion be t he elect r onat ion
r eact ion. In t he elect r odic evolut ion of hydr ogen, t he for mat ion of hydr ogen at oms
adsor bed on t he met al sur face is an essent ial int er mediat e st ep in elect r odic evolut ion
of hydr ogen.
But t her e is also a way in fr om t he sur face wher e t he adsor bed hydr ogen at oms can
dissolve int o t he met al t o for m absor bed hydr ogen. Since one has st ar t ed off wit h zer o
concent r at ion of absor bed hydr ogen inside t he bulk of t he met al, a gr adient of hydr ogen
concent r at ion develops bet ween t he sur face (wher e hydr ogen ent er s) and t he int er ior of
t he met al. It is t his concent r at ion gr adient which makes t he adsor bed hydr ogen t o
Fi g. 14.22 : Complet e pot ent ialpH diagr ams
indicat e t he condit ions of oxide for mat ion at t he
sur face which is a pr ecur sor t o passivit y.
Corrosion
Corrosion ?
Corrosion
P
o
t
e
n
t
i
a
l
Passivity
possible
Immunify
pH
diffuse int o t he met al. Thus t he diffusion of hydr ogen in t he bulk of t he met al is a fair ly
fast pr ocess.
The penet r at ion of hydr ogen int o t he int er ior of a met al is quit e simple. A t hin met al
membr ane separ at es t wo vessels cont aining an elect r olyt e. Hydr ogen is elect r odically
evolved on one side.
The pot ent ial differ ence acr oss t he ot her membr ane elect r olyt e int er face is adjust ed
for t he de-elect r onat ion (or ionizat ion of any absor bed hydr ogen: H
ads
H
+
+ e, coming
t hr ough t he met al fr om t he ent r y side of t he membr ane. Thus, t he ionizat ion cur r ent
is t he manifest at ion of t he hydr ogen penet r at ion t hr ough t he met al membr ane fr om t he
sur face on which hydr ogen is evolved.
(ii) Preferential Diffusion of Absorbed Hydrogen to Regions of Stress in a
Metal
In a polycr yst alline mat er ial, it is consider ed t hat t he gr ain boundar ies ar e ir r igat ion
channels for t he diffusing hydr ogen yet it is found t hat t he diffusion coefficient for
hydr ogen is t he same for polycr yst alline and single cr yst al ion. Thus, t he hydr ogen
would be diffusing t hr ough t he lat t ice int er st it ial diffusion. When a hydr ogen at om
occupies an int er st it ial sit e, t her e is a cer t ain displacement of t he at oms ar ound t he
int er st it ial at om. It appear s t hat some at oms moved apar t a lit t le t o accomodat e t he
int er st it ial hydr ogen at om. Hence it is expect ed t hat t her e is same change in volume
due t o t he ent r y of hydr ogen at om int o t he lat t ice. The net change in volume so r esult ing
due t o one gr am at om of hydr ogen, is t he par t ial molar volume of hydr ogen in t he met al.
Corrosion 215
CHAPTER 15
CONVERSION AND STORAGE OF
ELECTROCHEMICAL ENERGY
SECTION A
15.1 PRESENT STATUS OF ENERGY CONSUMPTION:
The t her mal combust ion of coal, oil and nat ur al gas have been t he main sour ces of
ener gy which is being consumed by man. What is being consumed is ener gy capit al and
not ener gy income, and, t her efor e, a day might come when t he r eser ves of fossil fuels
ar e exhaust ed. Specially, t he easily t r anspor t able and usable oil and nat ur al gas.
It is also impor t ant t hat , in ener gy conver sion, t he efficiency of t he pr ocess of t he
t her mal combust ion of t hese fossil fuels be cr it ically examined.
The ener gy is pr oduced when fossil fuels under go chemical r eact ion wit h oxygen, at
fir st in t he for m of heat . This is t hen conver t ed in an engine t o mechanical ener gy. The
conver sion of mechanical t o elect r ical ener gy is a pr ocess in which t he efficiency of
conver sion is almost unit y. Hence it is t he conver sion of t he heat ener gy given out in
t he chemical r eact ion of combust ion t o mechanical ener gy or wor k. The essence of heat
engine is a pist on or t ur bine r ot or which is for ced t o move by t he expansion of a gas.
This act ually occur s as a consequence of a r ise of t emper at ur e due t o heat given out
in t he chemical r eact ion t aking place bet ween t he fuel and oxygen. The combust ion
pr ocess can t ake place eit her (i) out side t he engine or (ii) inside t he engine. In case
(i) t hat is in an ext er nal-combust ion engine, t he fuel is bur ned out side t he engine and
t he heat gener at ed is t r ansfor med t o t he so-called wor king subst ance. This is t hen
conduct ed int o t he cylinder or t ur bine and is allowed t o expand. This t hen pr oduces
mechanical wor k. The example of such an ext er nal combust ion engine is t he steam
engine, t he essent ial inst r ument by which man made machines wor k for him. This has
been cont inuing since ninet eent h cent ur y. In t he second case (ii) t hat is in t he int er nal
combust ion engine, an appr oximat e mixt ur e of air and t he fuel for example t he
hydr ocar bon mixt ur e gasoline is eit her ignit ed inside t he cylinder by an elect r ic spar k
or compr ession or cont inuously bur ned inside a gas t ur bine. The expansion of t he gas
t her e is due t o t he heat given out in t he r eact ion of hydr ocar bon and oxygen t o car bon
dioxide causes t he pist on or t he r ot or t o move. The int er nal-combust ion engine has
been t he basis of t he t r anspor t r evolut ion of t he t went iet h cent ur y.
At pr esent , elect r icit y is gener at ed most ly by ut ilizing mechanical ener gy fr om t he
ext er nal and somet imes t he int er nal combust ion of fossil fuels t o dr ive gener at or s.
Ther e is a common feat ur e t o bot h t he ext er nal and int er nal combust ion engine is:
t hat t he chemical ener gy cont ained in t he fuel in fir st conver t ed int o heat and t hen t his
heat ener gy is used t o pr oduce mechanical power t hr ough t he for ce associat ed wit h t he
expansion of a heat ed gas. Act ually heat is essent ially an int er mediat e for m of ener gy
in t he conver sion t o mechanical wor k of t he differ ence bet ween t he ener gy of t he r eact ant s
and t hat of pr oduct s in chemical r eact ions, hence it s conver sion by t he gener at or t o
elect r icit y. Spont aneous r eact ion bet ween t he t wo subst ances. The st or er s t ake in
elect r icit y when an elect r ic cur r ent is passed t hr ough t hem fr om an out side sour ce and
give back elect r icit y when r equir ed by allowing t o r un spont aneously in t he for war d
dir ect ion t he r eact ion which had been made t o go backwar d dur ing char ging. In conver t er s
or so t o say gener at or s, t he cost of subst ances under going r eact ion t he fuels is of
impor t ance. It det er mines t he cost of elect r icit y and power pr oduced. The cost of subst r at e
by which t he r eact ions ar e cat alyzed is also of gr eat impor t ance in det er mining t he
init ial cost of t he conver t er . In st or er s, t he cost of t he subst ances under going t he r eact ions
at t he elect r odes det er mines t he init ial cost of t he device but it only secondar ily influences
t he cost of t he elect r icit y given back fr om t he st or age.
15.2 STATUS OF ENERGY CONSUMPTION
Pollution Problems
Some dir ect negat ive r esult s ar ise fr om t he pr esent pr edominant for m of ener gy
conver sion.
(a) Pr oduct s of combust ion ot her t han car bon dioxide. Gasoline and diesel oil which
is being used in pr esent int er nal combust ion engines do not under go 100% conver sion
t o CO
2
. The or ganic compounds r emaining incomplet ely bur ned ar e sever al dozens in
number and include par t icular ly unsat ur at ed compounds. Oxides of car bon, nit r ogen,
sulphur and a lead cont aining compound [fr om t he Pb (C
2
H
5
)
4
added t o fuels t o br eak
up chains in t he combust ion r eact ions] ar e also pr esent in significant amount s. However ,
it is known t hat cer t ain of t hese or ganic compounds under go a phot ochemical r eact ion
of oxides of nit r ogen t o pr oduce a complex addit ion compound which is t he or igin of
smog. Evidence suggest s t hat some of t he compounds fr om aut omobile exhaust s ar e
car cinogenic.
The pr oduct ion of smog is favour ed for pr oduct ion of smog ar e sunlight and a lar ge
concent r at ion of exhaust gases like oxides of nit r ogen and t he unsat ur at ed compounds
fr om aut omobiles. Smog condit ions would be expect ed t o t hr eat en many ur ban ar eas.
Ca r b on Di oxi d e This gas is an inevit able consequence of t he met hod of obt aining
mechanical ener gy by bur ning coal and oil. Absor bs r adiant ener gy in t he infr ar ed. The
t emper at ur e of t he ear t hs at mospher e is t he net consequence of a number of influences
which include t he amount of solar r adiat ion r eflect ed back t o space. The gr eat er t he
concent r at ion of CO
2
in t he at mospher e, t he less of t his r eflect ed ener gy escapes. i.e.,
t he mor e is st or ed in t he ear t hs at mospher e. The ener gy t hus absor bed degr ades t o
heat . All ot her t hings being equal, t he aver age t emper at ur e of t he at mospher e is expect ed
t o incr ease.
Conversion and S t orage of Elect rochemical Energy 217
Uncertainties in Predicting the future Pollution of the Atmosphere
An assessment of t he pr oblem of t ime dependence of t he gr owt h of at mospher ic
pollut ion is difficult because of t he unsat ur at ed compounds pr oduced in int er nal
combust ion engines a nd t heir dist r ibut ion in t he a t mospher e. Wha t ever be t he
consequence pr edict ed for t he incr ease in car bon dioxide concent r at ion r esult ing fr om
bur ning hydr ocar bons, t hey would seem t o be difficult .
Thermal-Combustion Engines Waste the Chemical Energy Available from
Burning the Hydrocarbons in Air
Suppose t hat combust ion engines can be so modified in design so t hat t hey do not
pollut e t he at mospher e and even t he effect s of t he absor pt ion of r eflect ed solar ener gy
by CO
2
can somehow be significant ly delayed so t hat int er nal combust ion could cont inue
t o be used t ill t he end of t he pr esent cent ur y.
15.3 DIRECT ENERGY CONVERSION BY ELECTROCHEMICAL MEANS
A chemical r eact ion pr oduces heat which causes a gas t o expand and t hus push for war d
a par t of a machine. This machine t hen dr ives anot her which pr oduces t he elect r icit y.
It would be pr efer able t o at t empt t o devise a means of conver t ing dir ect ly t o elect r icit y
t he ener gy r eleased dur ing most chemical r eact ions wit hout involving a second machine
and also pr efer ably wit hout moving par t s for t hese ar e subject t o er osion and mechanical
failur e.
Sever al such met hods, called dir ect ener gy-conver sion met hods, have been known
since past . Compar ed wit h t he convent ional met hod, t he pr esent met hods r epr esent an
impr ovement and give r ise t o much moder n int er est . However , r at her t han dir ect ener gy-
conver sion met hods, a bet t er t er m would be direct heat to electricity conver sion. What
act ually needed is a met hod in which t he ener gy r eleased in chemical r eact ions is
indeed conver t ed dir ect ly t o elect r icit y wit hout moving par t s, but also in a way which
avoids t he loss of ener gy due t o t he int r insic Car not lenit at e.
15.4 DIRECT ENERGY CONVERSION BY ELECTROCHEMICAL MEANS
Of t he t hr ee t ypes of elect r ochemical syst ems t hat ar e known, t he ener gy pr oducer , is
a spont aneously wor king self-dr iving elect r ochemical syst em Fig. 15.1.
In it t her e is a spont aneous occur ence of a de-elect r onat ion r eact ion at t he elect r on-
sink elect r ode and an elect r onat ion r eact ion at t he elect r on-sour ce elect r ode. If an
ext er nal load is connect ed t o t he t wo elect r odes, a cur r ent elect r ons flows in t he ext er nal
cir cuit . Thus, t he elect r ode r eact ion at t he t wo elect r odes br ing about t he conver sion
of t he differ ence in t he chemical ener gy (Gibbs fr ee ener gy) of t he r eact ant s and pr oduct s
dir ect ly int o a flow of elect r icit y (and t her eaft er , by a mot or , t o mechanical ener gy).
Ther e is no int er mediat e st ep in which t he ener gy has t o br ing it self t o power by
expansion of a gas conver t ing t her eby only par t of it s t her mal ener gy t o mechanical
wor k.
Electron
sink
electrode
e
Load
Solution
e + O
I
R
I
R O
II II
+e
Electron
source
electrode
Fi g. 15.1 : Schemat ic diagr am of an elect r ochemical ener gy pr oducer .
15.5 THE MAXIMUM INTRINSIC EFFICIENCY OF AN ELECTROCHEMICAL
CONVERTER
An essent ial t her modynamic equat ion is r ecapit ulat ed e.g.,
G = W
rev
PV ...(1)
This means t hat t he change in fr ee ener gy in a r eact ion is equal t o t he t ot al reversible
work obt ainable fr om t he r eact ion. This includes all kinds of wor k i.e., gr avit at ional,
elect r ical, sur face, et c., and also t he wor k of expansion diminished by t he wor k of
expansion, PV.
Hence G = W
rev
...(2)
wher e W
rev
st ands for all t he wor k obt ainable fr om t he r eact ion exclusive of any wor k
which can be obt ained fr om a possible volume change in t he syst em.
If a chemical r eact ion is car r ied out in an elect r ochemical way, t hen in t he example
of t he r eact ion:
2H
2
+ O
2
2H
2
O ...(3)
t her e will be t wo par t ial r eact ions
2H
2
4H
+
+ 4e ...(4)
and O
2
+ 4H
+
+ 4e 2H
2
O ...(5)
In fact aft er car r ying out t he over all r eact ion 2H
2
+ O
2
2H
2
O and hence, t he
nor mal change of fr ee ener gy associat ed wit h t his r eact ion at a given t emper at ur e and
pr essur e has occur r ed.
15.6 THE ACTUAL EFFICIENCY OF AN ELECTROCHEMICAL ENERGY
CONVERTER
It has been alr eady shown in t he pr evious sect ion t hat in an elect r ochemical ener gy
conver t er , t he maximum cell pot ent ial is t he value Ve obt ainable when t he r eact ion in
t he cell is elect r ically balanced out t o equilibr ium. This means t hat no cur r ent is being
dr awn fr om t he cell. As soon as t he cell devices a cur r ent t hr ough t he ext er nal cir cuit ,
t he cell pot ent ial falls fr om t he equilibr ium value Ve t o V. The value of t he act ual
pot ent ial V at which t he cell wor ks when deliver ing a cur r ent i is always less t han t he
equilibr ium pot ent ial Ve
Hence fr om equat ion:
E
max
=
G nFVe
= ,
H H

E
0
=
nFVe V
H Ve
...(6)
or E
0
= E
max
E
p
...(7)
wher e E
max
is t he maximum efficiency given by t he above equat ion* and E
p
is known as
t he volt age efficiency given by
E
p
=
V
Ve
...(8)
The pict ur e is t r ue if t he over all r eact ion is fully accomplished and none of t he
elect r ons t ake par t in some alt er nat ive r eact ion. Consider ing t he cur r ent or far adaic
efficiency E
f
int o account t he incomplet e conver sion of r eact ant s int o pr oduct s. The
over all efficiency is t hen given as :
E
0
= (E
max
E
p
) E
f
In many r eact ions t hat may be of int er est , E
f
is vir t ually unit y.
15.7 PHYSICAL INTERPRETATION OF THE ABSENCE OF THE CARNOT
EFFICIENCY FACTOR IN ELECTROCHEMICAL ENERGY
CONVERTERS
The mechanism of ener gy conver sion, in t he t her mal r eact ion, may be visualized on a
molecular scale in t he way t hat t he change in ener gy bet ween pr oduct s and r eact ant s
is r eleased in t he for m of t he heat or kinet ic ener gy of t he const it uent gases. These t hen
impact upon some mechanical and movable object (e.g., t he pist on in an int er nal
combust ion engine), but in t hese collisions, t her e is a ser ies of glancing angles of incident
of t he molecules on t he cylinder and t he t r ansfer of moment um t o t he pist on fr om t he
(hot ) molecules is not complet e. The degr ee of it s complet eness is measur ed by t he
change in t he kinet ic ener gy of t he par t icles aft er t hey have st r uck t he pist on. The
t emper at ur e of t he gases init ially i.e., befor e st r iking t he pist on is T
1
or t he kinet ic
ener gy per par t icle is 3/ 2 k T
1
. Aft er war ds, it is T
2
, or t he kinet ic ener gy per par t icle,
3/ 2 kT
2
. The point is t hat only a par t of t he kinet ic ener gy, 3/ 2 kT
2
, or heat ener gy was
t r ansfer r ed t o t he pist on t he r est of t he ener gy escaped, i.e., r emained as heat in t he
gas t hat was r eject ed t o t he heat sink (t he pr oduct s of t he r eact ion ar e emit t ed fr om t he
r eact ion chamber at a lower t emper at ur e t han t he maximum but st ill cont aining much
of t he r eact ions ener gy, i.e., st ill hot )
The efficiency of t he conver sion pr ocess is given by
E =
1 2 1 2 1 2
1 1 1 1
3 2 k . T 3 2 k . T Q Q T T W
= = =
3 2 k T Q Q T

