VOLATMMETRY

V.S.MURALIDHARAN
CSIR EMERITUS SCIENTIST
 Electro analytical Methods

Quantity measured in parentheses.

I = current, E = potential, R = resistance,
G = conductance, Q = quantity of
charge, t = time, vol = volume of a
standard solution, wt = weight
of an electrodeposited species
METHOD MEASUREMENT PRINCIPLE QUALIT- DESIRED DETECTION COMMENTS
APPLICATIONS ATIVE MINIMUM LIMIT
INFORM- SAMPLE
ATION SIZE
Voltammetry Current as a function of Quantitative analysis of Reversibility of 100 mg 10-1-10 –3 ppm A large number of voltage
(Polarography) voltage at a polarized electrochemically reaction 10 mg programs may be used.
(amperometric electrode reducible organic or Pulse Polarography and
titrations) inorganic material Differential Pulse
(chronoamperometry) Polarography improve
detection limits.

Potentiometry Potential at 0 current Quantitative analysis of Defined by 100 mg 10-2 -102 ppm Measures activity rather than
(potentiometric ions in solutions, pH. electrode (e.g., concentration.
titration) F-, Cl-, Ca2+)
(chronopotentiometry)

Conductimetry Resistance or Quantification of an Little qualitative 100 mg Commonly used as a

(conductometric conductance at inert ionized species, titrations identification detector for ion
titrations) electrodes information chromatography.

Coulometry Current and time as Exhaustive electrolysis Little qualitative 100 mg 10-9 -1 g High precision possible.
number of Faradays identification
information

Anodic Stripping Weight Quantitative trace Oxidation 100 mg 10-3 -103 g Electro deposition step
Voltammetry analysis of potential permits 10 ng provides improved detection
(Electrodeposition) electrochemically identification of limits over normal
reducible metals that metal. voltammetry.
form amalgams with
mercury
 Reactions which affect working range for
polarisable electrodes
 Solvent
2 H+ + 2 e - H2 E° = 0.00 V
O2 + 4 H+ + 4 e ---- >2 H2O E° = +1.23 V
O2 + 2 H+ + 2 e ---- > H2O2 E° = +0.70 V
 Electrode
Hg2+ + 2 e --- Hg E° = +0.80 V
Hg2Cl2 + 2 e ---2 Hg + 2 Cl – E° = +0.27 V
Pt2+ + 2 e --- Pt E° = +1.20 V

4 VSMuralidharan
 Working Range for Polarizable Electrodes

SCE = +0.244 V
5 VSMuralidharan
Summary of Voltammetric Techniques

6 VSMuralidharan 21/05/1439
 POLAROGRAPHY

V.S.MURALIDHARAN

7 V.S.MURALIDHARAN 2/6/2018
 Voltammetric Methods
•Historical
•Electrolysis at DME -1920’s
•Usually 3-electrode cells

•Measurement of current that results from the application of

potential.
Different voltammetric techniques are distinguished primarily
by the potential function that is applied to the working
electrode and by the material used as the working electrode.

8 V.S.MURALIDHARAN 2/6/2018
 Polarography uses mercury
droplet electrode that is regularly
renewed during analysis.
Applications:Metal ions
(especially heavy metal
pollutants) - high
sensitivity.Organic species able to
be oxidized or reduced at
electrodes: quinones, reducing
sugars and derivatives, thiol and
disulphide compounds, oxidation
cofactors (coenzymes etc),
vitamins,
pharmaceuticals.Alternative when
spectroscopic methods fail.

9 V.S.MURALIDHARAN 2/6/2018
 History
Jaroslav Heyrovský was the inventor of the
polarographic method, and the father of
electroanalytical chemistry, for which he was the
recipient of the Nobel Prize. His contribution to
electroanalytical chemistry can not be
overestimated. All modern voltammetric methods
used now in electroanalytical chemistry originate
from polarography.

On February 10, 1922, the "polarograph" was born as Heyrovský recorded the current-voltage curve
10 V.S.MURALIDHARAN
for a solution of 1 M NaOH. Heyrovský correctly interpreted the current increase between -1.9 and -
2/6/2018
+
2.0 V as being due to deposition of Na ions, forming an amalgam.
 Typical polarographic curves (dependence of current I on the voltage E applied to the
electrodes; the small oscillations indicate the slow dropping of mercury): lower curve
- the supporting solution of ammonium chloride and hydroxide containing small
amounts of cadmium, zinc and manganese, upper curve - the same after addition of
small amount of thallium.

Swedish king Gustav Adolf VI awards the Nobel Prize to

Heyrovský
11 V.S.MURALIDHARAN 2/6/2018
in Stockholm on 10.12.1959
 Potential Ramps

Linear sweep Polarography

In order to derive the the current response one must
account for the variation of drop area with time:

A = 4 (3mt/4 d)2/3 = 0.85(mt)2/3

Density of drop Mass flow rate of drop

using Cottrell Equation

12 V.S.MURALIDHARAN i(t) = nFACD1/2/ 1/2t1/2

2/6/2018
 We also replace D by 7/3D to account for the compression of the diffusion
layer by the expanding drop

Giving the Ilkovich Equation:

id = 708nD1/2m2/3t1/6C
I has units of Amps when D is in cm2s-1,m is in g/s and t is in
seconds. C is in mol/cm3
This expression gives the current at the end of the drop life. The average
current is obtained by integrating the current over this time period

iav = 607nD1/2m2/3t1/6C

13 V.S.MURALIDHARAN 2/6/2018
 The diffusion current is determined by subtracting away the residual
currentFurther improvements can be made by reducing charging currents

E1/2 = E0 + RT/nF log (DR/Do)1/2 (reversible couple)

Usually D’s are similar so half wave potential is similar to formal potential.
Also potential is independent of concentration and can therefore be used
as a diagnostic of identity of analytes. For example
Class Functional Group E1/2 (v
SCE)
Azo -N=N- -0.4
carbonyl >C=O -2.2
Nitro NO2 -0.9
Quinone C=O -0.1

15 V.S.MURALIDHARAN 2/6/2018
 •Organic reductions often involve hydrogen ions

•R + nH+ + ne  RHn

• Good buffering reqd in organic polarography

Metal Complexes
•MLp + ne + Hg  M(Hg) + pL

•Difference between half-wave potential for complexed and

uncomplexed metal ion is given by:
•E1/2(c) - E1/2(free) =RT/nF ln Kd - RT/nF p ln [L] +RT/nF ln (D free/D (c))1/2
Stoichiometry can thus be determined by plotting
E1/2 versus [L]
•Also possible to improve resolution between neighbouring waves
by carefully choosing ligand and concentration
16 V.S.MURALIDHARAN 2/6/2018
 Heyrovsky-Ilkovich Equation
• Describes wave shape for reversible systems (with fast electron
transfer kinetics)
• E = E1/2 + RT/nF ln((id - i)/i)
• Plot E vs log((id - i)/i) gives straight line of slope 0.059/n
•Convenient way to get n
• Intercept is half wave potential
•Irreversible systems
•The waves are more “drawn out” than for reversible systems
•Limiting currents still show a linear function of concentration
• Shape of polarogram is given by:

•E = E0 + RT/ nF ln (1.35kf((id - i)/i)(t/D)1/2)

•transfer coefficient forward rate constant

17 V.S.MURALIDHARAN 2/6/2018
 Charging Currents : first look

• Drop acts as capacitor

• Double layer
• Since potential change during drop life is very small we can
neglect charging changing with potential
• charging thus depends on time and electrode area

ic = dq/dt = (E-Epzc)Cdl dA/dt

but A = 4 (3mt/4 d)2/3 = 0.85(mt)2/3

ic = 0.00567 (E-Epzc) Cdl m2/3t-1/3

so I(total) = id + ic = kt1/6 + k’t-1/3

18 V.S.MURALIDHARAN 2/6/2018
 Charging current sets limit of detection
Various ways of reducing it
e.g., Sample current at end of drop life (TAST
polarography)

19 V.S.MURALIDHARAN 2/6/2018
 VOLTAMMETRY
A.) Comparison of Voltammetry to Other Electrochemical Methods

1.) Voltammetry: electrochemical method in which information about an analyte is

obtained by measuring current (i) as a function of applied potential
- only a small amount of sample (analyte) is used

Instrumentation – Three electrodes in solution

containing analyte

Working electrode: microelectrode whose potential

is varied with time

Reference electrode: potential remains constant

(Ag/AgCl electrode or calomel)