...(9)
As a mat t er of fact t hese ar e no collisions, in t he elect r ochemical conver t er , bet ween
t he par t icles e.g., H
2
and O
2
, which r eact t o for m H
2
O. They simply under go elect r on
supplying for t he H
2
and elect r on accept ing for t he O
2
r eact ion on t he elect r odes. These
elect r ons t r avel r ound an ext er nal cir cuit and, while doing so, pass t hr ough a load (e.g.,
t he ar mat ur e of a mot or ) and t her eby do wor k. They complet e t he r eact ion and allow
t he pr oduct i.e., wat er t o be for med. Hence t her e is no analog of any pr ocess of incomplet e
t r ansfer of t he ener gy differ ence bet ween t he t wo sides of a r eact ion t o t he out side of
t he conver t . This is because t her e is in t her mal conver sion. The elect r ons t hus pass
Fig. 15.2 : The power versus cur r ent -densit y and efficiency versus cur r ent -
densit y r elat ions for t he elect r ochemical ener gy conver t er .
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
E
f
f
i
c
i
e
n
c
y
P
o
w
e
r
,
w
a
t
t
s
Curent density, amp cm
2
t hr ough t he ent ir e pot ent ial differ ence gener at ed by t he cell r eact ion and not t hr ough
a par t of it only.
The quest ion ar ises as t o why t he elect r ochemical conver t er wor king under ideal
condit ions does not conver t int o elect r ic ener gy all t he ener gy r eleased in a chemical
r eact ion, H, but only t he fr ee ener gy change in t he r eat ion, F. This of cour se happens
because t he r eact ion t aking place is st ill t he same over all chemical r eact ion as in t he
t her mal case i.e., t he r eact ion is st ill 2H
2
+ O
2
2H
2
O. The ent r opy change r emains
unalt er ed. A par t of t he H is used up in t he unavailable ener gy connect ed wit h t he
differ ences in or der and disor der bet ween t he pr oduct s and t he r eact ant s, and t his
unavoidably so, independent of any met hod of ener gy conver sion.
15.8 THE POWER OUTPUT OF AN ELECTROCHEMICAL ENERGY
CONVERTER
When elect r ochemical ener gy conver t er s ar e t o be consider ed for use. As for example, in
dr iving t r ucks it is t he power out put or t he r at e at which t hey ar e able t o do wor k t hat
has t o be examined. The power P of an elect r ochemical ener gy conver t er is t hus defined:
P = IV
fr om which it follows t hat t he power is small when I is small even t hough V is near t he
maximum Ve. But t he power out put is also small when I is ver y lar ge because of t he
sudden gr owt h of concent r at ion over pot ent ial when t he cur r ent densit y appr oaches i
L
t ends t o dr ive V t o zer o. Thus t he P ver sus I cur ve should pass t hr ough a maximum.
The dist inct ion bet ween t he sit uat ion in which one want s high power becomes clear
when one compar es t he P ver sus I and E ver sus I cur ves Fig. 15.2. When it s efficiency
is at a maximum, t he elect r ochemical ener gy conver t er is a less good power sour ce. As
t he cur r ent densit y is incr eased, t he power out put incr eases, but t he efficiency decr eases,
of cour se, at highest cur r ent dr ains, bot h power and efficiency fall t owar d zer o.
SECTION B
Electrochemical Generators (Fuel Cells)
Fuel cells ar e elect r ochemical bat t er ies, in which t he necessar y r eact ant s ar e supplied
cont inuously fr om out side t o non-consumable elect r odes. Fr om which t he final pr oduct s
of cur r ent gener at ing r eact ions ar e r emoved away cont inuously. By such a dir ect
conver sion (which avoids t her mal ener gy) fuel cells ar e not limit ed by t he Car not fact or
pr ohibit ing high conver sion-efficiency. Easily oxidizable compounds such as hydr ogen,
hydr ozine, and met hanol and oxidant s such as oxygen or air ar e pr efer r ed as fuels. Out
of t hese t echnical development is most advanced in t he case of hydr ogen-oxygen cells
oper at ing at ambient t emper at ur e and low over at mospher ic pr essur e.
As alr eady indicat ed differ ent mat er ials can be used as oxidant s in fuel cells. Yet it
is desir able, if possible, t o use O
2
fr om air at one elect r ode in ever y ear t h bound fuel cell
because t his avoids t he necessit y of car r ying a second fuel for t he cat hodic r eact ion.
Hence t he cat hodic r educt ion of O
2
has a special impor t ance in elect r ochemical r eact or s.
The over all r eact ion is, in acid solut ion
O
2
+ 4H
3
O
+
+ 4e 6H
2
O ...(1)
and in alkaline solut ion,
O
2
+ 2H
2
O + 4e 4OH
...(2)
Ther e is a gr eat disadvant age in t his impor t ant elect r ode r eact ion. It has an i value
in t he r egion of 10
10
amp cm
2
, and hence t he r eact ion usually cont r ibut es consider ably
t o t he over pot ent ial in t he funct ioning of an air bur ning elect r ochemical conver t er .
Elect r ocat alysis of t his r eact ion is needed mor e t han any ot her in ener gy conver t er s.
As alr eady st at ed, among fuels alr eady used in fuel cells, besides hydr ogen, t her e
ar e many hydr ocar bons, sever al lower alcohols, hydr azine; and ammonia. A r epr esent at ive
t able is given her e. Table 15.1.
TABLE 15.1
Cells Usin g Fu els Ot h er t h a n Hydr ogen *
Fuel and t ype of cell Electrolyte Catalysts Av. power densit y
Hydr ocar bons CH
4
, Conc. H
3
PO
4
Anode, Pt; 1060 mW cm
2
C
2
H
6
, C
3
H
8
, et c., solut ion wit h Cat hode, Pt at 0.40.5 V
t emp 100200C low vapor
pr essur e
Alcohols CH
3
OH, 6N KOH Anode, Pt , Pd, and Ni; 20100 mW cm
2
C
2
H
4
(OH)
2
, and Cat hode, C, Ag, Pt , at 0.60.7 V
ot her alcohols and and Pd oxides
der ivat ives, 7N H
2
SO
4
Anode, Pt ; 1050 mW cm
2
t emp 2080C Cat hode, Pt at 0.40.6 V
Nit r ogen der ivat ives 612N KOH Anode, Ni and Co; 60200 mW cm
2
NH
2
NH
2
, Cat hode, C and Ag at 0.80.9 V
t emp 2060C
NH
3
, Molt en Anode, Pt ; 100200 mW cm
2
t emp 200400C hydroxides Cat hode, NiO + Li at 0.70.8 V
Special fuels and 6 t o 12N KOH Anode, St eel; 100300 mW cm
2
Alkali met als, Cat hode, C, Ag, et c. at 1.01.2 V
2060C
* Table based on Piles combustible, Par is, 1965.
Cells using fuels other than Hydrogen
These fuels ar e gener ally used as anodically r eact ing mat er ials in combinat ion wit h an
oxygen cat hode.
A r ough division of pr esent elect r ochemical gener at or s could be made depending on
t emper at ur e. As such if t his is below 150C, t he device is called a low t emper at ur e fuel
cell and above about 500C a high t emper at ur e fuel cells.
Thus, for low t emper at ur e cells, t he main pr oblem is t hat of elect r ocat alysis i.e., how
t o r aise t he exchange cur r ent densit y for t he oxidat ion of r elat ively cheap fuels by using
elect r ode mat er ials which do not make t he init ial cost of a device t oo high. The st abilit y
of const r uct ion mat er ial is not t o cr it ical. For t he high t emper at ur e cells, t he t emper at ur e
alone causes t he exchange cur r ent densit ies t o be sufficient ly high t hat t her e can be
pr oduct ion of ener gy at a suit able r at e wit hout using expensive mat er ials as cat alyst s.
The count er pr oblem could be t he cor r osive act ion of t he elect r olyt es.
The Hydrogen-Oxygen Cell
This is t he best known of elect r ochemical gener at or s, t he fir st t o r each meaningful
pr act ical power levels.
Sever a l t ypes of hydr ogen-oxygen fuel cells ha ve been developed since t he
accomplishment by Bacon, of which t he Gemini and Apollo syst ems of t he Amer ican
space pr ogr amme ar e out st anding. A schemat ic diagr am of a single Gemini cell is shown
in t he Fig. 15.3 below.
e
Load
H O
2
+
O
2
H
2
e
Titanium screen
coated with Pt catalyst
Polystyrene sulfonic acid
ion-exchange membrane
O + H O
2 2
H
2
Wicks for maintaining
water balance
HO 2
Fi g. 15.3 : Schemat ic r epr esent at ion of a single Gemini hydr ogen-oxygen fuel cell.
The unique feat ur e of t his cell is t he use of a t hin cat ion exchange membr ane as
elect r olyt e (polyst yr ene sulphonic acid int imat ely mixed wit h a Kel F
+
spine). Each side
of t his r ect angular membr ane is cover ed by a t it anium scr een coat ed wit h a plat inum
cat alyst . The t hickness of t he ent ir e cell is about
1
2
mm. The r eact ions t hat ar e t aking
place ar e :
at anode 2H
2
4H
+
+ 4e ...(3)
at cat hode O
2
+ 4H
+
+ 4e 2H
2
O ...(4)
The conduct ivit y of t he membr ane is st r ongly dependent on t he wat er cont ent .
Hence t he wat er balance is maint ained by supplying wat er by capillar y act ion.
The per for mance of a single cell is shown in t he figur e below:
Fi g. 15.4 : The cell-pot ent ial versus cur r ent -densit y r elat ions for a Gemini
hydr ogenoxygen fuel cell.
An impor t ant over pot ent ial loss is, in t hese cells, due t o membr ane r esist ance also,
as usual, t o oxygen elect r ode. A st or age syst em built of t hese cells, having an aver age
power of about 900 W and a maximum power of 2 kW. At pr esent , some hydr ogen-
oxygen fuel cells have at t ained a power level of 1W cm
2
.
Hydrogen Air cells
Pur e hydr ogen is expensive, alt hough it is an excellent fuel because of it s lar ge i
0
value and t he r esult ing possibilit y of cat alyzing it s dissolut ion well (i.e., wit h small over
pot ent ial on cheap mat er ials such as nickel. In or der t o over come t his sit uat ion, a ser ies
of fuel cells ut ilize a syst em in which a cheap hydr ocar bon fuel is t he or igin of t he
hydr ogen. This is pr oduced in an adjoining appar at us, separ at ed fr om ot her gases, and
fed int o t he cell.
The st eam hydr ocar bon pr ocess is as follows:
C
n
H
2n+2
+ nH
2
O (2n + 1) H
2
+ nCO ...(5)
CO + H
2
O CO
2
+ H
2
...(6)
The CO
2
may be r emoved by absor pt ion in et hylamine or by hydr ogen separ at ed by
diffusion t hr ough palladium or silver -palladium membr anes.
Apar t fr om t hese ammonia or met al hydr ides may also be used as chemicals since
bot h ar e in fact hydr ogen car r ier s.
0
0.2
0.4
0.6
0.8
1.0
1.2
0.02 0.04 0.06 0.08 0.10 0.12
C
e
l
l
p
o
t
e
n
t
i
a
l
,
v
o
l
t
Current density, amp cm
2
CHAPTER 16
ELECTROCHEMICAL ENERGY STORAGE:
THE IMPORTANT QUANTITIES IN
ELECTRICITY STORAGE
16.1 ELECTRICITY STORAGE DENSITY
The elect r icit y st or age densit y is t he amount of elect r icit y (Coulombs) per unit weight
which t he st or er can hold. It st at es not hing concer ning t he ener gy (wat t s or kilowat t -
hour s) which it can st or e per unit weight . The elect r icit y st or age densit y act ually r efer s
t o a measur e of t he maximum t ot al amount of elect r icit y which can be wit hdr awn fr om
unit weight of a subst ance when (in conjunct ion wit h anot her subst ance in a cell) it
under goes an elect r ochemical r eact ion.
Thus, let one for mula weight mole of subst ance ent er int o an elect r odic r eact ion in
which t hey accept or r eject n elect r ons t o pr oduce ot her subst ances in one of t he t wo
elect r ode r eact ions in a cell. Then,
M [g of subst ance] = nF [Coulomb of elect r icit y] ...(1)
or 1 kg = | |
96,500 1000n
C
M
Elect r icit y st or age densit y is
-1
96.5
Ck g
6
10
n
M
(

Suppose t he pot ent ial differ ence t hr ough which t he amount of elect r icit y st or ed
passed (t he cell pot ent ial) was par t icular ly small for a given syst em, t hen it s elect r icit y
st or age densit y could be high but t he ener gy is st or ed (t he coulombs flowing t imes t he
pot ent ial differ ence passed t hr ough) would be small.
It is t o be not ed t hat t he elect r icit y st or age densit y, e.g., says lit t le of t he act ual
behaviour of t he subst ance at an elect r ode or t he possibilit ies of making an elect r ode
fr om it . Elect r icit y st or age densit y may be t her efor e only a paper par amet er , useful as
an indicat ion of what might be possible wit h cer t ain subst ances if t hey ar e made t o r eact
r ever sibly at elect r odes which give t he r eact ion lar ge i
0
s.
16.2 ENERGY DENSITY
This r efer s t o t he ener gy which may be ext r act ed fr om a given weight of a subst ance
or a device per unit weight . Elect r ical ener gy is measur ed by t he quant it y of elect r icit y
(cur r ent mult iplied by t ime) mult iplied by t he pot ent ial differ ence t hr ough which such
a quant it y passes. Thus
Ener gy densit y = Elect ricit y st orage densit y cell pot ent ial ...(2)
or Maximum ener gy densit y =
7
9. 65 10 n V e
Mole
...(3)
wher e Ve is t he r ever sible elect r ode pot ent ial of t he mat er ial in t he r eact ion concer ned.
It is also t o be not ed t hat t he ener gy densit y of a single elect r ode is fict it ious quant it y
since Ve depends on t he ar bit r ar ily select ed r efer ence elect r ode (e.g., a nor mal hydr ogen
elect r ode). The value of t he above equat ion is in coulomb volt s per kilogr am (if Hole is
expr essed in kilogr ams). The same may be expr essed as amper e second volt per
kilogr am = amper e volt second per kilogr am = wat t second per kilogr am. Hence,
maximum ener gy densit y is, in kilowat t hour s per kilogr am,
7
1
9.65 10
=26. 8 k Wh k g
6 0 6 0 1 0 0 0
n
Ve n V e
M Mole
(

...(4)
This maximum ener gy densit y for an elect r ode mat er ial under going an elect r ode
r eact ion involving n elect r ons is only an indicat ion of it s abilit y t o act as a vessel loaded
wit h r ealizable elect r icit y.
Values of such maximum ener gy densit ies of cer t ain mat er ials in cer t ain r eact ions
ar e shown in t he following Table (16.1). On t he ot her hand t he maximum ener gy densit y
of t he best combinat ions of elect r ode r eact ions ar e given in Table 16.2.
The r eal ener gy densit ies of cells ar e less t han t he values given in Tables 16.1 & 16.2
and somet imes by a fr act ion e.g., some one fift h Table 16.3.
TABLE 16.1
Idea lized Ma ximu m En er gy-Den sit y Va lu es for Some Elemen t s, a t 25C
Thermodynamic Idealized maximum
Element Reaction potential E
0
, energy densit y,*
V kWh kg
1
Lit hium Li Li
+
+ e 3.045 11.76
Sodium Na Na
+
+ e 2.714 3.16
Pot assium K K
+
+ e 2.925 2.00
Beryllium Be Be
2+
+ 2e 1.847 10.98
Magnesium Mg Mg
2+
+ 2e 2.363 5.21
Calcium Ca Ca
2+
+ 2e 2.866 3.83
Aluminum Al Al
3+
+ 3e 1.662 4.95
Manganese Mn Mn
2+
+ 2e 1.18 1.15
Ir on Fe Fe
2+
+ 2e 0.440 0.42
Nickel Ni Ni
2+
+ 2e 0.250 0.23
Contd.
Electrochemical Energy S torage the important Quantities in Electricity S torage 227
Thermodynamic Idealized maximum
Element Reaction potential E
0
, energy densit y,*
V kWh kg
1
Zinc Zn Zn
2+
+ 2e 0.763 0.63
Cadmium Cd Cd
2+
+ 2e 0.403 0.19
Lead Pb Pb
2+
+ 2e 0.126 0.03
Silver Ag
+
+ e Ag + 0.799 0.20
Mer cur y
2+
2
Hg + 2e 2Hg + 0.789 0.11
Br omine Br
2
+ 2e 2Br
+ 1.065 0.36
Chlorine Cl
2
+ 2e 2Cl
+ 1.359 1.03
Fluorine F
2
+ 2e 2F
+ 2.87 4.05
* In a hypot het ical cell wit h t he nor mal hydr ogen elect r ode.
TABLE 16.2
Idea lized Ma ximu m En er gy Den sit y of Hypot h et ica l Elect r ode Cou ples a t 25C
Reaction Cell potential Ve, Energy densit y,
V2 kWh kg
1
2Li + F
2
2LiF 6.05 6.03
2Li + CuCl
2
2LiCl + Cu 3.06 1.11
2Li + CuF
2
2LiF + Cu 3.55 1.66
2Li + NiF
2
2LiF + Ni 2.83 1.34
3Li + CoF
3
3LiF + Co 3.64 2.12
2Li + CoF
2
2LiF + Co 2.88 1.40
2Li + CuO Li
2
O + Cu 2.25 1.30
Mg + CuF
2
MgF
2
+ Cu 2.92 1.25
3Mg + 2CoF
3
3MgF
2
+ 2Co 2.89 1.52
Mg + AgO MgO + Ag 2.98 1.08
Ca + CuF
2
CaF
2
+ Cu 3.51 1.33
Ca + CuO CaO + Cu 2.47 1.11
Some of t he r easons for t his ar e obvious. The idealized maxima of t he calculat ion of
t he hypot het ical maximum power densit y t ake int o account t he weight of t he act ive
mat er ials wit h no account ing for gr id, cont ainer , solut ions connect ions et c.
In addit ion, t he Ve value, must be r educed by t he pr evailing over pot ent ial for t he
given condit ions of t he r at e or cur r ent densit y at which it is desir ed t o supply elect r icit y.
However , t hese fact or s do not alone account for t he differ ences bet ween t he idealized
maxima and t he r eal ener gy densit y of elect r icit y st or er s.
In br ief calculat ed maximum ener gy densit ies ar e indicat ive lar gely of what syst em
t o invest igat e in consider ing t he development of fut ur e elect r icit y st or er s. Values
obt ainable in pr act ice Table 16.3 ar e at pr esent one half t o one-fift h t he ideal values and
must be est ablished empir ically. Once measur ed at a given cur r ent densit y, t he ener gy
densit ies can, even t hen be used only as r ough guides. This is because t he available
pot ent ial is r educed by t he over pot ent ial which ar ises wit h incr ease of cur r ent densit y,
[Equat ion r epr esent ing a cell pot ent ial cell cur r ent r elat ion be consult ed for fur t her
det ails], so t hat , int r insically a var iat ion of ener gy densit y wit h power will t end t o occur .
TABLE 16.3
Rea lized a n d Idea lized En er gy-St or a ge-Den sit y P a r a met er s for Some Cell Syst ems
Thermo- Realized Idealized Ratio of
S ystem dynamic energy densit y energy realized t o
reversible (mean), density, idealized
potential Ve, V kWh kg
1
kWh kg
1
energy densit y
S ingle discharge
M-O
2
KOHZn 1.64 0.15 0.44 0.34
m-DNBMgBr
2
Mg 2.84 0.22 1.54 0.14
Ag
2
O
2
KOHZn 1.81 0.11 0.22 0.50
HgOKOHZn 1.34 0.11 0.22 0.50
Hypothetical single discharge
LiF
2
6.0 1.5
MgO
2
3.1 1.3
Bem-dinit r obenzene 2.6 3.1
Benit r obut anol 2.3 3.7
Multiple chargedischarge
PbO
2
H
2
SO
4
Pb 2.04 0.02 0.18 0.11
NiO(OH)KOHCd 1.48 0.04 0.22 0.18
Ag
2
O
2
KOHZn 1.70 0.11 0.44 0.23
Hypothetical multiple
charge-discharge
BeBeF
2
F
2
4.5 3.30
AlAlCl
3
Cl
2
3.02 2.20
Power
The cr it er ia for a good elect r ically st or er given above r elat es t o t he quest ion as t o
how much elect r icit y, or say elect r ic ener gy, can t he device hold and deliver per unit
weight . This quest ion is pr imar y one of t he device is for t he st or age of elect r icit y.
Anot her , differ ent quest ion which r elat es t o t he r at e at which t he st or er would be able
t o r elease t he ener gy again.
In fact t he power is t he pr oduct (for each single cell) of t he wor king pot ent ial of t he
cell i.e., t he maximum pot ent ial diminished by t he sum of t he over pot ent ials at and
bet ween t he elect r odes in t he cell mult iplied by t he cur r ent of each cell, which is it self
a funct ion of over pot ent ial. The power incr eases wit h cur r ent densit y and passes t hr ough
a maximum Fig. 16.1.
Fig. 16.1 : The power versus current -densit y relat ions for an elect rochemical
ener gy conver t er (calculat ed for cur ve 1 of Fig. 11.71)
In fact Rat e in t he for m of cur r ent t imes pot ent ial is t he r at e of deliver ing ener gy,
i.e., t he power . A device could be imagined which has an excellent ener gy st or age
densit y but can only r elease t his ener gy at a slow r at e. The disadvant age of such a
device would be t hat only a sit uat ion r equir ing low power could be coped wit h by it .
Hence t he power densit y of a st or er (t he number of kilowat t s, r at her t han kilowat t
hour s, it can put out per unit weight ) is also an impor t ant index of it s mer it as a device.
The differ ence in funct ion bet ween elect r icit y st or er s and elect r ochemical ener gy
conver t er s has been r epr esent ed in Figs. given; ahead. The elect r icit y st or er wor king in
t he supply mode and t he elect r ochemical gener at or or conver t er ar e bot h elect r ochemical
cells wor king as ener gy pr oducer s.
Electricity Storage
In t he elect r ochemical conver t er s alr eady descr ibed, t he t wo r eact ant s ar e st or ed
out side t he cell and ar e fed t o each elect r ode r espect ively e.g., see Figs. 16.2 and 16.3.
In case, inst ead of feeding t he r eact ant s t o t he elect r odes cont inuously t he r eact ant s
ar e placed on t he elect r odes. When cat hode and anode ar e joined t hr ough an ext er nal
cir cuit , t he t wo fuels, each on one iner t elect r ode, will r eact elect r odically at t he r espect ive
elect r ode solut ion int er faces and a cur r ent will flow, just as in an elect r ochemical
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
P
o
w
e
r
,
w
a
t
t
s
Current density, amp cm
2
conver t er . An example could be, on one iner t elect r ode subst r at e, powder ed cadmium
had been placed (in analogy in t he fuel of a conver t er ) and, on t he ot her elect r ode, an
oxide of nickel (t he ot her fuel). When t he ext er nal cir cuit is closed as shown in Fig.
16.4(a) t he elect r ode on which t he cadmium has been placed under goes an anodic r eact ion,
if t he de-elect r onat es wit h t he following over all char ge t r ansfer r eact ion.
e
Load
H O
3
+
O2
H
2
e
Titanium screen
coated with Pt catalyst
Polystyrene sulfonic acid
ion-exchange membrane
O + H O
2 2
H
2
Wicks for maintaining
water balance
HO 2
Fi g. 16.2. Schemat ic r epr esent at ion of a single Gemini hydr ogenoxygen fuel cell.
Cd + 2OH
Cd(OH)
2
+ 2e ...(5)
Cor r espondingly, at t he elect r odes on which t he nickel oxide has been placed, an
elect r onat ion r eact ion occur s and could be r epr esent ed as an over all r eact ion:
2NiOOH + 2H
2
O + 2e 2OH
+ 2Ni(OH)
2
...(6)
In case when an ext er nal sour ce of elect r ic power is used t o push elect r icit y int o t he
cell Fig. 11.88(b) in t he opposit e way t o t hat in which it passes if t his cell is allowed t o
funct ion spont aneously.
While dealing wit h an elect r ochemical conver t er wit h decane as t he anodic fuel, t he
pr oduct of t he over all cell r eact ion would be CO
2
and H
3
O
+
. If t he pH is acidic, CO
2
is
evolved and expelled fr om t he syst em (in an alkaline solut ion, t he CO
2
would of cour se
fr om car bonat e and event ually pr ecipit at e in t he cell). Thus in t he case decane, when
one uses t he aid of an ext er nal power sour ce t o push a cur r ent in a dir ect ion opposit e
t o t hat in which t he gener at or has been funct ioning spont aneously, t her e is no chance
of r ever sing t he over all r eact ion of decane oxidat ion which means r educing CO
2
t o
decane at t he cat hode, while evolving oxygen at t he anode. Apar t fr om ot her r easons,
t he CO
2
has escaped fr om t he syst em int o t he at mospher e. On t he ot her hand not hing
escapes fr om t he syst em dur ing t he spont aneous funct ioning of t he elect r ode r eact ion
(t he cell dischar ging). This happens in a device in which, as wit h t he cell Fig. 16.4(a)
whose elect r odes cont ain Cd(OH)
2
and Ni(OH)
2
, t he pr oduct s of spont aneous funct ioning
of t he cell ar e held on t he elect r odes.
e
Load
H +CO
2
e
CO +O N
2 2 2
+
H
2
+
C
O
Water
Purifier
Natural gas
Nickel catalyst
Stainless steel cathode
current collector
Porous Ni
Ag paint
Molten carbonates
with MgO
CO +O +N
2 2 2
Carbon steel anode
current collector
Fi g. 16.3 : Schemat ic r epr esent at ion of a high-t emper at ur e (500C) nat ur al-gas fuel cell.
Hence, on t he cadmium elect r ode, t he r eact ion in t he elect r ode plat e cover ed wit h
cadmium hydr oxide can be, when elect r icit y is put int o device, Fig. 16.4(b)
Cd(OH)
2
+ 2e Cd(OH)
...(7)
and on t he nickel elect r ode dur ing cor r esponding cir cumst ances,
2Ni(OH)
2
+ 2OH
NiOOH + 2H
2
O + 2e ...(8)
The device is an elect r icit y st or er . On t he one hand, t he subst ances on it s elect r odes
can r eact t o elect r icit y sent in fr om an ext er nal sour ce by under going t r ansfor mat ion.
On t he ot her hand, upon demand, t he st or er can allow it s elect r ode r eact ions t o occur
spont aneously and send out t hr ough an ext er nal cir cuit (Fig. 16.4(a) t he elect r icit y
which was put int o it pr eviously. Thus elect r icit y is st or ed in chemicals on t he elect r odes
because t hey have a cer t ain for m. In char ging over t o anot her , t hey give out elect r icit y.
The essent ial and consider able differ ence bet ween elect r ochemical ener gy conver t er s
and elect r icit y st or er s can be made clear . The conver t er s t ake in subst ances, usually
st or ed ext er nally, and pr oduce elect r ic ener gy dir ect ly fr om t he spont aneous r eact ion
bet ween t he t wo subst ances.
Classical Batteries
Inert electrodes
e
Load
Cd
NiOOH
e
KOH solution
Porous separator
Fi g. 16.4(a ) : A nickel cadmium cell at t he Fi g. 16.4(b) : A nickel cadmium cell at t he
beginning of dischar ging. At t he cat hode, beginning of charging. At t he cat hode, Cd(OH)
2
2NiOOH + 2H
2
O + 2e 2Ni(OH)
2
+ 2OH
; + 2e Cd + 2OH
; at t he anode, 2Ni(OH)
2
+
at t he anode, Cd + 2OH
Cd(OH)
2
+ 2e. 2OH
2NiOOH + 2H
2
O + 2e.
(b)(i) Lea d -Aci d St or a ge Ba t t er y. This elect ricit y st orer was invent ed by Plant e as
ear ly as 1860 and it is t he one most used st or er at t he pr esent t ime, par t icular ly for
dr iving t he elect r ic mot or by which int er nal cumbust ion engine ar e made t o fir e.
It consist s of t wo elect r odes of lead sheet and elect r olyt ic solut ion H
2
SO
4
sat ur at ed
wit h PbSO
4
bet ween t hem. Upon char ging, Pb
++
is deposit ed on t he lead sheet which is
made cat hodic by t he applicat ion of a pot ent ial fr om an out side power sour ce. That is
elect r onat ion occur s. At t he ot her elect r ode, t he Pb
2+
ions pr esent in solut ion, dur ing
char ging, yield elect r ons t o t he anodic lead plat e and become Pb
4+
. Aft er war ds hydr olysis
t akes place t o for m cr yst alline PbO
2
, which deposit s on t he plat e.
Ther efor e, t he elect r ode r eact ions dur ing char ging would be:
at cat hode, Pb
2+
+ 2e Pb ...(9)
at anode, Pb
2+
+ 6H
2
O PbO
2
+ 4H
3
O
+
+ 2e ...(10)
Dur ing dischar ge, t he r ever se of t he above r eact ions occur . Relat ively high cur r ent
densit ies can be r eached dur ing dischar ge, i.e., t he over pot ent ial developed dur ing t he
r eact ion is small. The impor t ance of t he fact t hat t he exchange-cur r ent densit y for t he
dischar ge of H
3
O
+
on lead is low may be seen for , at t he cat hode (dur ing char ging) t he
r eact ion Pb
2+
+ 2e Pb occur s and not t he r eact ion H
3
O
+
+ e
1
2
H
2
+ H
2
O (i.e., t his
lat t er r eact ion occur s t o a negligible ext ent because t he r elat ion i = i
0
e
n/RT
. Also because
t he exchange-cur r ent densit y for t he r eact ion of hydr ogen evolut ion on lead is low.
Inert electrodes
e
Source+
Cd( OH)
2
Ni ( OH)
2
e
KOH sol uti on
Porous separator
Ther e ar e t wo main difficult ies which make it desir able t o develop elect r icit y st or er s
ot her t han t he lead-acid st or age syst em as quickly as possible. The impor t ant one is t he
weight of t he cell per unit of ener gy pr oduced which gives poor value of t he r eal ener gy
densit y. The pr act ical value is 0.022 t o 0.026 kWh kg
1
.
The second difficult y being; t hat t he plat es under go a pr ocess called sulphanat ion.
When t he st or er is not supplying elect r icit y, spont aneous dischar ge t akes place at t he
lead elect r ode:
Pb +
2
4
SO PbSO
4
+ 2e ...(11)
2H
3
O
+
+ 2e 2H
2
O + H
2
...(12)
At t he PbO
2
elect r ode,
PbO
2
+ H
2
SO
4
+ 2e PbSO
4
+ 2H
2
O +
2
4
SO ...(13)
Pb +
2
4
SO PbSO
4
+ 2e ...(14)
The life of t he cell get s limit ed wit h such pr ocesses like gr adual conver sion of lead
and lead dioxide t o lead sulphat e of lar ge par t icle size t akes place.
The lead acid bat t er y is used for so long, t he r eason being t hat t he bat t er y gives ver y
high cur r ent densit ies per unit ar ea, lit t le power is needed t o st ar t an aut omot ive
engine, it is just what is needed.
Zinc Manganese Dioxide
Dr y cells ar e elect r ochemical ener gy st or er s in which t he elect r olyt e is immobilized
in t he for m of a past e. A t ypical of t hese cells is t he Leclanche cell. A schemat ic diagr am
of t he cell is shown in Fig. 16.5
e
Load
e
Carbon rod
Zinc can
(MnO+C+NH ) mix
2 4 2
Cl+H O
Porous partition
Immobilized electrolyte
(NH Cl+ZnCl )
4 2 2
+ H O
Fi g. 16.5 : Schemat ic diagr am of a Leclanche cell.
The r eact ions t hat occur in t he cell dur ing dischar ge ar e
At anode Zn + Zn
2+
+ 2e ...(15)
At cat hode 2MnO
2
+ 2H
3
O
+
+ 2e Mn
2
O
3
+ 3H
2
O ...(16)
The following ir r ever sible side r eact ions also occur since hydr oxide ions ar e pr oduced
dur ing wor king:
OH
+ NH
4
+
H
2
O + NH
3
...(17)
Zn
2+
+ 2NH
3
+ 2Cl
Zn(NH
3
)
2
Cl
2
...(18)
Zn
2+
+ 2OH
ZnO + H
2
O ...(19)
ZnO + Mn
2
O
3
Mn
2
O
3
. ZnO ...(20)
The cell is only par t ially r echar geable because of t he above r eact ions and as such it
is never done in pr act ice. These cells ar e ext ensively used as pr imar y bat t er ies, inspit e
of t his disadvant age. They have an ener gy densit y of about 0.14 kWh kg
1
if dischar ged
at low cur r ent densit ies.
Relatively New Electricity Stores Silver Zinc Cell
An elect r ochemical ener gy st or er which is par t icular ly not ed for high power densit ies
in pr act ice is t he silver -zinc cell. The mat er ials used as fuels on t he elect r ode subst r at es
ar e zinc and AgO. Sat ur at ed KOH is t he elect r olyt e. Schemat ic diagr am is given below :
React ions occur ing in t he cell dur ing char ging ar e descr ibed as:
Ag
e
Load
AgO
Zn
e
Porous separator
KOH sol uti on
Fi g. 16.6 : Schemat ic diagr am of a silver -zinc cell.
at anode Ag + 2OH
AgO + H
2
O + 2e ...(21)
at cat hode ZnO + H
2
O + 2e Zn + 2OH
...(22)
While dischar ging t he r ever se of t he above r eact ion t akes place.
The exchange cur r ent densit ies of t he cell r eact ions ar e r elat ively lar ge and side
r eact ions ar e compar at ively slow in t he r at e. These cells have an ener gy densit y in t he
r egion of 0.1 kWh kg
1
. The disadvant age being, t he small number of char ge-dischar ge
cycles which t his cell is able t o st and befor e it s r eact ant mass under goes some for m of
det er ior at ion. The advant age in having t he highest ener gy densit y and power densit y
of commer cially available cells. It is t o be not ed t hat t he number of cycles which t he cell
under goes befor e br eakdown is a funct ion of t he degr ee t o which it is dischar ged.
Storers with Zinc in Combination with an Air Electrode
Among t he mor e act ive met als is zinc (Ve = 0.76 V for t he r eact ion Zn Zn
++
+ 2e.
And in an alkaline solut ion coupled wit h an air elect r ode, t he r ever sible t her modynamic
cell pot ent ial is 1.62 V. A schemat ic diagr am of such a cell is shown in t he Fig. 16.7. The
r eact ion upon char ging would be
at anode, 4OH
2H
2
O + O
2
+ 4e ...(23)
at cat hode, 2Zn(OH)
2
+ 4e 2Zn + 4OH
...(24)
Air compressor
e
Load
Insert electrodes
Zn
e
Circulating electrolyte (KOH)
Pump
Air in
Electrolyte
reservoir
Porous Ni
Air (from compressor)
Fi g. 16.7 : Schemat ic r epr esent at ion of a zinc air cell.
Those upon dischar ging would be t he r ever se.
The deposit ion and dissolut ion of zinc is empir ically well under st ood, lar gely fr om
st udies concer ned wit h t he silver -zinc cell (in compar ison wit h which t he zinc air cell
would have an obvious economic advant age).
In fact such zinc-air cells have been known for many year s, but r egar ded as syst ems
able t o give r ise only t o low power .
The difficult ies t hat ar e faced on such syst ems ar e lar gely concer ned wit h t he
di ffi cu l t i es a r i s en on r epea t i n g ma n y t i mes (i . e. , t h e cel l i s ch a r ged) t h e
elect r ocr yst allizat ion r eact ion associat ed wit h t he cat hodic for mat ion of zinc. These ar e
oxygen side of t he st or er makes t he ener gy densit y of such a hypot het ical st or age device
depend on t he weight of t he cont ainer mat er ial used t o st or e hydr ogen. If volume
consider at ions ar e not impor t ant , t he hydr ogen could be st or ed at low pr essur e in
r elat ively light cont ainer s. Even somet imes balloon st or age could be favour able. The
pr oblem is lar gely one of t he weight of a cont ainer wit h sufficient st r engt h. One could
also cont emplat e under gr ound st or age of hydr ogen pr oduced by elect r olysis, per haps of
sea wat er . Anot her difficult y of t he hydr ogen-oxygen cell is t he slow kinet ics of t he
oxygen elect r ode. Doped non st oichiomet r ic oxides of t r ansit ion met als have been shown
t o have cat alyt ic pr oper t ies compar able wit h t hose of plat inum.
The favour able kinet ics of t he r eact ion 2H
+
+ 2e H
2
wit h high i
0
value on cheap
subst r at e mat er ial like nickel oxide or nickel for bot h anodic dissolut ion as well
a s ca t hodic evolut ion. The pr ospect s for hydr ogen a ppr oa ch t o t he st or a ge of
elect r icit y have r at her been favour able pr ospect s due t o t he absence of cr yst allizat ion
or cor r osion.
Storage by Using Alkali Metals
Among t he r equir ement s of a desir ed ener gy st or er ar e a high r ever sible cell pot ent ial
a nd high i
0
values for bot h t he elect r ode r eact ions. An appr oach of t his ideal can be
obt ained by combining t he alkali met al-dissolut ion r eact ions e.g.,
M M
+
+ e ...(25)
wit h halogen-dissolut ion r eact ion in a molt en
X
2
+ 2e 2x
...(26)
salt Mx.
Such a device not only fulfills t he t wo cr it er ia ment ioned e.g., Li LiCl
1
2
Cl
2
at
600C has an open cir cuit pot ent ial of about 3.5 V and an i
0
value of about 0.1 amp
cm
2
(on car bon) for t he Cl
2
elect r ode, but also has a fur t her unique pr oper t y. Ther e is
no solut ion in nor mal sense in which t he diffusion of a solut e t o and fr om t he elect r odes
gives limit ing mass-t r anspor t r at es which define t he maximum r at e of char ge and
dischar ge of devices. In pur e Mx e.g., liquid LiCl at 650C, t he supply of mat er ial t o t he
elect r odes is in effect gover ned by t he ionic-conduct ance par amet er s. These ar e about
t en t imes higher in molt en salt s in t he r egion of t he t emper at ur e ment ioned t han in t he
cor r esponding aqueous elect r olyt e at lower t emper at ur es.
Elect r icit y st or er s involving alkali met als and halogens have advant ages in power
densit ies which is difficult t o find in any ot her dir ect ions. The st abilit y of mat er ial is
ver y impor t ant and elect r ochemical r eact ions which ar e t he or igin of inst abilit y of t he
mat er ials have t o be looked aft er . Examples could be of nonconduct ing or ganic mat er ials
may pr ovide st able subst r at es in a number of inst ances. The difficult y has been t he
t her mal inst abilit y of subst ances ar ises above 250 t o 300C. However , t he example could
be of polyphenylene t ype of compounds give t her mal st abilit y int o t he r ange of 500 t o
600C.
Storers involving Non-aqueous Solutions
The aim for an elect r icit y st or er would be t hat it s elect r odes should have widely
differ ent and highly r ever sible elect r ode pot ent ials i.e., t he lat t er is equivalent t o having
high exchange-cur r ent densit ies. A r eact ion is used wit h oxygen at t he cat hodic dischar ge
st ep and it should be fr ee of t he mat er ial inst abilit y and br eakdown pr oblems associat ed
wit h t he pr esence of high t emper at ur es. The for mer condit ion is t o avoid t he weight of
cont ainer s for a second fuel.
The fir st r equir ement s indicat es t he pr oject ed alkali met al cells, t he use of t he
met als like t hat of Lit hium and Ber yllium gr oup. The difficult y t hat ar ises is t hat t hese
met als cor r ode violent ly in aqueous solut ions t o give hydr ogen fr om t he par allel cat hodic
r eact ion like 2H
+
+ 2e H
2
, which must occur if t he cent r al cor r osive r eact ion M M
+
+ e is t o t ake place. The explosion is caused by t he heat engender ed t oget her wit h t he
pr esence of oxygen fr om air .
Anot her solut ion could be obt ained by t he use of non-aqueous solvent s. Acet onit r ile
could be an example in which t he cor r osion r eact ion and t her efor e t he pr esence of
evolved H
2
ar e suppr essed t o zer o velocit y. A number of non-aqueous solvent s ar e known.
The aim is t o discover a way of making oxygen t o dissolve cat hodically in a non-aqueous
medium. Cor r osion pr oblems at r oom t emper at ur e ar e small so long as t hat of t he alkali
or alkaline ear t h met al is avoided by t he use of a non-aqueous solut ion in which hydr ogen-
evolut ion r eact ion is absent . An excellent hypot het ical elect r icit y st or er would be a
r echar geable cell of ber yllium wit h air .
Ag mesh
e
Load
Li sheet
CuF + Cu powder mix (sintered)
e
Porous separation (glass filter paper)
Solution of NaPF in
propylene carbonate
6
Fi g. 16.9 : Schemat ic diagr am of an or ganic elect r olyt e ener gy st or er .
Sat isfact or y funct ioning of an oxygen elect r ode in a non-aqueous solut ion has not yet
been made. The cat hodic r educt ion of O
2
usually for ms wat er , so t hat a solvent syst em
would have t o be devised t o pr ovide an analogous solvent -for ming r eact ion. Then dur ing
char ging, t he anodic r eact ion would have t o be t he evolut ion of oxygen. The solubilit y
of salt s in non-aqueous solut ion is oft en less t han t hat in aqueous solut ions. A r elat ively
small limit ing cur r ent and hence power would be expect ed wit h devices using non-
aqueous solut ions.
The basic advant age of elect r icit y st or er s wit h non-aqueous solut ions is t hat t hey
can involve, high elect r icit y st or age capacit y of t he alkali and alkaline ear t h cont ainer s.
Wit h t his t he pr oblem of t he weight of cont ainer s for hydr ogen or t he mat er ial inst abilit y
pr oblems of high t emper at ur e cells. Development s in t he past few year s have led t o t he
development of liquid ammonia cells which oper at es under high pr essur e and or ganic
solvent s like pr opylene car bonat e, dimet hyl for mamide dimet hyl sulphoxide, acet onit r ile
and met hyl for mat e which cont ain dissolved or ganic and inor ganic salt s. A schemat ic
diagr am of an or ganic elect r olyt e elect r icit y st or er is given her e. Fig. using t hese
elect r olyt es, it is possible t o oper at e syst ems in which t heor et ical ener gy densit ies ar e
about five t imes higher t han t hose of convent ional cells oper at ing in aqueous media. A
hybr id sit uat ion could also be possible, wher e alkali met al in cont act wit h a non-aqueous
solut ion an oxygen elect r ode in cont act wit h an aqueous one. The t wo being separ at ed
by some kind of membr ane. This device may give t he advant age of t he lar ge amount of
elect r icit y per unit weight char act er ist ic of alkali met als. This may avoid car r ying t he
cat hodic cell. Cor r espondingly, t he difficult y of finding a suit able r eact ion for a non-
aqueous sit uat ion and oxygen dissolut ion, including cor r osion-inhibt ion pr oblems of
molt en-salt cells would be avoided.
CHAPTER 17
KINETICS OF ELECTRODE PROCESS
INTRODUCTION
The br anch of chemist r y concer ned wit h t he int er r elat ion of elect r ical and chemical
effect s is act ually t he elect r ochemist r y. Most of t he st udy in t his field deals wit h t he
st udy of chemical char ges caused by t he passage of elect r ic cur r ent and t he pr oduct ion
of elect r ical ener gy by chemical r eact ions. A huge ar r ay of differ ent phenomena ar e
begin displa yed in t his field. The exa mples a r e : elect r ophor esis a nd cor r osion,
elect r oanalyt ical sensor s, bat t er ies and fuel cells. The t echnologies ar e elect r oplat ing of
met als and t he lar ge scale pr oduct ion of aluminium and chlor ine. Many elect r ochemical
met hods have been devised. Their applicat ion r equir es an under st anding of t he
fundament al pr inciples of elect r ode r eact ions and t he elect r ical pr oper t ies of elect r ode-
solut ion int er faces. In elect r ochemical syst ems t her efor e, t he main concer n is bet ween
t he chemical phases for example bet ween an elect r onic conduct or (an elect r ode) and an
ionic conduct or (an elect r olyt e). As such t he main feat ur e r emains wit h t he elect r ode/
elect r olyt e int er face and t he event s t hat occur when an elect r ic pot ent ial is applied and
cur r ent passes. Typical elect r ode mat er ials used ar e solid met als e.g., Pt , Au and liquid
met als like Hg, amalgams. Car bon (gr aphit e) and semi conduct s like indium-t in oxide
and si. In t he elect r olyt e phase, char ge is car r ied by t he movement of ions. The
elect r olyt es, t hat ar e most fr equent ly used, ar e liquid solut ions cont aining ionic species
s u ch a s H
+
, Na
+
, Cl
eit her in wa t er or in non-queous solvent s. For a useful