Counter electrode: Hg or Pt that completes circuit,

conducts e- from signal source through solution to
the working electrode

Supporting electrolyte: excess of nonreactive

electrolyte (alkali metal) to conduct current
 Potentiostat

 Counter electrode carries most of the current

 Reference electrode must be physically close to working electrode
 Virtually no current flows between working and reference electrodeaccurate
potential measurement

21 VSMuralidharan vsm
Apply Linear Potential with Time Observe Current Changes with Applied Potential
 B.) Theory of Voltammetry

1.) Excitation Source: potential set by instrument (working electrode)

- establishes concentration of Reduced and Oxidized Species at electrode
based on Nernst Equation:

Eelectrode = E0 - log (aP)p(aQ)q …

0.0592 (aR)r(aS)s …
n
- reaction at the surface of the electrode

Apply

Potential
 1) Differences from Other Electrochemical Methods
a) Potentiometry: measure potential of sample or system at or near zero
current.

voltammetry – measure current as a change in potential

b) Coulometry: use up all of analyte in process of measurement at fixed current

or potential

voltammetry – use only small amount of analyte while vary potential

2) Voltammetry first reported in 1922 by Czech Chemist Jaroslav Heyrovsky

(polarography). Later given Nobel Prize for method.
Current is just measure of rate at which species can be brought to electrode surface

Two methods:
Stirred - hydrodynamic voltammetry
Unstirred - polarography (dropping Hg electrode)

Three transport mechanisms:

(i) migration – movement of ions through solution by electrostatic attraction to
charged electrode
(ii) convection – mechanical motion of the solution as a result of stirring or flow
(iii) diffusion – motion of a species caused by a concentration gradient
 At Electrodes Surface: Mox + e-  Mred

0.0592log [Mred]s
Eappl = Eo - at surface of electrode
n [Mox]s
Applied potential

If E appl = Eo:
0.0592
[Mred]s
Eappl = E0 - log
[Mox]s
n

[Mox]s = [Mred]s
 Apply

Potential
E << Eo

If Eappl << Eo:

[Mred]s
Eappl = E0 - 0.0592 log
n
[Mox]s

[Mred]s >> [Mox]s

2.) Current generated at electrode by this process is proportional to concentration at
surface, which in turn is equal to the bulk concentration

For a planar electrode:

measured current (i) = nFADA ( dCA )

dx
where:
n = number of electrons in ½ cell reaction
F = Faraday’s constant
A = electrode area (cm2)
D = diffusion coefficient (cm2/s) of A (oxidant)

dCA = slope of curve between CMox,bulk and CMox,s

dx

dx

dCA
As time increases, push banding further and further out.
Results in a decrease in current with time until reach point where convection of analyte takes over and
diffusion no longer a rate-limiting process.
 Thickness of Diffusion Layer (d):
nFADox
i= (cox, bulk – cox,s)
d

- largest slope (highest current) will occur if:

Eappl << Eo (cox,s . 0)

nFADox
then
d
i= (cox, bulk – 0)
nFADox
where:
k= d

so:
i = kcox,bulk

therefore:
current is proportional to bulk concentration

- also, as solution is stirred, d decreases and i increases

 Voltammetry Apparatus
 Various working
microelectrodes used: hanging
mercury drop (depicted),
glassy carbon, etc.
 Typically small volume (1-10
mL)

31 VSMuralidharan 21/05/1439
3.) Combining Potential and Current Together

Limiting current
Related to concentration

E½ at ½ i
Half-wave potential : E1/2 = -0.5 . E0 - Eref

E0 = -0.5+SCE for Mn+ + me-  M(n-m)+

Potential applied on the working electrode is usually swept over (i.e. scan) a pre-defined
range of applied potential

0.001 M Cd2+ in 0.1 M KNO3 supporting electrolyte

Electrode become more and more
reducing and capable of reducing Cd2+
All Cd2+ around the electrode has
Cd2+ + 2e- Cd already been reduced. Current at
Current starts to be registered at the the electrode becomes limited by
i (mA)
electrode the diffusion rate of Cd2+ from the
Working electrode is E½ bulk solution to the electrode.
no yet capable of Thus, current stops rising and
reducing Cd2+  levels off at a plateauid
Current at the working
only small residual
electrode continue to rise as
current flow through
the electrode become more
the electrode Base line
reducing and more Cd2+
around the electrode are being of residual
reduced. Diffusion of Cd2+ current
does not limit the current yet