elect r ochemical cell t he solvent /elect r olyt e syst em must be so chosen which is of
sufficient ly low r esist ance i.e., it should be sufficient ly conduct ive for t he exper iment
chosen. Fused salt s like molt en NaCl-KCl (eulect ic) and ionically conduct ive polymer s
like Nafion, polyet hylene oxide LiClO
4
ar e less convent ionally used elect r olyt es. In
gener al, a differ ence in elect r ic pot ent ial can be measur ed bet ween t he elect r odes in an
elect r ochemical cell, which is done wit h a high impedance volt met er . This cell pot ent ial
is measur ed in volt s (V), wher e IV = 1 joule/coulomb (J /c). It is a manifest at ion of t he
collect ed differ ences in elect r ic pot ent ial bet ween all t he var ious phases in t he cell. The
t r ansit ion, in elect r ic pot ent ial, in cr ossing fr om one conduct ing phase t o anot her usually
occur s almost ent ir ely at t he int er face. The measur ement and cont r ol of cell pot ent ial
is one of t he most impor t ant aspect s of exper iment al elect r ochemist r y.
Taking an example of chemical r eact ion t aking place in a cell is has been obser ved
t hat it is made up of t wo independent half r eact ions, which descr ibe t he r eal chemical
changes t aking place at t he t wo elect r odes. Each half-r eact ion (and, consequent ly, t he
chemical composit ion of t he syst em near t he elect r odes) r espond t o t he int er facial
pot ent ial differ ences at t he cor r esponding elect r ode. The elect r ode at which it occur s is
called t he wor king elect r ode, or indicator electrode. Because, most ly one is int er est ed
in (one of t hese r eact ions), and t he elect r ode at which it occur s.
The ot her half cell is st andar dized by using an elect r ode known as reference elect rode
made up of phases having essent ially const ant composit ion.
The int er nat ionally accept ed pr imar y r efer ence is t he st andard hydrogen elect r ode
(SHE), or normal hydrogen electrode (NHE), which has all component s at unit act ivit y :
PH/H
2
(a = 1) H
+
a = 1, aqueous ...(1)
Pot ent ials ar e oft en measur ed and quot ed wit h r espect t o r efer ence elect r odes ot her
t han t he NHE. A common r efer ence elect r ode is t he saturated calomel electrode (SCE),
which is
Hg/Hg
2
Cl
2
/KCl (sat ur at ed in wat er )
It s pot ent ial is 0.242 V vs. NHE. Anot her is silver silver chlor ide elect r ode : wit h
a Ag/AgCl/KCl (sat ur at ed in wat er )
pot ent ial of 0.197 V vs. NHE.
Pt
AgBr
Ag
v
i
Power
supply
1 HBr M
Fi g. 17.1 : Schemat ic diagr am of t he elect r ochemical cell Pt / HBr (1 M)/AgBr /Ag at t ached t o
power supply and met er s for obt aining a cur r ent -pot ent ial (i-E) cur ve.
Since t he r efer ence elect r ode has a const ant make up, it s pot ent ial is fixed. Ther efor e
any changes in t he cell ar e ascr ibed t o t he wor king elect r ode only.
Consider , a t ypical elect r ochemical exper iment in Fig. 17.1 wher e a wor king elect r ode
and a r efer ence elect r ode ar e immer sed in solut ion and t he pot ent ial differ ence bet ween
wher e i
a
is t he anodic component t o t he t ot al cur r ent .
Thus t he net r eact ion r at e is
v
net
= v
f
v
b
= k
f
C
0
(O, t) k . C
R
(O, t) =
a
i
nFA
...(9)
and t he over all equat ion is r epr esent ed as :
i = i
e
i
a
= nFA[k
f
C
0
(O, t) k
b
C
R
(O, t)] ...(10)
It is t o be not ed t hat t he het er ogeneous r eact ions ar e descr ibed differ ent ly t han
homogeneous ones. Hence t hey have unit s of mols
1
cm
2
. As such het er ogeneous r at e
const ant s must car r y unit s of cm/s, if t he concent r at ion in which t hey oper at e ar e
expr essed in mol/cm
3
. This is because t he int er face can r espond only t o it s immediat e
su r r ou n din gs, t h e con cen t r a t ion en t er in g r a t e expr ession s a r e a lwa ys su r fa ce
concent r at ions which may differ fr om t hose of t he bulk solut ion.
17.2 BUTLER VOLMER MODEL OF ELECTRODE KINETICS R
Fr om exper ience it can be demonst r at ed t hat t he pot ent ial of an elect r ode st r ongly
affect s t he kinet ics of r eact ions occur ing on it s sur face. Hydr ogen evolves r apidly at
some pot ent ials, but not at ot her s. Copper dissolves fr om a met allic sample in a clear ly
defined pot ent ial r ange; yet t he met al is st able out side t hat r ange. So it is for all
far adiac pr ocesses. It is because t he int er facial pot ent ial differ ence can be used t o
cont r ol r eact ivit y and hence one can pr edict t he exact way in which k
f
and k
b
depend
on pot ent ial.
Effects of Potential on Energy Barriers
The idea t hat r eact ions can be visualized in t er ms of pr ogr ess along a r eact ion
coor dinat e connect ing a r eact ion configur at ion t o a pr oduct configur at ion on an ener gy
sur face implies t o elect r ode r eact ions t oo. But t he shape of t he sur face t ur ns out t o be
a funct ion of elect r ode pot ent ial.
By consider ing t he r eact ion,
Na
+
+ e
Hg
Na(Hg) ...(11)
t he effect can easily be seen wher e Na
+
is dissolved in acet onit r ile or dimet hylfor mamide.
The r eact ion coor dinat e can be t aken as t he dist ance of t he sodium nucleus fr om t he
int er face. It is t hen t he fr ee ener gy pr ofile along t he r eact ion coor dinat e would r esemble
t he Fig. 17.2(a)
To t he r ight , Na
+
+ e can be ident ified. This configur at ion has an ener gy t hat depends
lit t le on t he nuclear posit ion in solut ion, unless t he elect r ode is appr oached so closely
t hat , t he ion must be par t ially or wholly desolvat ed. To t he left , t he configur at ion
cor r esponds t o a sodium at om dissolved in mer cur y. Wit hin t he mer cur y phase, t he
ener gy depends only slight ly on posit ion. But if t he at om leaves t he int er ior , it s ener gy
r ises as t he favour able mer cur y sodium int er act ion is lost . The cur ves cor r esponding
Reduction
Oxidation
Na(Hg)
Na
+
+ e
Oxidation
Na(Hg)
Na
+
+ e
Reduction
Na(Hg)
Na
+
+ e
(a)
(b)
(c)
Amalgam Solution
Reaction coordinate
S
t
a
n
d
a
r
d
f
r
e
e
e
n
e
r
g
y
Fi g. 17.2 : Simple r epr esent at ion of st andar d fr ee ener gy changes dur ing a far adaic pr ocess.
(a) At a pot ent ial corresponding t o equilibrium. (b) At a more posit ive pot ent ial t han t he equilibrium
value. (c) At a mor e negat ive pot ent ial t han t he equilibr ium value.
Kinet ics of Elect rode Process 245
Consider ing a special case in which t he int er face is at equilibr ium wit h a solut ion
in which
* *
O R
C C = . In such a sit uat ion, E = E
0'
and
* *
K C K C , = So t hat k
f
= k
b
.Thus
E
0
is t he pot ent ial wher e t he for war d and r ever se r at e const ant s have t he same value.
That value is called st andar d r at e const ant , k
05
. The r at e const ant at ot her pot ent ials
can t hen be expr essed simply in t er ms of K
0
.
k
f
= k
0
exp[f (E E
0
)] ...(19)
k
b
= k
0
exp[(1 )
f
(E E
0'
)] ...(20)
Inser t ion of t hese r elat ions int o equat ion :
i = i
c
i
a
= xFA = [k
f
C
0
(O,t) k
b
C
r
(O,t)] (20')
Yields t he complet e cur r ent -pot ent ial char act er ist ic
( )
( )
0

0
0
=F A ,
f E E
e
i k C O t
( )
( )
( )
0
1 f E E
R
e
C O,t
= = (
...(21)
This r elat ion is ver y impor t ant since t his or a var iat ion der ived fr om it is ver y useful
for ever y pr oblem r equir ing an account of het er ogeneous kinet ics. These r esult s and t he
infer ences der ived fr om t hese ar e br oadly known as Bu t l e r -Vol me r for mulat ion of
elect r ode kinet ics.
17.3 IMPLICATIONS OF THE BUTLER-VOLMER MODEL FOR THE ONE
STEP, ONE ELECTRON PROCESS
Eq u i li b r i u m Con d i t i on s . The Exchange Cur r ent at equilibr ium, t he net cur r ent is
zer o, and t he elect r ode is known t o adopt a pot ent ial based on t he bulk concent r at ion
of O and R as dict at ed by t he Ner nst equat ion.
Since equilibr ium applies, t he bulk concent r at ions of O and R ar e found also at t he
sur face; hence
et(E
eq
E
0
)
*
*
CO
CR
...(22)
which is simply an exponent ial for m of t he Ner nst r elat ion
E
eq
= E
0
' +
RT
F
ln
*
*
CO
CR
...(23)
Even t hough t he net cur r ent is zer o equilibr ium t he balanced far adic at act ivit y t hat
can be expr essed in t er ms of t he exchange current, i
0
. which is equal in magnit ude t o
eit her component cur r ent i
0
or i
a
. That is .
( ) 0
o * o'
oc eq
i FAK C f E E = ...(24)
If bot h sides of t he equat ion ar e r aised t o t he power , what is obt ained is
e
f
(E
eq
E
0
) =
Co*
CR *
| |
|
\ .
...(25)
Subst it ut ion of above equat ion int o gives
i
0
= Fak
( ) 1 *
**
o R
C C
...(26)
The exchange cur r ent is t her efor e pr opor t ional t o k
0
and can oft en be subst it ut ed for
k
0
in kinet ic equat ions. For t he par t icular case wher e
*
o
C
*
R
C C, = =
i
0
= Fak
0
C ...(27)
Oft en t he exchange cur r ent is nor malized t o unit ar ea t o pr ovide t he exchange
cur r ent densit y, j
0
= i
0
A.
17.4 THE CURRENT OVERPOTENTIAL EQUATION
An advant age of wor king wit h i
o
r at her t han k
0
is t hat t he cur r ent can be descr ibed in
t er ms of t he deviat ion fr om t he equilibr ium pot ent ial, t hat is, t he over pot ent ial, ,
r at her t han t he for mal pot ent ial E
0'
.
The r at ios
( )
* *
o R
C C and
( )
( ) 1
* *
o R
C C

can easily be evaluat ed fr om t he equat ion e
f
(E
eq
E
0
) =
Co*
CR *
and
t he equat ion e
ft
(E
eq
E
0'
) =
Co*
CR *
| |
|
\ .
,
and by subst it ut ion what is obt ained is
( ) ( )
( ) 1 f n o R f n
o
o R
C O,t C O,t
i i e e
C * C *
(
=
(

...(28)
wher e = E E
eq
. This equat ion is known as t he cur r ent -over pot ent ial equat ion. It is
t o be not ed t hat t he fir st t er m descr ibes t he cat hodic component cur r ent at any pot ent ial,
and t he second gives cat hodic cont r ibut ion
8
.
17.5 THE STANDARD RATE CONSTANT
The physical int er pr et at ion of k
0
is st r aight for war d. It is simply a measur e of t he
kinet ic facilit y of a r edox couple. A syst em wit h a lar ge k
0
will achieve equilibr ium in
a shor t t ime scale but a syst em wit h small k
0
will be sluggish. The lar gest measur ed
st andar d r at e const ant s ar e in t he r ange of 1 t o 10 cm/s and ar e associat ed wit h
par t icular ly simple elect r on t r ansfer pr ocesses. The st andar d r at e const ant s for r educt ion
and oxidat ion of many ar omat ic hydr ocar bons, such as subst it ut ed ant hr acenes, pyr ene
and per ylene t o t he cor r esponding anion and cat ion r adicals fall in t his r ange(Ref.1-4).
These pr ocesses involve only elect r on t r ansfer and r esolut ion. These ar e no significant
alt er at ions in t he molecular for ms. Similar ly, some elect r odes pr ocesses involving t he
for mat ion of amalgam e.g., t he couples Na
+
/Na(Hg), Cd
2+
/Cd (Hg), a nd Hg
2
2+
/ (Hg) a r e
r at her facile [25,26] R.
It is t o be not ed t hat k
f
and k
b
can be made quit e lar ge, even if k
0
is small. This is
possible by using a sufficient ly ext r eme pot ent ial r elat ive t o E
0
.
17.6 THE TRANSFER COEFFICIENT
The t r ansfer coefficient , is a measur e of t he symmet r y of t he ener gy bar r ier . This idea
can be implied by consider ing in t er ms of t he geomet r y of t he int er sect ion r egion as
shown in t he Fig 17.4.
Fi g. 17.4 Relat ionship of t he t r ansfer coefficient t o t he
angles of int er sect ion of t he fr ee ener gy cur ves.
If t he cur ves ar e locally linear , t hen t he angles and ar e defined by
t an = FE/x (29)
when = (1) FE/x (30)
hence
=
t an
t an t a n
+
(31)
If t he int er sect ion is symmet r ical, = and =
1
2
, ot her wise
1 1
0 1
2 2
or S , <
, (32)
as shown in Fig. 17.5 (next page) in most syst ems t ur ns out t o be bet ween 0.3 and
0.7, and it can usually be appr oximat ed by 0.5 in t he absence of act ual measur ement s.
Fig. 17.5 The t r ansfer coefficient as an indicat or of t he symmet r y of t he bar r ier t o
r eact ion. The dashed lines show t he shift in t he cur ve for O + e as t he pot ent ial is made
mor e posit ive.
The fr ee ener gy pr ofiles ar e not likely t o be linear over lar ge r anges of t he r eact ion
co-or dinat e, t hus t he angles and can be expect ed t o change as t he int er sect ion
bet ween r eact ant and pr oduct cur ves shift s wit h pot ent ial. Consequent ly should
gener ally be a pot ent ial dependent fact or . However , in t he gr eat major it y of exper iment s,
FE
R
E=E
E=0
O + e
(1)FE
Length=x
Reaction coordinate
S
t
a
n
d
a
r
d
f
r
e
e
e
n
e
r
g
y
appear s t o be const ant , if only because t he pot ent ial r ange over which kinet ic dat a can
be collect ed ar e fair ly nar r ow.
Fig. 17.5
In a t ypical chemical syst em, t he fr ee ener gy of act ivat ion ar e in t he r ange of a few
elect r on volt s, but t he full r ange of measur able kinet ics usually cor r espond t o a change
in act ivat ion ener gy of only 50-200 meV, or a few per cent of t he t ot al. Thus, t he
int er sect ion point var ies only over a small domain, such as t he boxed r egion Fig. 17.3
wher e t he cur vat ur e in t he pr ofiles can har dly be seen. The kinet ically oper able pot ent ial
r ange is nar r ow in most syst ems because t he r at e const ant for elect r on t r ansfer r ises
exponent ially wit h pot ent ial. Not far beyond t he pot ent ial wher e a pr ocess fir st pr oduces
Fig. 17.6. Cur r ent -over pot ent ial cur ves for t he syst em O + e R wit h = 0.5, T = 298 K, i
l, c
= i
l, a
= i
l
and i
0
/ i
l
= 0.2. The dashed lines show t he component cur r ent s i
c
and i
a
.
O+e
R
S
t
a
n
d
a
r
d
f
r
e
e
e
n
e
r
g
y
=
1
2
O+e
R
<
1
2
O+e
R
>
1
2
Reaction coordinate
400 300 200 100
100 200 300 400
. mV
1.0
0.8
0.6
0.4
0.2
0.2
0.4
0.6
0.8
1.0
ia
i0
E
eq
i
l
i
l
i/i
l
Total current
i
c
a det ect able cur r ent , mass t r ansfer becomes r at e-limit ing and t he elecr t r on t r ansfer
kinet ics no longer cont r ols t he exper iment . In few syst ems, mass t r ansfer is not an issue
and kinet ics can be measur ed over ver y wide r ange of pot ent ial. In cases involving
sur face-bound elect r oact ive species, lar ge var iat ion of wit h pot ent ial have also been
obser ved.
The behaviour pr edict ed in t he last equat ion is depict ed in t he ensuing Fig. 17.6 The
solid cur ve shows t he act ual t ot al cur r ent which is t he sum of t he component s i
c
and i
a
,
as ar e shown in dashed t r aces. For lar ge negat ive over pot ent ials, t he anodic component
is negligible. Hence t he t ot al cur r ent cur ve mer ges wit h t hat for i
c
. At lar ge posit ve
over pot ent ials, t he cat hodic component is negligible, and t he t ot al cur r ent is essent ially
t he same as i
a
. In going eit her dir ect ion fr om E
eq
, t he magnit ude of t he cur r ent r ises
r apidly, because exponent ial fact or s dominat e t he behaviour , but at ext r eme , t he
cur r ent levels off. In t hese level r egions, t he cur r ent is limit ed by mass t r ansfer r at her
t han het er ogeneous kinet ics. The exponent ial fact or s in t he for going equat ion ar e t hen
moder at ed by t he fact or s
C
0
(o,t)/
*
o
C and C
R
(O, t)C
R
*
, which manifest t he r eact ant supply.
17.7 APPROXIMATE FORMS OF THE i EQUATION
(a) No Mass-Transfer Effects
If t he solut ion is well st ir r ed or cur r ent s ar e kept so slow t hat t he sur face
concent r at ions do not differ appr eciably fr om t he bulk valves, t hen t he pr evious equat ion
becomes
( ) 1 f
f e
o
i i e

(
=
(

...(33)
which is hist or ically known as t he But ler -Volmer equat ion.
Since mass-t r ansfer effect s ar e not included her e, t he over pot ent ial associat ed wit h
any given cur r ent ser ves solely t o pr ovide t he act ivat ion ener gy r equir ed t o dr ive t he
het er ogeneous pr ocess at t he r at e r eflect ed by t he cur r ent . The lower t he exchange
cur r ent , t he mor e sluggish t he kinet ics. Hence t he lar ger t his act ivat ion over pot ent ial
must be for any par t icular net cur r ent .
(b) Linear characteristic at small
For small values of x; t he exponent ial e
x
can be appr oximat ed as 1 + x, hence for
sufficient ly small , t he above equat ion can be expr essed as
i = i
0
+ f ...(34)
which shows t hat t he net cur r ent is linear ly r elat ed t o over pot ent ial in a nar r ow pot ent ial
r ange near E
eq
.The r at io /i has unit s of r esist ance and is oft en called t he char ge
t r ansfer r esist ance, R
ct
0
ct
RT
R
Fi
=
...(35)
Fig. 17.7 : Effect of exchange cur r ent densit y on t he act ivat ion over pot ent ial r equir ed t o deliver
net cur r ent densit ies. (a) j
o
= 10
3
A/cm
2
(Cur ve is indist inguishable fr om t he cur r ent axis),
(b) j
0
= 10
6
A/cm
2
, (c) j
0
= 10
9
A/cm
2
. For all cases t he r eact ion is O +e
R wit h = 0.5
and T = 298 K
This par amet er is t he negat ive r ecipr ocal slope of t he in cur ve wher e t hat cur ve
passes t hr ough t he or igin ( = 0, i = 0). It can be evaluat ed dir ect ly in some exper iment s,
and it ser ves as a convenient index of kinet ic facilit y. For ver y lar ge K
0
, it appr oaches
zer o Fig. 17.7.
(c) Tafel Behaviour at Large
For lar ge values of (eit her negat ive or posit ive), one of t he br acket ed t er ms in
equat ion becomes negligible. For example at lar ge negat ive over pot ent ials,
exp (af) >> exp[(1)f ] and t he equat ion Fig. 17.8 becomes:
f
o
i i e

= ...(36)
or
o
RT RT
l n i l n i
F F
=

...(37)
A successful model of elect r ode kinet ics must explain t he fr equent validit y of t he
above equat ion, known as Ta fe l e q u a t i on . The empir ical t afel const ant s : equat ion
= a + b logi can be ident ified fr om t heor y as
=
2 3
log
o
i
. RT
F
2 3 . RT
b
F
...(38)
400 300 200 100
100 200 300 400
. mV
0.8
0.6
0.4
0.2
0.2
0.4
0.6
0.8
j,A/cm
2
(c)
(a)
(b)
The t afel for m can be expect ed t o hold whenever t he back r eact ion (i.e., t he anodic
pr ocess, when a net r educt ion is consider ed, and vice ver sa) cont r ibut es less t han 1% of
t he cur r ent . Tafel r elat ionships cannot be obser ved fr o such cases, because t hey r equir e
t he absence of mass-t r ansfer effect s on t he cur r ent . When elect r ode kinet ics ar e sluggish
and significant act ivat ion over pot ent ials ar e r equir ed, good Tafel r elat ionships can be
seen. This point explains t he fact t hat Tafel behaviour is an indicat or of t ot ally ir r ever sible
kinet ics. Syst ems in t hat cat egor y allow no significant cur r ent flow except at high
over pot ent ials, wher e t he far adaic pr ocess is effect ively unidir ect ional and, t her efor e,
chemically ir r ever sible.
(d) Tafel Plots
A plot of log i. vs. , known as Tafel plot , is a useful device for evaluat ing kinet ic
par amet er s. In gener al, t her e is an anodic br anch wit h a slope (1)F/2.3RT and a
cat hodic br anch wit h slope F/ 2.3RT. As shown in Fig. 17.8 bot h linear segment s
ext r apolat e t o an int er cept of log i
0
.
Fi g. 17.8 : Tafel plot s for anodic and cat hodic br anches of t he cur r ent -over pot ent ial cur ve for
O + e

R wit h = 0.5, T = 298 K, and j
0
= 10
-6
A/cm
2
.
9
Not e t hat for = 0.5, b = 0.118 V, a value t hat is somet imes quot ed as t ypical
Tafel slope.
The plot s deviat e shar ply fr om linear behaviour as appr oches zer o, t his is because
t he back r eact ions can no longer be r egar ded as negliglible. The t r ansfer co-efficient
and t he exchange cur r ent , i
0
are obviously readily accessible from t his kind of present at ion
when it can be applied.
Exchange Current Plots (Tafel Plots)
This kind of plot is useful for obt aining fr om exper iment s in which i
0
is measur ed
essent ially dir ect ly. Fr om t he equat ions it r ecognized t hat t he exchange cur r ent can be
r elat ed as :
200 150 100 50 50 100 150 200
log i
0
5.5
4.5
3.5
6.5
Slope =
(1 )F
2.3RT
Slope =
F
2.3RT
log |i|
, mV
2 3 2 3
o * o'
o o eq
F F
log i log FAk log C E E
. RT . RT

= + +
...(39)
Ther efor e, a plot of log i
0
vs. E
eq
at const ant C* should be linear wit h a slope of
23 F / . RT
. The equilibr ium pot ent ial E
eq
can be var ied exper iment ally by changing t he
bulk concent r at ion of species R, while t hat of species O is held const ant . This kind of
plot is useful for obt aining fr om exper iment s in which i
0
is measur ed essent ially
dir ect ly.
17.8 EFFECTS OF MASS TRANSFER
A mor e complet e 1- r elat ion can be obt ained fr om
( ) ( )
( ) 1 f o R f
o
* *
o R
C o,t C O,t
i i e e
C C

(
= (
(

...(40)
(wher e = E E
eq
) by subst it ut ing for
( )
*
o o
C O,t C and
( )
*
R R
C O,t C
Accor ding t o
( ) 0
R
x
o
*
C
Co
=
1
i
il
...(41)
and
( ) 0
1
x
R
R*
C
i
C il,a
=
= ...(42)
( ) 1
1 1
e
f
o
i i i
e
i il,c i l ,a

| | | |
=
| |
\ . \ .
...(43)
This equat ion can be r ear r anged easily t o give i as an explicit funct ion of over t he
whole r ange of .
For small over pot ent ials, a linear ized r elat ion can be used.
In t he Tafel r egions, ot her useful for ms of t he above equat ion can be obt ained. For
t he cat hodic br anch at high values, t he anodic cont r ibut ion is insignificant and as such
t his equat ion becomes
( ) 1 1 1
f
o l c l,a
i i i
e e fn
i i , i
| |
| |
=
|
|
\ .
\ .
...(44)
This equat ion can be useful for obt aining kinet ic par amet er s for syst ems in which
t he nor mal Tafel plot s ar e complicat ed by mass-t r ansfer effect s.
References
1. B.E. Conway, Theor y and Pr inciples of Elect r ode Pr ocesses, Ronald, New Yor k,
1965, Chap. 6.
2. H.R. Thir sk, A Guide t o t he St udy of Kinet ics, Academic, New Yor k, 1972, Chap. 1.
3. J . Om. Bockr is and A.K.N. Reddy, Moder n Elect r ochemist r y, Vol. 2, Plenum, New
Yor k, 1970, Chap. 8.
4. K. J . Vet t er , Elect r ochemical Kinet ics, Academic, New yor k, 1967, Chap. 2.
5. C.N. Reilley in Tr eat ise on Analyt ical Chemist r y, Par t I, Vol. 4, I.M. Kolt hoff and P.J .
Elving Eds., Wiley-Int er science, 1963, Chap. 42.
6. T. Er dey-Gr uz, Kinet ics of Elect r ode Pr ocesses, Wiley-Int er science, New Yor k, 1972,
Chap.1 & 4.
7. W.J . Alber y, Elect r ode Kinet ics, Clar endon, Oxfor d, 1975.
J .E.B. Randles, Trans. Faraday S oc., 48,828 (1952).
H. Kojima and A.J . Bar d, J . Am. Chem. S oc., 97, 6317 (1975).
8. M. E. Peover , Electroanal. Chem., 2, 1 (1967).
N. Koizumi and S. Aoyagui, J . Electroanal. Chem., 55,452 (1974).
CHAPTER 18
BIOELECTRODICS
INTRODUCTION
Elect r ochemist r y as we have come t o know it consist s in t he st udy of ionic solut ions, and
elect r odes wher e ions and elect r ons combine and separ at e. Galvani fr om Bologna, It aly,
in 1791, put for t h t hat bio elect r ochemist r y has been a par t of elect r ochemist r y.
It would be not t oo much t o say t hat t her e ar e elect r ochemical event s going on in
living syst ems wher e ever you pr y int o t hem. The ner vous syst em is cer t ainly based on
t he flow of elect r ic cur r ent s and it is not of all fanciful t o see ner ves as t he wir es t hat
r un bet ween t he enzymes, t he elect r odes of t he body. Bodies ar e full of membr anes, 100,
and so ar e elect r ochemical cells. Some r eact ions in t he body baffle chemist s by going up
t r ee ener gy gr a dient s, but a ga in t ha t is just wha t ha ppens in elect r olysis, in
elect r ochemical r eact or s.
We can st udy elect r ochemical phenomena in t he immense complexit y of living syst ems
when all we know is how t o explain simple syst ems like fuel cells and cor r osion seems
t o be t he cr assest ar r ogance.
The science of biology is a t r uly gigant ic edifice, so big, in fact , t hat it includes all
of or ganic chemist r y and uses it t o explor e ver y ver y complicat ed int er act ions.
USEFUL PRELIMINARIES
The aminoacid glycine i.e., NH
3
+
CH
2
COO
would be simplest example excluding of

cour se H
3
O
+
, H
2
O, and O
2
of an ent it y t hat t akes par t in bior eact ions,
A St r uct ur al element wit hin t he amino acid is t he pept ide gr oup
N C
H O
| |

which is impor t ant because when many of t hese gr oups occur in a chain, and such
chains for m a polymer , one has a pr ot ein. Pr ot eins for m skin, nails, and skelet al
st r uct ur es. Enzymes biocat alyst s ar e pr ot eins, Hemoglobin, which car r ies O
2
ar ound t he
body is a pr ot ein. Pr ot eins can have molecular weight s as law as 10,000 but some ar e
r eally ver y lar ge wit h molecular weight s of 50 10
6
. The cor r esponding r adii of t he
lar ger of t hese ent it ies (when t hey get for med spher ically), would be in t he hundr eds of
angst or ms. Examples of some amino acids ar e shown in t he Fig. 18.1. St r uct ur es t hat
Fi g. 18.1 Examples of some amino acids. (Repr int ed wit h per mission fr om Account s of Chemical
Resear ch 21 copyr ight 1989, Fig. 1, Amer ican Chemical Societ y)
a pr ot ein, for example in glycine. The pr ot eins found in nat ur e ar e made up of only
about 20 differ ent individual amino acids. On t he ot her hand, a t ypical pr ot ein consist s
of sever al hundr eds of t hese 20 dist inguishable amino acids. These pr ot eins (cont aining
sever al hundr eds of t he 20 special amino acids) might be t hought at fir st t o be long, long
chains cont aining r epeat ed pept ide gr oups (see last fig.) 18.2 which can be wr it t en mor e
Fi g. 18.2 Pept ide
explicit ly as wher e t he Rs may be hydr ocar bon chains on ot her pept ide element s and
t he shaded ar ea denot es t he bond bet ween t he t wo pept ides. However t hese long flexible
chains ar e neit her linear nor r andom in shape. They coil and st r et ch in a way t hat
gr eat ly affect s t he pr oper t ies of t he pr ot ein i.e., how it does it s wor k. Among t he most
impor t ant of t hese st r uct ur es is an ar r angement called t he -helix (accor ding t o pauling
and Cor ey 1951) but of t he element s in cells, t he mit ochondr ion. These mit ochondr ia ar e
t he ent it ies in cells wher e ener gy is made fr om t he oxidat ion of or ganics der ived fr om
int ake of food and oxygen.
H
2
NCCOOH
H
|
|
H
H
2
NCCOOH
H
|
|
CH
CH
3
CH
2
CH
3
H
2
NCCOOH
H
|
|
CH2
|
OH
H
2
NCCOOH
H
|
|
(CH
2 4
)
|
NH
2
H
2
NCCOOH
H
|
|
CH
2
N
H
H
2
NCCOOH
H
|
|
CH
2
|
COOH
Glycine (gly) Isoleucine(ile) Serine (ser)
Tryptophan (trp) Aspartic acid (asp) Lysine (lys)
Peptide
HNCCNCCOH
R
|
|
H
|
H
||
O
|
H
|
H
||
O
R
|
Membrane Potentials
The measur ement and int er pr et at ion of t he pr ot ent ials acr oss biological membr anes
has been going on for about a cent ur y. A r emar kable suggest ion was put for war d by
Bois-Raymond in 1868, whose concept was t hat a cell sur face could be well looked at as
t hough it wer e an elect r ode.
The pr incipal element s in biological cells is shown in Fig. 18.3. A Sect ion of a yeast
cell wit h it s membr ane is shown in Fig. 18.4.
Fi g. 18.3 : The scheme of an animal cell. Fi g. 18.4 : Elect r on micr ogr aph of a sect ion
r epr int ed fr om J . Kor yt a, Ions, Electrodes fr om a yeast cell. The out er envelope is t he
And Membranes Fig. 69. Copyr ight cell wall. The inner double line is t he cyt o-
J . Wiley & Sons, Lt d. 1991. Repr oduced plasmat ic membr ane. (Repr int ed fr om
wit h per mission of J . Wiley & Sons, Lt d.) J . Kor yt a, Ions, Electrodes and Membranes,
Fig. 70. Copyr ight J . Wiley & Sons, Lt d.
1991. Repr oduced wit h per mission of
J . Wiley & Sons, Lt d.)
Fr om t hese t wo figur es it is infer r ed t hat t he animal cells ar e r at her complex, each
one cont a ining t he her idit a r y ma t er ia l a nd in pa r t icula r t he ent it ies known a s
mit ochondr ia. It is infact t he ener gy pr oducing pr oper t ies of t hese ar e discussed in
for t hcoming sect ions.
Membr anes, t he subject of t his sect ion, can be r elat ively t hick (0.1mm) of made
chemically). Biological membr anes ar e ver y much t hinner (50100) of t he same
(35 nm) r ange as t hat of passive oxide. The figur e shows t he essent ial const it uent s of
t he biological membr anes. These ar e lipids and pr ot eins. In myet in membr ane t he lipid
cont ent is 80% while at t he ot her end t he r ange, in mit ochondr ia t her e is an inner
membr ane cont aining only about 20% lipid. Ther e ar e many kinds of lipids as well as
ver y many kinds of pr ot eins. In membr anes ar e usually phospholipids Fig 18.5. The
1 m
Bioelectrodics 259
nucleolus
nucleus
mitochondrium
endoplasmatic
reticulum
Golgi
complex
Cytoplasmic
membrane
Lysosome
approx. 10 m
Fig. 18.6: Pr epar at ion of a
bila yer lipid membr a ne.
(Repr int ed fr om J . Kor yt a,
I on s , E l ect r od es a n d
Mem br a n es , F i g. 84.
Copyr ight J . Wiley &
Sons Ltd. 1991. Reproduced
wit h permission of J . Wiley
& Sons, Lt d.)
IB
1
IN
IM
IC
P
IB
2
polar head
Hydrophobic end
Teflon septum
window
aqueous
solution
(a)
drop of lipid solution
BLM
(b)
(c)
Plateau-Gibbs boundary
H
2
COCR
O
||
H
2
COPOX
RCOCH
|
|
|
O
O
||
O
||
F i g. 18.5: Typical biological
membrane st ruct ures. A liquid-
mos a i c model i n t h e for m
pr oposed by A. Kor t ya wit h
differ ent t ypes of disposit ion of
membr a n e pr ot ei n ) (ph os -
pholipids ar e shown as dar k
circles wit h t wo wavy t ails); IB
1
,
int egr al, membr ane-br idging
pr ot ein, wit h a single poly-
pept ide span; IB
2
, t he sa me
wit h sever al spans; IN and IC,
int egr al noncyt oplasmic and
cyt opl a s mi c pr ot ei n s ; I M,
int egr al bur ied pr ot eins; P,
per ipher al pr ot ein. (Repr int ed
fr om J . Kor yt a, Ions, Electrodes
an d Mem br an es , Fi g. 81.
Copyr ight Lt d. 1991. Repr o-
duced wit h per mission of J .
Wiley & Sons, Lt d.)
Fig. 18.5(a ): A scheme of t he
bilayer lipid membr ane. The
black cir cles indicat e t he
polar heads (t he hydr ophilic
part ) consist ing of phosphoric
a cid, et ha nol a mine, a nd
a n logu e der iva t ives . Th e
wavy lines are t he long alkyl
chains of fat t y acids (t he
hydrophobic part ) (Reprint ed
from J . Koryt a, ions, Electro-
des and Membranes, above.
Copyright J . Wiley & Sons
Lt d. 1991.
st r uct ur e oft en cont ains an H at om and t his allows t he phosphor ic acid element t o
ionize. In t he membr ane st r uct ur e, t he alkyl gr oups R and R ar e dir ect ed inwar d while
t he popular gr oups ar e on t he sur face.
A scheme of bilayer and lipid membr ane. The black cir cles indicat e t he polar heads
(t he hydr ophilic par t ) consist ing of phosphor ic acid, et hanol amine; and analogue
der ivat ives. The wavy lines ar e t he long alkyl chains of fat t y acids (t he hydr ophoblic
par t ).
[Taken fr om J . Kor yt a, Ions Elect r odes and Membr anes.]
The most common model syst em t o act as a smiplified biological membr ane is t he
bilayer Lipid membr ane (BLM) which was fir st pr epar ed Mueller in 1962. It consist s
of t wo lipid molecules t ail t o t ail Fig. 18.6 wit h t he polar gr oups or ient ed t o face t he
solut ion. In t he basic BLM individual, compounds of a biological syst em can be built and
examined.
The BLMs, alt hough ver y t hin exhibit ver y high r esist ance, up t o 10
10
ohms.
Never t heless, some por es do develop in t hese membr anes and wat er , followed by ions,
ent er s t her e and r educes t he r esist ance. Applicat ion of a pot ent ial incr eases t he flow of
ions t hr ough t he por es and t he number of por es. This fur t her r educes t he r esist ance.
Fi g. 18.7 : Pr epar at ion of a bilayer lipid membr ane
[Taken fr om J . Kor yt a Ions, Elect r odes and Membr anes.
The met hod of measur ing a membr ane pot ent ial is simple. A calomel elect r ode is
placed in a solut ion (if t he solut ion cont ains Cl
) on eit her side of membr ane, which

usually occupies a hole about 1 mm in diamet er in a t eflon sheet . Since t he pot ent ial
of t he calomel elect r ode is accur at ely known and var ies accoding t o Ner nst pot ent ial
wit h logd
Cl
-, t he differ ence in pot ent ial ar ising fr om t he t wo differ ent Cl
concent r at ions
in each side of t he membr ane is easily known and can be subt r act ed fr om t he t ot al
pot ent ial differ ence r egist er ed bet ween t he t wo elect r odes t o give t he value due t o t he
membr ane. Most of t he membr ane pot ent ials r ecor ded in t he lit er at ur e lie wit hin values
of t ens t o hundr eds of milli volt s.
Simplistic Theory
The t heor y of an equilibr ium on one species bet ween each side of t he membr ane was
formulat ed by Donnan in 1925 unt il 1955, it reigned as t he t heory of membrane pot ent ials.
It s demise came when r adiot r acer measur ement s showed t hat all r elevant ions (e.g., K
+
,
Na
+
, and Cl
) per meat ed mor e t han a dozen act ual biological membr anes, alt hough each
ion had a char act er ist ic per meabilit y coefficient in each membr ane accor ding t o Hodg
kin and Keynes 1953.
Unt il 1950s Some bio-elect r ochemist s confident ly explained membr ane pot ent ials by
assuming t hat only one ion like K
+
in KCl per meat ed t he membr ane. If so, t hen

= + = + + In
i
ui nF * ic RT a nF (1)
Teflon septum
window
aqueous
solution
(a)
drop of lipid solution
BLM
(b)
(c)
Plateau-Gibbs boundary
Bioelectrodics 261
would be t he expr ession for elect r ochemical pot ent ial of t he per meable ion i, on one side,
, on t he ot her side , t he cor r esponding expr ession for elect r ochemical pot ent ial of t he
same ion, t her e would be
oj
i i
b F b R T l n nF

= + = + +
As long as equilibr ium can be assumed bet ween per meat ing ions, i on each side e.g,
on t he and t he side r espect ively
i
bi b

=
Hence
R i
i
RT
ln
F
...(2)
Being developed in par allel wit h t he r ise and fall of t he Donan equilibr ium t heor y
of membr ane pot ent ials was t he applicat ion of liquid funct ion. Pot ent ial t heor y t o
membr anes. This was pr oposed as far back as 1888 by gr eat Ner nst himself. The t heor y
gr ew by applicat ion of t he Ner nst -Planck equat ion t o t ake int o account t he dr iving
for ces due t o concent r at ion and pot ent ial gr adient s.
Modern Approaches to the Theory of Membrane Potentials
Accor ding t o (J ahn, 1962) t her e is found t o be a poor mat ch bet ween t heor y and
exper iment . Ionic concent r at ion differ ences alone, t hen, do not complet ely det er mine
membr ane pot ent ials in living syst ems.
Some membr a n e pot en t i a l s a r e
a ffect ed by l i gh t , j u s t a s i f t h e
membr anes wer e semi-conduct or s. This
is ent ir ely out side t he capabilit ies of
t heor ies t hat depend on t he int er play of
pot ent ial and concent r at ion gr adient s in
1949 Al ber t Szen t -Gyogyi ma de a
suggest ion t hat some biomat er ials might
be r egar ded as semiconduct or s. This was
cr it icized and anot her view was t hat
bioma t er ia ls could be t hought of a s
possible elect r onic conduct or s and hence
elect r odes. This was consist ent wit h t he
idea t hat t he fir st st ep in phot osynt hesis
is t he phot o-elect r ochemical decomposi-
t ion of wat er , and it would account in
pr inciple, for t he phot osensit ivit y of
membr anes.
In case Szent Gyor gyis concept is
a ccept ed t o int er pr et t he elect r onic
Fig. 18.8: Schemat ic diagram showing t he oxidat ion
and r educt ion r eact ions occur ing at a membr ane
solut ion int erface on sides 1 and 2 of t he membrane.
(Repr int ed fr om M.A. Habibi and OM. Bockr is,
J . Bi oel ect r i ci t y 2:66 (1984). Repr i n t ed by
per mission of Mar cel Dekker .)
E = E
a' 2 R3
e
B
B A
A
Membrane
E = E
AA R1
E
1
E
2
conduct ion of some biomat er ials, t he
idea t hat ar ose was t hat elect r onic
t r a n s fer a t t h e s ol i d/s ol u t i on
int er face could occur wit h t he solid
being a biomat er ial. J ahn in 1962
wa s t h e fi r s t t o come u p wi t h
di ffer en t t h eor y of membr a n e
pot ent ials. J ahns concept s pict ur ed
t he membr ane as a bioelect r ode,
wit h each side t he sit e 1 differ ing
(but coupled) r edox r eact ions, t he
membr ane it self act ing somewhat
like t he membr ane in a fuel cell Fig.
A mor e det ailed view, due t o Tien is
shown in Fig. 18.8.
The equat ions deduced for t he
t wo r eact ions making up a cor r osion
couple ar e specialized in t he sense
t hat t he cat hodic r eact ion is t aken
t o be hydr ogen evolut ion and t he
anodic one, met al dissolut ion. The
values being assumed t o be one half,
but one can dr op t hese assumpt ions
a nd a ssume t ha t t he membr a ne
pot en t i a l s i s s i mpl y t h a t of a
bioelect r ode.
Somewhat similar r easoning can
be applied t o t he comings and goings
of t he Na
+
, K
+
and Cl
ions which
(i n t h i s vi ew) det er mi n e t h e
pot ent ial of t he membr ane. Kor yt a
h a s for mu l a t ed t h i s t h eor y by
wr it ing elect r ode kinet ic equat ion
similar t o t hose t hat lie behind t he
But ler -Volmer equat ion. The movement of ions occur s acr oss t he membr ane of wor king
elect r ochemical cells and in t hese cases cer t ainly t he ions ar e dr iven by t wo int er facial
cooper at ing pr ocesses. Such movement s occur as a r esult of event s elsewher e. The
differ ences in concent r at ion in which t hey or iginat e ar e not t he causes of t he pot ent ials
wit h which t hey ar e associat ed. These causes ar e sur face elect r on-t r ansfer r eact ions
t hat occur at t he int er faces, i.e., at int er faces on eit her side of t he membr anes. Such
sit es of elect r on t r ansfer ar e pr obably at enzymes absor bed at t he membr ane sur faces.
Thus in t his view, t he act ual or igin of membr ane pot ent ials lies in t he fr ee-ener gy
changes in r edox r eact ions occur ing r espect ively, on each of t he t wo membr ane sur faces.
Fi g. 18.9 : Tr ansmembr ane elect r on movement and
r edox r ea ct ion s. Also sh own sch ema t ica lly a r e
elect r odes and cir cuit diagr am for cyclic volt ammet r y.
WE, wor king elect r ode; SCE, sa t ur a t ed ca lomel
elect r ode; AE, auxiliar y elect r ode. , and a r e
chemical and elect r ochemical pot ent ials, r espect ively.
Bulk concent r at ions of r educed (RED) and oxidized
(OX) species on eit her side of t he membr ane as
i n di ca t ed by s u bs cr i pt s 1 a n d 2; i n t er fa ce
concent r at ions ar e designat ed by a super scr ipt s
(Repr int ed fr om H.T. Tien, Aspects of Membrane
Chemistry, Kluwer Academic Publishers, 1991.)
Bioelectrodics 263
A
E
To
Instruments
To
Instruments
Outer
Aqueous
Solution (1)
We
Inner
Aqueous
Solution
(2)
(SCE) (SCE)
AE
(SCE)
1
,
2
,
2
[Red]
s
1
[Red]
s
2
[Red]
1
D [Red]
2
E
0
1 E
0
2
A
D [OX]
+
2
A [OX]
1
[OX]
s
2
Electron
Conducting
BLM
e
[OX]
s
1
E
0
a
E
a
a
E
i
a
1
,
s
1
2
,
s
2
Electrical Conduction in Biological Organisms
El e ct r on i c. The init ial r eact ion t o t he pr oposit ion t hat elect r onic cur r ent s flow in
biological or ganisms under st andably negat ive. In ear ly invest igat ions of t his subject , t he
common view seemed t o be just ified for pr ot eins t hat wer e cr yst allised out fr om t he
dissolved for m and t hor oughly dr ied show an ext r emely high r esist ivit y.
In 1960s, some evidence of a significant
elect r ica l conduct a nce in bioma t er ia ls wa s
available. Significant conduct ance was found
in cr ust aceans. Indir ect suppor t also came fr om
mecha nisms involving elect r on flow which
seemed necessar y t o explain phenomena in
phot osynt hesis, in enzyme r eact ivit y and in t he
ener gy pr oducing act ivit ies in mit ochondr ia.
Ros en ber g a n d P os t ow r ea l i zed t h a t
pr ot eins in t he body ar e far fr om dr y, and a
near er appr oximat ion t o t he in vitro sit uat ion
would be t o find out t he elect r onic conduct ivit y
of wet pr ot eins. However , t he difficult y t hat
a r ose wa s t ha t since pr ot ein is wet , t he
conduct ance measur ed may be par t ly ionic.
Rosenber g and Post ow managed t o separ at e
out t he ionic component of conduct ivit y. They
found t hat t he ener gy of act ivat ion for t he
elect r onic par t of t he conduct ance went linear ly
downwar d as t he wat er cont ent of t he pr ot ein
incr eased. It appear ed as t hough wat er , or it s
ionized const it uent s act ed like doping agent in
increasing t he elect rical conduct ance of int rinsic
semi-conduct or s. Thus an incr ease of ~10
8
times
in conduct ance can ar ise in t his way. Fig. 18.10.
However , in r espect t o t he mechanism for
t he r educt ion of O
2
in biosyst ems. Szent -Gyor gyi suggest ed t hat met hyl glyoxal, r at her
t han O
2
accept s elect r ons fr om enzyme
H C = O
|
C = O
|
CH
3
sur faces and t her eaft er r educes O
2
homogeneously. This kind of biochemical appr oach
t o cancer pr edat ed t he r ecognit ion of DNA, which r edir ect ed t he at t ent ion fr om
biochemist r y t o genet ics.
In t he account of elect r ical conduct ance in biological or ganisms, it is impor t ant t o
st r ess: t he usefulness of examining semiconduct ion by means of t he Hall effect . Thus,
Fig. 18.10 The log of cur r ent plot t ed
against 1/T(K) for a var iet y of biological
subst ances. The act ivat ion ener gies ar e
calculat ed fr om t he slopes of t he lines.
(Re p r i n t e d wi t h p e r mi s s i on fr om
B. Rosenber gh and E. Post ow, Ann.N.Y.
Acad. S ci. 158:61, 1969, p. 162, Fig. 1.)
10
4
10
6
10
8
10
10
10
12
10
14
2.7 3.0 3.5 4.0
1000
TK
Fully Hydrated
Hemoglobin
1.2 eV
Fully Hydrated
Cholesterol
Palmitate 0.9 eV Dry
Synthetic
Melanin
1.5 eV
Partially Hydrated
Synthetic Melanin
1.2 eV
Dry Sheep Root
2.3 eV
All Trans -
Carotene
1.5 eV
Retinal- Aniline
Protonated
Schiffs Base
Complex 2.1 eV
Dry Hemoglobin
2.4 eV
Dry Cholesterol
Palmitate 3.6 eV
Bioelectrodics 265
if an elect r ic cur r ent flows t hr ough a body in t he x dir ect ion, and a magnet ic field is
applied nor mal t o t he body in t he z dir ect ion, an ext r a elect r ic field is caused t o exist
in t he y dir ect ion. Fr om measur ement s made, t hen, on t he effect of applying t his magnet ic
field t o a cur r ent flowing t hr ough a body, it is possible t o det er mine t he char ge car r ier
concent r at ion in t he body. Mor eover , t he sign of t he char ge car r ier s, whet her elect r ons
(negat ive) or holes, (posit ive) can be det er mined. Knowing t he conduct ance, t he applied
field st r engt h and t he concent r at ion and sign of t he char ge car r ier s, it is possible t o
ca lcula t e t heir mobilit y va lues r a nge bet ween 0.01 cm
2
/V
s
t o 10 cm
2
/V
s
at r oom
t emper at ur e. The car r ier concent r at ion var ies over a r ange of 10
8
10
18
sec. The biological
mat erials measured (a comprehensive dat a set was gat hered for t he first t ime by Gut mann
Lyons and Keyzer in 1983) show a wide var iet y of behaviour s as t o conduct ance in which
eit her elect r ons or holes pr edominat e.
How does elect r onic conduct ance occur in biological mat er ials in t his r espect , t he
basic mechanism of conduct ance in an impur it y-cont aining pr ot ein is similar t o t hat of
a doped semiconduct or such as silicon. However , complicat ions occur in r espect t o t he
dist ance bet ween sit es fr om which elect r ons or iginat e and t hose in which t hey may be
r eceived. Basically, elect r ons t end t o t r ansfer t hr ough ener gy bar r ier s wit hin t he st r uct ur e
by quant um mechanism t unneling. However , a r ough r ule t he maximum jump lengt h for
t he t unneling elect r on is about 20. If t her e is no r eceiver st at e for an elect r ons wit hin
t hat dist ance, t he pr obabilit y of a successful t unnel t r ansfer will be so slow t hat t he
dominant mechanisms of t r anspor t may change fr om t hat of a t unneling t o t hat of
elect r on hopping bet ween neighbor ing at oms. Syst ems t hat allow t unneling will gener ally
show a much higher value of char ge-car r ier mobilit y t han t hose in which at om-t o-at om
elect r on hopping is t he pr efer r ed mode. Anot her fact or is cr yst allogr aphic and concer ns
t he shape and size of or der ed ar eas in t he pr ot ein in which t her e ar e r espect ive gr oups,
giving r ise t o band for mat ion, which t hen enhances t he concent r at ion of elect r ons able
t o t r avel under a field gr adient .
ELECTRICAL CONDUCTION IN BIOLOGICAL ORGANISMS PROTONIC
Ther e ar e possibilit ies in biological st r uct ur es in which t he char ge car r ier is neit her an
elect r on nor a hole, but a pr ot on as per Nagle and Mor owiz in 1978 and Pet hing in 1998.
Because quant um mechanical t unneling is a fr equent mode of t r anspor t wit h elect r ons,
it may be asked if it is likely t hat pr ot eins could also t unnel. Thus, t he Gamow fact or
for t he pr obabilit y of t unneling is given by t he equat ion.
T
4
2
e
l
P mE
...(3)
wher e m is t he mass t unneling par t icle, l is t he t r ansfer dist ance, and E is t he ener gy
of t he ent it y t unneling. The pr ot on is ~ 1840 t imes heavier t han t he elect r on. Assuming
t hat t he dist ance of t r ansfer for t he pr ot on is about one t ent h t hat for t he elect r on, and
t he E value is t he same, t he t unneling pr obabilit y for individual pr ot eins will be about
e
4
t hat for elect r ons. However , in pr ot eins even if t hey ar e wet , so t hat t he act ivat ion
ener gy for elect r ical conduct ance is only ~0.5eV, t he pr obabilit y of act ivat ing an elect r on
t o t he conduct ance band will be as lit t le as about 10
7
at r oom t emper at ur e. Par t icular ly,
it pr ot eins, it may i.e., t hat t he pr ot on concent r at ion exceeds t hat of conduct ance-band
elect r ons so t hat conduct ance via pr ot on t unneling mechanism becomes likely. Det ailed
invest igat ion suggest s t hat t he r at e det er imining st ep is usually some comfor mal char ge
r at her t han t he t unneling st ep. This would be similar t o t he sit uat ion of pr ot ons
conduct ing in aqueous solut ions, wher e t he r ot at ion of a wat er molecule under t he
field of t he appr oaching pr ot on, is r at e det er mining, not t he r at e of pr ot on t unneling.
Similar confor mat ional changes ar e necessar y in a pr ot ein st r uct ur e, in which elect r on
a nd pr ot on t r a nsfer a r e t he
impor t ant st eps in elect r ical
conduct ance. A possible pr ot on
conduct ing pat hway wit hin a
cyt opl a s mi c membr a n e i s
shown in t he Fig. 18.11.
Speci fi c con du ct a n ce i n
biological or ganisms cover s t he
enor mous r ange of 10
15
. It is
possible t o under st and why t he
r ange is so lar ge. The specific
conduct ance will depend on t he
pr ot ei n s s t r u ct u r e. I s i t
suit able for band for mat ion as
it seems t o be in many pr ot eins.
However , it will also depend on t he degr ee and t ype of doping, not t he int ent ional
addit ion of t r ace addit ives as in t he or ganic semiconduct or s, but t he pr esence of ot her
ent it ies (wat er , ext r a or ganic subst ances, fr agment s et c.) in t he st r uct ur e. Finally, pr ot ons
may add t o t he t r anspor t because alt hough t he pr obabilit y of t unneling of t he individual
pr ot on is much smaller t han t hat of an elect r on, t he number of available.
THE ELECTROCHEMICAL MECHANISMS OF THE NERVOUS SYSTEM
AN UNFINISHED SECTION
Elect r ical act ivit ies ar e an int egr at ed par t of t he act ivit y of t he br ain, but t her e t he
amplit ude of t he encephalogr aphic oscillat ions is in t he micr ovolt r egion, wher eas t ens
of millivolt s ar e needed t o t r igger passage of a pulse t hr ough t he ner vous syst em. Ber n-
st ein, in 1962 fir st focused at t ent ion on t he alleged impor t ance of t he r at ios of t he Na+
and K+ concent r at ions of t he int r a and ext r acellular fluids of t he ner ve axon and r elat ed
t hem via a Ner nst t ype equat ion t o t he elect r ical pot ent ial measur ed acr oss it . Thus t he
t heor et ical appr oach t o t he passage of elect r icit y t hr ough ner ves become elect r ochemical.
Hodgkin and Huxley, Nobel pr ize winner s published seminal exper iment s on t he
cur r ent pot ent ial r elat ion acr oss t he membr ane of t he ner ve sheat h dur ing 1952. At t ached
t o t he or iginal and elegant expeir ment s t hey descr ibed was a phenomenological t heor y
of t he sur pr ising r esult s wer e r epor t ed t he r esult infer r ed t he int er pr et at ion of t he
var iat ion of pot ent ial acr oss t he membr ane cont aining t he int r acellular fluid when t he
Fig. 18.11 : A ser ies of H bonds (...) ser ving as a pr ot on-
conduct ing pat hway wit hin a cyt oplasmic or int r amem-
brane prot ein. (Reprint ed wit h permission from J .F. Nagle
and H.J . Mor owit z, proc. Nat. Acad. S ci. U.S .A. 78, 298,
1978, p. 299, Fig.3.)
O=C
|
C
N
H
H
R
C
|
OH
O
H
C
R
O
H
O
C
|
R O
H
O
C
H
O
|
C
R
H
H
|
N
N
H
H
C
|
N
H C
R
Di recti on of proton f l ow
passage of cur r ent t hr ough a ner ve was t r igger ed and t his confir med as t o what has
been found exper iment ally and was expr essed impr essively mat hemat ically also.
The Hodgkin-Huxley (H-H) t heor y of t he ner vous syst em was an example of bio-
elet r ochemist r y gliller ing wit h t he vir t ue, a wor k t r uly t o be compar ed in st at us wit h
t he best known piece of elect r ochemist r y t he Debye-Hickel t heor y of ionic solut ions. It
appear ed lat er t hat t he t heor y was unt est able. The elect r ophysiologist s st ill use t he H-
H t heor y.
ENZYMES AS ELECTRODES
Enzymes:
Enzymes ar e cat alyst s for r eact ions in t he body in fact t hey ser ve t o make t he
nat ur e of biochemical act ivit ies differ ent and fast er . Enzymes ar e pr ot eins and t heir
molecular weight var ies gr eat ly, fr om 10
3
t o 10
6
: Apar t fr om t heir acceler at ion of a
r eact ion br ought about by enzymes, t her e is t heir ast ounding specificit y: They ar e t ur ned
on and of by t iny changes in t he st r uct ur e of t he ent it ies t aking par t in t he bior eact ion
being cat alysed. Apar t fr om t his t her e ar e coenzymes, by which is meant anot her
subst ance, most ly a vit amins, t hat has t o be pr esent t o make t he enzyme wor k. Enzyme
cat alyst s have yet anot her , puzzling feat ur e, r eact ions cat alyzed by t hem do indeed
incr ease in r at e, wit h t emper at ur e. However , pr ot eins t end t o unfold at cer t ain
t emper at ur e known as denat ur at ion, when t his occur s, t he enzyme loses it s act ivit y.
They st ill r et ain t heir ext r aor dinar y act ivit y and specificit y for r eact ion wit h a subst ance
in solut ion t hat it is meant t o cat alyze.
Electrodes Carrying Enzymes:
The 1980s wer e spent in discover ing what not t o do if one wished t o car r y enzymes
in elect r ode and use t heir power s as elect r ocat alyst s.
1. Single elect r on t unneling jumps gr eat er t han about 20 do not happen, alt hough
much can be alone (Heller and Delgani, 1987) t o facilit at e successive jumps.
2. Even par t ial decomposit ion of an enzyme upon adsor pt ion must be pr event ed
because t he fr agment s pr oduced fr om a passive layer on t he elect r ode and in
act ivat e any enzymat ic act ivit y t her e.
3. Far -r eaching decomposit ion of t he enzyme upon adsor pt ion must obviously be
avoided, for it occur s, it dest r oys t he enzymes cat alyt ic power .
Ther e ar e only t wo ways t o obt ain a successful, adsor bed enzyme act ing as an
elect r ocat alyst (Rusling 1997).
1. The enzyme it self and t he elect r ode syst em upon which it is t o adsor b must be
highly pur ified.
2. The most impor t ant point (much applied by Eddowes and Hill at t he Univer sit y
of Oxfor d) is t o have a suit able pr omot or s as t he elect r ode. It is t his pr elayer
t hat encour ages complicat ed lar ge bimolecules t o adsor b and st ill r et ain some of
t he pr oper t ies as cat alysis t hat t hey show in solut ion.
It has been known t hat one way t o make model membr anes is t o use bilayer s of
phospholipids placed t ail t o t ail and inser t pr ot eins is t o t hem. Fig: 18.12.
Bioelectrodics 267
Fig. 18.14 : Cyclic volt mmograms
at 100mVs
-1
inpH 5.5 buffer. a, pH
5. 5 bu ffer on ba r e pyr ol yt i c
gr a phit e (PG); b, 0.5 mMMB
(hor se, fr om Sigma) in buffer on
bare PG; c, MB-DDAB film on PG
in buffer , no MB in solut ion.
(r epr int ed fr om J .F. Rusling,
Elect rochemical Enzyme Cat aly-
sis, Interface, 6(4): 26-312, Fig. 2
1997. Reproduced wit h permission
from t he Elect rochemical Societ y,
Inc.)
10
5
0
5
10
0.40 0.20 0.00 0.20 0.40
E, V vs SCE
C
u
r
r
e
n
t
,
A
Fe(III) Fe(II)
c b a
Fe(II) Fe(III)
Bioelectrodics 269
act ive in elect ron exchanges in chlorophyll and bact eria,
and r esult ing in t he pr oduct ion of H.
Why is it t hat t he pr e adsor bed sur fact ant layer on
t he elect r ode (e.g., t he DDAB), has such a helpful effect
in facilit at ing t he r eact ions of enzyme elect r ode? For
one t hing, t he sur fact ant is a good, adsor ber on t he
met al or gr aphit e elect r ode. Cor r espondingly, if, upon
adsor pt ion, t her e is some par t ial dissociat ion of t he
complex enzyme, t he pr e adsor bed sur fact ant makes it
difficult for such fr agment s t o build up passive layer s
on t he elect r ode layer s t hat could diminish elect r on
t r ansfer .
Anot her fact or t hat has t o be cont r olled, in case
one wishes t o obt ain t he maximum r eact ion r at e, is
pH. At a pH <4.6, MB is par t ly unfolded and can be
r educed dir ect ly. However , at a pH > 9, t he r educt ion
involves pr ot onat ion. The r at es of t hese r eact ions ar e
ver y high, a r at e const ant of 8000m-1cc
-1
, equivalent
t o an i
0
of 10
5
A cm
2
if t he r eact ant concent r at ion is
10
3
M.
The Electrochemical Enzyme-Catalyzed
Oxidation of Styrene
St yr ene is a phenyl et hylene,
CC
6
H
11
Ch = CH
2
, a compound impor t ant in a number of polymer izat ion. In t he
body t he cyt ochr ome P
450
enzyme in t he liver can for m st yr ene oxide, which t hen may
r eact wit h or ganisms DNA, i.e., become a car cinogen. The use of MB in lipid films t o
oxidize st yr ene has been achieved by Rust ing et .al. (1997) in a ser ies of r eact ions t hat
can be wr it t en as follows:
X-MB Fe(III) + e

X-MB Fe
(II)
(at elect r ode)
X-MB Fe(II) + O
2
X MB Fe(II) O
2
X-MB Fe(II) O
2
+ 2e
+ 2H
+
X MB Fe(II) + H
2
O
2
(at elect r ode)
H
2
O
2
+ X MB Fe(III) X MB Fe(IV) = O + H
2
O
2X MB Fe(IV) = O + H
2
O
2
2HX MB Fe(IV) = O + O
2
St yr ene + X MB Fe(IV) = O X MB Fe(III) + st yr ene oxide
It can r esonably be concluded t hat t he inclusion of enzyme pr ot eins in SAMs pr ovokes
fast elect r ode r eact ions.
APPENDIX
Ta b le 1 : Va lu e s of I mp or t a n t Con st a n t s
(N, F a n d R for t h e ch e mi ca l mole )
Avogadr os Number
N = (6.023 0 0.000 2) 10
23
mole
1
Char ge on t he Elect r on
e = (4.802 94 0.000 08) 10
10
e.s.u.
= (1.602 09 0.000 03) 10
20
e.m.u.
= (1.602 09 0.0003 03) 10
19
coulomb
Far aday Const ant
F = (9,649.3 0.2) e.m.u. equivalent
1
= (96,493 2) coulomb equivalent
1
Gas Const ant
R = (8.3147 0.000 05) joule deg.
1
mole
1
= (1.987 2 0.000 01) cal. deg.
1
mole
1
= (0.082 057 0.000 000 5) l.at m.deg.
1
mole
1
Bolt zmanns Const ant
k = (1.380 49 0.000 05) 10
16
er g deg.
1
Ice Point
T
0
C = (273.150 0 0.000 2) K
Velocit y of Light
C = (2.997 928 0.000 004) 10
10
cm sec
1
Plancks Const ant
h = (6.6254 0.000 2) 10
27
er g sec
St andar d At mospher e
1 at m. = 1,013,250 dyne cm
2
St andar d Gr avit at ional Acceler at ion
g
0
= 980.665 cm sec
1
Defined Calor ie
1 cal. = 4.1840 joules
Relat ion bet ween Chemical and Physical Mole
1 phys. mole = 1.000 275 chem. mole
Relat ion bet ween Lit r e and Cubic Cent imet r e
11. = (1,000.028 0.004) cm
3
TABLE 2
Elect r on Affin it ies of t h e At oms
The elect r on affinit y of an at om or r adical is t he ener gy absor bed in conver t ing t he
par t icular ion shown int o t he neut r al at om or r adical. Values under I ar e t hose given
by Fr it char d (Chem. Rev. 52 (1953) 529); values under II ar e t hose given in Landolt -
Br nst ein, I Band, 1 Teil, p. 213.
Ion I II II Ion I II II
kcal/ mole kcal/ mole eV kcal/ mole kcal/ mole eV
H
17.22 16.5 0.72 S

2
80 90 4
Li
12.5 10 0.5 Se
> 40?
Na
28 Se
2
97
K
16 Te
50?
Hg
35.4
C
48 20 28 1.2 F
83.5 2 94 4.1
C
4
708 Cl
88.2 1.5 87 3.78

N
16 Br
81.6 1.5 81 3.52

N
3
> 47 ?
74.6 1.5 72 3.12

Bi
> 17 ? CN
70 3
O
53.8 0.8 53.5 2.34 OH 45 2

O
2
210 150 6.5 HS
60 2.5
S
> 24 60 2.5
TABLE 3
Th e Wor k of Ext r a ct ion of a n Elect r on fr om va r iou s Met a ls in Elect r on Volt s
Ag 4.70 Cu 4.48 Nb 3.99 Si 3.59
Al 4.20 Fe 4.63 Nd 3.3 Sm 3.2
As 4.79 Ga 4.16 Ni 4.91 Sn 4.39
Au 4.71 Ge 4.62 Os 4.55 Sr 2.74
B 4.6 Hf 3.53 Pb 4.04 Ta 4.13
Ba 2.52 Hg 4.53 Pd 4.98 Te 4.73
Be 3.92 Ir 4.57 Pr 2.7 Th 3.47
Bi 4.34 K 2.25 Pt 5.36 Ti 4.16
C 4.36 La 3.3 Rb 2.13 Tl 4.05
Ca 3.20 Li 2.46 Re 4.97 U 3.45
Cd 4.04 Mg 3.70 Rh 4.65 V 4.11
Ce 2.88 Mn 3.95 Ru 4.52 W 4.53
Co 4.25 Mo 4.24 Sb 4.56 Zn 4.27
Cr 4.45 Na 2.28 Se 4.87 Zr 3.93
Cs 1.94
Appendix 271
TABLE 4
Dielect r ic Con st a n t of Aqu eou s Solu t ion s a t 25C
= 78.54 2Ac (va l i d c = 0.5 2.0)
S olute A S olute A
HCl 10 NaI 7.5
LiCl 7 KI 8
NaCl 5.5 MgCl
2
15
KCl 5 BaCl
2
14
RbCl 5 LaCl
3
22
NaF 6 NaOH 10.5
KF 6.5 Na
2
SO
4
11
TABLE 5
Dielect r ic Con st a n t s ( ) of some In or ga n ic Solven t s
Repr oduced fr om Har ned and Owen, Physical Chemistry of Electrolyte S olutions,
Fir st Edit ion, by cour t esy of Reinhold Book Division
S olvent tC S olvent tC
AsCl
3
12.8 20 NH
3
16.9 25
D
2
O 77.94 25 N
2
H
2
51.7 25
HCN 106.8 25 N
2
O
4
2.4 18
HF 83.6 25 NOCl 18.2 12
H
2
SO
4
101 25 POCl
3
13.3 22
HgBr
2
9.8 240 SO
2
14.1 20
I
2
11.1 118 SOCl
2
09.25 20
IF
5
36.2 25 SO
2
Cl
2
09.2 20
SeOCl
2
46.2 20
TABLE 6
Dielect r ic Con st a n t s of Mixt u r es of Wa t er a n d Or ga n ic Solven t s a t 25C
Non-aqueous Weight % of Non-aqueous Component
Component 10 20 30 40 50 60 70 80 90 100
CH
3
CH
2
OH 72.8 67.0 61.1 55.0 49.0 43.4 38.0 32.8 28.1 24.3
CH
3
CH
2
CH
2
OH 71.8 64.9 57.7 50.3 43.0 36.4 30.7 26.1 22.7 20.1
(CH
3
)
2
CHOH 71.4 64.1 56.9 49.7 42.5 35.3 28.7 23.7 20.3 18.0
(CH
3
)
3
COH 70.0 61.3 52.6 43.9 35.4 27.9 21.4 16.5 12.4 9.9
CH
2
OH. CH
2
OH 75.6 72.8 69.8 66.8 63.2 59.4 54.7 49.3 43.7 37.7
TABLE 7
P ola r ogr a ph ic Ha lf-Wa ve P ot en t ia ls (in Volt s vs. t h e n or ma l
Ca lomel Elect r ode) in Aqu eou s Solu t ion
Ion N A B
Li
+
2.31 2.31
Ca
2+
2.23 2.23
K
+
2.17 2.17
Na
+
2.15 2.15
Sr
2+
2.13 2.13
Cs
+
2.09 2.09
Rb
+
2.07 2.07
NH
+
4
2.08 2.15
b
2.29
NH
3
CH
+
3
2.8
a
NH
2
(CH
3
)
+
2
2.09
a
NH(CH
3
)
3
+
2.27
N(CH
3
)
+
4
2.7
N(C
2
H
5
)
4
+
2.71
N(C
3
H
7
)
4
+
2.56
N(C
4
H
9
)
4
+
2.61
Rar e Ear t h Met als 1.9 t o 2.0
Ba
2+
1.90 1.94 1.96
Ra
2+
1.89 1.89
Sc
3+
1.84
Zr
4+
1.7
TABLE 8
Anodic Depolar izat ion Pot ent ials
Process Solution E
1/ 2
+ Hg Cl HGCl + 0.21
+
3 3
Hg N HgN + 0.21
+ Hg CNS HgCNS + 0.14
+ Hg Br HgBr + 0.10
+ Hg 2OH HgO Anion concent r at ion + 0.04

Appendix 273
Process Solution E
1/ 2
+
2
3 3 2
Hg 2SO Hg(SO ) = 0.001 M 0.05
+ Hg HgI 0.07

+
2 2
2 3 2 3 2
Hg 2S O Hg(S O ) 0.18
+
2
Hg 2CN Hg(CN) 0.4
+
2
Hg S HgS 0.6
II III
Fe Fe 0.1 N KHF
2
+ 0.08
II III
Fe Fe C 0.38
II III
Mn Mn 2 N KOH, t ar t r at e 0.40
I II
Re Re 1 N HCiO
4
0.54
II III
Re Re 1 N HCiO
4
0.42
III V
Re Re 1 N HCiO
4
0.26
V VII
Re Re 1 N HCiO
4
0.0
II III
Cr Cr 0.1 N Na
2
SO
4
0.62
II IV
Sn Sn HCl 0.06
II IV
Sn Sn t ar t r at e pH = 2.3 0.18
II IV
Sn Sn t ar t r at e pH =7 0.48
II IV
Sn Sn t ar t r at e pH =13 0.75
II IV
Sn Sn 1 N KOH 0.77
II IV
Sn Sn F 0.24
III V
Sb Sb 0.5 N KOH 0.34
III V
As As 0.5 N KOH 0.25
III IV
Ti Ti HCl 0.18
IV V
V V pH = 6.8 + 0.07
IV V
V V C 0.36
IV V
V V 1 N KOH 0.46
TABLE 9
Inor ganic Oxidat ion Reduct ion Pot ent ials
Process Solution E
1/ 2
Cu
I
Cu
II
0.1 N Na
2
SO
4
0.06
Cu
I
Cu
II
C 0.25
Process S olution E
1/ 2
Cu
I
Cu
II
Cit r at e buffer pH = 7.0 0.21
Cu
II
Cu
III
Sat ur at ed CaCl
2
0.55
Cu
II
Cu
III
D 1.42
Mn
II
Mn
III
Tr iet hanolamine, 0.5 N NaOH 0.49
Fe
II
Fe
III
1 N Sodium oxalat e 0.30
Fe
II
Fe
III
Fe
II
Fe
III
Fe
II
Fe
III
Tar t r at e buffer pH = 10.0 0.9
Fe
II
Fe
III
1 N KOH 0.9
Ti
III
Tii
IV
Sat ur at ed CaCl
2
0.15
Ti
III
Tii
IV
0.1 N KCNS 0.49
Ti
III
Tii
IV
Cit r ic or t ar t ar ic acid 0.48
V
II
V
III
1 N H
2
SO
4
0.55
V
II
V
III
1 N oxalat e, pH = 4.5 1.16
U
III
U
IV
1 N HCl 0.93
Np
III
Np
IV
1 N HCl 0.10
Pu
III
Pu
IV
1 N HCl
Z
+ 0.65
TABLE 10
Elect r ode Pot ent ials and Elect r ical Conduct ivit ies
Electrode Electrode reaction Volts
Acid Solut ion
Li/Li
+
Li = Li
+
+ e
+ 3.045
K/K
+
K = K
+
+ e
+ 2.925
Ba/Ba
++
Ba = Ba
++
+ 2e
+ 2.906
Ca/Ca
++
Ca = Ca
++
+ 2e
+ 2.866
Na/Na
++
Na = Na
+
+ e
+ 2.7142
Mg/Mg
++
Mg = Mg
++
+ 2e
+ 2.363
Al/Al
3+
Al = Al
3+
+ 3e
+ 1.662
Mn/Mn
++
Mn = Mn
++
+ 2e
+ 1.180
Appendix 275
Electrode Electrode reaction Volts
Zn/Zn
++
Zn = Zn
++
+ 2e
+ 0.762 8
Cr /Cr
3+
Cr = Cr
3+
+ 3e
+ 0.744
Fe/Fe
++
Fe = Fe
++
+ 2e
+ 0.440 2
Cd/Cd
++
Cd = Cd
++
+ 2e
+ 0.440 9
Pb/PbSO
4
/SO
4
Pb + SO
4
= PbSO
4
+ 2e
+ 0.358 8
Pb/Pb
++
Pb = Pb
++
+ 2e
+ 0.126
Pt /H
2
/H
+
H
2
= 2H
+
+ 2e
0.000 0
Ag/AgBr /Br
Ag + Br
= AgBr + e
0.071 3
Cu/CuCl/Cl Cu + Cl
= CuCl + e
0.137
Pt /Cu
+
, Cu
++
Cu
+
+ Cu
++
+ e
0.153
Ag/AgCl/Cl
Ag + Br
= AgBr + e
0.222 5
Pt /Hg/Hg
2
Cl
2
/Cl
2Cl
2Hg = Hg
2
Cl
2
+ 2e
0.267 6
Cu/Cu
++
Cu = Cu
++
+ 2e
0.337
Pt /I
2
/I
31 = I
3
+ 2e
0.536
Pt /Fe
++
, Fe
3+
Fe
++
= Fe
3+
+ e
0.771
Ag/Ag
+
Ag = Ag
+
+ e
0.799 1
Au/AuCl
4
, Cl
Au + 4Cl
= AuCl
4
+ 3e
1.00
Pt /Cl
2
/Cl
2Cl
= Cl
2
+ 2e
1.359 5
Pt /Mn
++
, MnO
4
Mn
++
+ 4H
2
O = MnO
4
8H
+
+ 5e
1.51
Pt /F
2
/F
2F
= F
2
(g) + 2e
2.87
TABLE 11
Ion ic P r oper t ies of Wat er
Temperat ure C 0 10 20 25 30 50 100
Specific conduct ivit y, 1.2 2.3 4.2 5.5 7.0 17
ohm
1
cm
1
10
8
Ionic pr oduct 1.14 2.92 6.81 10.08 14.7 56 513
K
W
10
15
TABLE 12
Ion isa t ion Con st a n t s of Acids (a t 25C)
Acid log K Acid log K
Acet ic 4.76 Nit r ous 4.47
Benzoic 4.20 Oxalic K
1
1.19
Bor ic 9.24 K
2
4.21
Br omacet ic 2.87 Phenol 9.89
n-But yric 4.82 Phosphoric K
1
2.12
Car bonic K
1
6.37 K
2
7.21
K
2
10.25 K
3
12.32
Chloroacet ic 2.86 Phosphorus K
1
1.80
Chromic 6.49 K
2
6.15
Cinnamic (cis) 3.88 Phenolpht halein 9.70
Cinnamic (trans) 4.43 o-Pht halic K
1
2.89
Cit r ic K
1
3.06 K
2
5.41
K
2
4.74 Picr ic 0.38
K
3
5.40 Pr opionic 4.87
Dichlor oacet ic 1.30 Salicylic 2.97
For mic 3.75 Silicic C
a
9.7
Fumaric K
1
3.03 Succinic K
1
4.19
K
2
4.47 K
2
5.57
Glut ar ic 4.34 Sulfanilic 3.19
Glycine 9.78 Sulphur ic K
1
0.40
Hydr ocyanic 9.14 K
1
1.92
Hydrofluoric 3.14 Sulphurous K
1
1.76
Hydr osulphur ic K
1
7.24 K
2
7.20
(H
2
S)
K
2
14.92 Tart aric K
1
3.02
Maleic K
1
2.00 K
2
4.54
K
2
6.26 Trichloroacet ic 0.89
Malonic K
1
2.85 Ur ic 3.89
K
2
6.10
TABLE 13
Bu ffer Mixt u r es
Buffer Compositions pH
(After Clark and Lubs) (20C)
4.85 ml 0.2 N HCl + 25 ml 0.2 KCl dilut ed t o 100 ml 1.0
5.3 ml 0.2 N HCl + 25 Ml 0.2 KCl dilut ed t o 100 ml 2.0
Appendix 277
Buffer Compositions pH
(After Clark and Lubs) (20C)
46.70 ml 0.1 N HCl + 50 ml 0.1M KHC
8
H
4
O
4
dilut ed t o 100 ml 2.2
32.95 ml 0.1 N HCl + 50 ml 0.1M KHC
8
H
4
O
4
20.32 ml 0.1 N HCl + 50 ml 0.1M KHC
8
O
4
9.90 ml 0.1 N HCl + 50 ml 0.1M KHC
8
H
4
O
4
10.40 ml 0.1 N NaOH + 50 ml 0.1M KHC
8
H
4
O
4
22.15 ml 0.1 N NaOH + 50 ml 0.1M KHC
8
H
4
O
4
6.95 ml 0.1 N NaOH + 50 ml 0.1M KHC
8
H
4
O
4
43.00 ml 0.1 N NaOH + 50 ml 0.1M KHC
8
H
4
O
4
5.70 ml 0.1 N NaOH + 50 ml 0.1M KH
2
PO
4
17.80 ml 0.1 N NaOH + 50 ml 0.1M KH
2
PO
4
39.50 ml 0.1 N NaOH + 50 ml 0.1M KH
2
PO
4
45.20 ml 0.1 N NaOH + 50 ml 0.1M KH
2
PO
4
2.61 ml 0.1 N NaOH + 50 ml 0.1M H
3
BO
3
8.50 ml 0.1 N NaOH + 50 ml 0.1M H
3
BO
3
21.30 ml 0.1 N NaOH + 50 ml 0.1M H
3
BO
3
36.85 ml 0.1 N NaOH + 50 ml 0.1M H
3
BO
3
43.90 ml 0.1 N NaOH + 50 ml 0.1M H
3
BO
3
dilut ed t o 100 ml 100
QUESTIONS
Chapter 1
1. Descr ibe Polar ogr aphy giving applicat ions.
2. What is a Polar ogr aphic cell?
3. Descr ibe t he exper iment al set up of Polar ogr aphic cir cuit .
4. Descr ibe t he Half-wave pot ent ial and it s significance.
5. Descr ibe ionic st r engt h and also give t he influence of ionic st r engt h on half-
wave pot ent ials.
6. What ar e t he fact or s which affect t he half-wave pot ent ials?
Chapter 2
1. Descr ibe Dr opping Mer cur y Elect r ode (D.M.E.).
2. What ar e t he advant ages of D.M.E.?
3. What par t icular cell is used in Polar ogr aphy? What ar e it s advant ages?
4. Descr ibe t he var ious elect r odes giving t heir uses.
(a) Hanging Mer cur y Dr op Elect r odes.
(b) Car bon Elect r odes.
(c) Car bon Past e Elect r odes.
(d) Glassy Car bon Elect r odes.
(e) Mer cur y Pool Elect r ode.
(f) Calomel cell.
5. Which r efer ence elect r odes most ly used in Polar ogr aphy? Why?
6. How would you dist inguish bet ween wor king elect r ode and a r efer ence elect r ode?
Chapter 3
1. Descr ibe t he Polar ogr aphic cir cuit .
2. What is t he significance of diffusion in classical Polar ogr aphy?
3. What solvent s ar e most ly used in Polar ogr aphy?
4. Why suppor t ing elect r olyt es ar e used in Polar ogr aphy?
5. What is Polar ogr aphic maxima? What var ious t ypes of maxima ar e being obser ved
in Polar ogr aphy?
6. Innumer at e var ious non-aqueous solvent s.
7. Which ar e useful in Polar ogr aphy?
Chapter 4
1. Descr ibe t he Ilkovic equat ion? What ar e it s consequences?
2. Descr ibe t he cat hodic and anodic waves.
3. What ar e r ever sible and ir r ever sible elect r ode pr ocesses?
4. What is t he significance of r ever sible polar ogr aphic wave?
5. Descr ibe t he coupled chemical r eact ions and chemical r ever sibilit y.
Chapter 5
1. What ar e t he var ious cur r ent s t hat have some significance in Polar ogr aphy?
2. Descr ibe t he diffusion cur r ent and it s significance in Polar ogr aphy.
3. What ar e diffusion-cont r olled cur r ent s?
4. Descr ibe t he diffusion coefficient and it s significance.
5. What ar e t he var ious fact or s t hat affect t he diffusion cur r ent ?
Chapter 6
1. What is t he Polar izat ion of t he D.M.E.? Give an account of t he depolar izat ion
pr ocess.
2. What is hydr ogen over volt age and give an account of t he r educt ion of hydr ogen
ions?
3. Descr ibe double layer . How double layer affect s t he r educt ion pr ocess?
4. Give a br ief account of t he r educt ion of cat ion giving t wo examples.
Chapter 7
1. Descr ibe t he t heor y of amper omet r y.
2. Descr ibe t he t ypes of amper omet r ic t it r at ions.
3. What ar e r edox t it r at ions?
4. What ar e complexomet r ic and chelomet r ic t it r at ions?
5. Give an account of amper omet r ic t it r at ions wit h t wo polar ized elect r odes.
6. Descr ibe t he exper iment al set up of amper omet r ic t it r at ions.
7. What is chr onoamper omet r y?
Chapter 8
1. How met al complexes ar e det er mined by Polar ogr aphic met hod?
2. What is t he significance of r ever sible, diffusion-cont r olled syst em in met al
complex?
3. How t he for mulae and st abilit y const ant s of met al complexes ar e det er mined by
polar ogr aphy?
4. What met hods ar e employed in st udying mixed ligand complexes?
5. How t he co-or dinat ion number of met al complex could be det er mined?
Chapter 9
1. Which bond t ypes ar e r educible at D.M.E.?
2. Which funct ional gr oups ar e r educible at D.M.E.?
3. Can Polar ogr aphy be used t o det ect and follow int er mediat es in some r eact ions?
4. Descr ibe t he ut ilit y of Polar ogr aphic met hods in t he elect r osynt hesis of or ganic
compounds.
5. What ar e t he advant ages of elect r o-or ganic synt heses?
Chapter 10
1. What condit ions ar e r equir ed in or der t o use mat hemat ical analysis t o r esolve
over lapped fir st der ivat ive D.C. polar ogr ams?
2. What ar e t he advant ages of using Non-aqueous solvent s or solvent ext r act s in
D.C. Polar ogr aphy?
3. Descr ibe in br ief t heor y, pr inciples and applicat ions of cyclic and pulse t echniques.
4. What is st r ipping analysis? Descr ibe t he elect r odes used in t hese t echniques.
5. Give a br ief account of volt ammet r ic met hods. Also t he differ ent ial and der ivat ive
volt ammet r y.
Chapter 11
1. Innumer at e var ious t ypes of or ganic elect r ode r eact ions giving examples.
2. Wh a t a r e t h e va r iou s ca t egor ies of elect r olyt ic r ea ct ion pa t h a wa ys of
N-het er ocyclic r eact ions in gener al? Give examples.
3. Descr ibe t he exper iment al t echnique for r unning an elect r ochemical exper iment
wit h an or ganic syst em.
4. Give a cir cuit diagr am for galvanost at ic met hod (const ant cur r ent ).
5. Also give cir cuit for pot ent iost at ic met hod.
6. What is Polar izat ion st udy? How is it done?
PART II. ALLIED TECHNIQUES
Chapter 10
1. Define Kalouseks commut at or met hod. How is t he met hod r elat ed t o t he squar e
wave and pulse-polar ogr aphic t echniques.
2. What ar e char ging cur r ent s?
3. Give an account of t he sinusoidal A.C. Polar ogr aph?
4. Does t he A.C. Polar ogr aph const r uct ed fr om oper at ional amplifier pr ovide some
advant ages?
5. What is t he disadvant age of oper at ional amplifier employed in most exist ing
elect r oanalyt ical inst r ument s?
281
6. What ar r angement is named as milli- or micr ocoulomet r y?
7. Innumer at e t he var ious met hods for det er mining n by elect r olysis.
Chapter 11
1. Descr ibe chr onopot ent iomet r y in br ief. What ar e it s analyt ical applicat ions?
2. What ar e t he advant ages of chr onopot ent iomet r y over polar ogr aphy for a
par t icular t ype of exper iment ?
3. What t ype of cells ar e used for chr onopot ent iomet r y?
4. What is t he significant use of pulse polar ogr aphy and differ ent ial pulse
polar ogr aphy wit h D.C. Polar ogr aphy?
5. Give an account of elect r olyt ic cur r ent s and kinet ic cur r ent s.
6. Give br ief account of pulse polar ogr aphy and oscillogr aphic Polar ogr aphy.
Chapter 12
1. What is volt ammet r y?
2. Descr ibe in br ief coulomet r ic met hods.
3. Dist inguish bet ween differ ent ial and der ivat ive volt ammet r y.
Chapter 13
1. Give a br ief account of t he t echnique applied in elect r o-or ganic synt hesis.
2. What ar e t he main r eact ions t hat t ake place in elect r o-or ganic synt hesis?
3. What is t he main elect r ochemical act ivit y in het er ocyclic syst ems?
4. Descr ibe t he exper iment al t echnique.
5. How is t he cur r ent efficiency det er mined?
6. What is polar izat ion st udy?
Chapter 14
1. What ar e ion select ive elect r odes?
2. What par t is played by hydr ogen in cor r osion?
3. How is cor r osion cont r olled?
4. Give an account of pot ent ial-pH diagr ams applied in cor r osion pr ocesses.
5. What ar e elect r onat ion r eact ions in cor r osion?
6. What ar e t he fact or s t hat affect t he r at e of cor r osion.
7. Give some common examples of cor r osion?
8. What is passivat ion?
Chapter 15
1. What pollut ion pr oblems ar ise fr om t he pr edominent for m of ener gy conver sion?
2. What uncer t aint ies ar e t her e in pr edict ing t he fut ur e pollut ion of t he at mospher e?
3. What is t he power out put of an elect r ochemical ener gy conver t er ?
4. What ar e fuel cells?
5. Give a br ief account of some impor t ant fuel cells?
Chapter 16
1. Descr ibe ener gy densit y.
2. Elect r icit y st or age densit y.
3. Give an account of some impor t ant st or age bat t er ies.
4. What ar e new elect r icit y st or er s?
5. Descr ibe lead-acid st or age bat t er y.
Chapter 17
1. Dist inguish bet ween far adic and non-far adic pr ocesses.
2. What is an ideal polar ised elect r ode?
3. Descr ibe br iefly t he elect r ical double layer .
4. What ar e t he fact or s which affect t he r at es of elect r ode r eact ions and cur r ent ?
5. Give a br ief account of t he following given one example of each.
(i) For mal pot ent ial
(ii) Elect r ochemical pot ent ials
(iii) Absolut e pot ent ial
(iv) Cell pot ent ial
(v) Liquid junct ion pot ent ial.
6. Give t he cur r ent over pot ent ial equat ion.
7. What ar e t he implicat ions of But ler -Volmer equat ion?
General Question
1. Define Far adays laws of elect r olysis.
2. Define EMF of a cell.
3. Descr ibe Ficks laws of diffusion and t heir use in t he st udy of polar ogr aphy.
Describe:
4. Ner nst equat ion.
5. Act ivit y and act ivit y coefficient .
6. Ionic st r engt h and ionic equlibr ium.
7. Bolt zmans const ant .
8. Avogadr os number .
9. Elcovic equat ion.
10. Solubilit y and solubilit y pr oduct .
11. Buffer solut ions. Give t wo examples.
12. Polar it y of an elect r ode.
13. Half wave pot ent ial.
14. D.M.E. it s advant ages and disadvant ages.
15. Elect r ode pot ent ial and st andar d elect r ode pot ent ial.
16. Indicat or elect r ode and r efer ence elect r ode.
17. Liquid junct ion.
18. Rever sible and ir r ever sible elect r ode r eact ions.
283
19. Double layer and it s par t played dur ing elect r olysis.
20. Over volt age.
21. Fr ee ener gy.
22. Concent r at ion polar izat ion.
23. Hydr ogen over -volt age.
24. Cur r ent efficiency. How it is det er mined?
25. Advant ages and disadvant ages of D.M.E.
26. Dielect r ic const ant .
27. Why t her e ar e no st andar d pot ent ials mor e negat ive t han about 3 volt s and
mor e posit ive t han about +2 volt , in aqueous solut ion?
28. What is pH? How can one det er mines pH of solut ion?
29. How does a t hr ee elect r ode syst em differ s fr om t he t wo elect r ode syst em? What
ar e t hese named as? Give advant ages of choosing t he t hr ee elect r ode syst em.
30. What is t he significance for t he use of nor mal hydr ogen elect r ode?
31. Differ enciat e bet ween D.C. and A.C. polar ogr aphy.
32. Why in polar ogr aphic exper iment s, it is desir able t o r emove dissolved oxygen
fr om t he elect r olyt e by bubbling an iner t gas t hr ough it ?
33. Why is it necessar y t o add an iner t elect r olyt e t o t he exper iment al solut ion of
polar ogr aphy befor e car r ying out t he act ual exper iment ?
34. When Ed. vs log
i i d -i
, is plot t ed, t he linear plot for r eact ion t hat behaves
r ever sibly under diffusion cont r olled condit ions. What would be t he value of t he
slope of t his linear plot and what would be t he expr ession and it s value at t he
int er cept ? Explain giving an example.
35. Describe t he various t ypes of current s t hat have some significance in polarography
and allied t echniques.

Polarography

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7+,6 3$*( ,6

that for ms an i nsol ubl e

(Product of el ectrode reacti on)

i s reached for the care of stati onary

of the jth i on i n a sol uti on i s al so gi ven by the equati on.

Fi g 8.1 : Effect of complexat ion on

. By using t he convent ional DeFor d-

for t he ir r ever sible

ion concent r at ion, t he Fe(OH)

[alkaline solut ion]

ions for any concent rat ion rat io of

eit her in wa t er or in non-queous solvent s. For a useful

would be simplest example excluding of

) on eit her side of membr ane, which

17.22 16.5 0.72 S

88.2 1.5 87 3.78

81.6 1.5 81 3.52

74.6 1.5 72 3.12

53.8 0.8 53.5 2.34 OH 45 2

+ Hg CNS HgCNS + 0.14

+ Hg 2OH HgO Anion concent r at ion + 0.04

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