-0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4

V vs SCE
Why peak
comes?
 Voltammetry

 Slow E scan at constant fixed

electrode surface, or
 Fast E scan at DME during the
lifetime of a single drop
 Negligible bulk electrolysis of
solution

35 VSMuralidharan 21/05/1439
How to calculate peak currents?
Current is a function of concentration gradient

FOR SECOND
PEAK
CURRENT FUNCTION FOR A REVERSIBLE
PROCESS
(t )
mv mv
120 0.009 0.008 -5 0.400 0.548
100 0.020 0.019 -10 0.418 0.596
120 0.016 0.041 -15 0.432 0.641
110 0.024 0.087 -20 0.441 0.685
100 0.035 0.124 -25 0.445 0.725
90 0.05 0.146 -28.5 0.4463 0.7516
80 0.073 0.173 -30 0.446 0.763
70 0.104 0.208 -35 0.443 0.796
60 0.145 0.236 -40 0.438 0.826
50 0.199 0.273 -50 0.421 0.875
40 0.264 0.314 -60 0.399 0.912
35 0.300 0.375 -80 0.353 0.957
30 0.337 0.403 -100 0.312 0.980
25 0.372 0.451 -120 0.280 0.991
20 0.406 0.499 -150 0.245 0.997
 i  nFAC00 D0  (t )  nFAD0 C00 (t ) r0

The second term in the right hand side is for spherical diffusion. This correction
is small when the electrode radius is large Then

0
nFAD0 C
i P  i planar  (0.725  10 ) 5 0

r0
1.857 RT 47.7
EP  EP 2   mV
cF c
 Cyclic Voltammetry
1) Method used to look at mechanisms of redox reactions
in solution
2) Looks at i vs. E response of small, stationary electrode
in unstirred solution using triangular waveform for excitation

Cyclic voltammogram
 Excitation Cyclic Voltammetry
E2
(CV)
Eapp, V

 Important parameters:
E1  Epa and Epc
Time, s
 ipc and iac
Response Epa  E’
 DE = |Epa - Epc|
I, A

E1 E2

Epc
R - ne -=O
Eapp, V

21/05/1439 VSMuralidharan 40
 Analysis of an Example K3Fe(CN)6
• Starting at an initial voltage (A), the
potential is scanned in the negative
direction.

• At B, the potential has become negative

enough to start a cathodic current between
the species, reducing the analyte at the
working electrode.
• The cathodic current continues to slowly
• The reaction continues at the electrode decay until the potential reaches a point to start
until most of the species has been reduced, the oxidation of the analyte (E).
peaking the cathodic current at (C).
• The anodic current is then measured as the
• The current then decays for the rest of the concentration of the reduced species is
forward scan until the potential scan is significantly diminished (F).
reversed (D). The scan in the positive
direction proceeds similarly to that of the •The anodic current then decays from this peak,
negative scan. 2/6/2018 41
and the potential completes its cycle.
V.S.MURALIDHARAN
 Cyclic Votammetry
 Continuous, cyclic sweeping of
potential
 Especially useful for reversible
reactions
 Can provide information about
transient electroactive species

42 VSMuralidharan 21/05/1439
Start at E >> E0 Mox + ne-  Mred
- in forward scan, as E approaches E0 get current due to
Mox + ne-  Mred
driven by Nernst equation
 concentrations made to meet
Nernst equation at surface
eventually reach i max
< solution not stirred, so d grows with time and
see decrease in i max
- in reverse scan see less current as potential increase until
reduction no longer occurs
< then reverse reaction takes place (if
reversible reaction)
< important parameters
 Epc – cathodic peak potential
 Epa – anodic peak potential
 ipc – cathodic peak current
 ipa – anodic peak potential
< ipc . ipa
< d(Epa – Epc) = 0.0592/n,
where n = number of electrons in reaction
< E0 = midpoint of Epa  Epc
 Voltammetric Parameters
 The peak potential,
is offset about 28 mV at 25°C

 The peak current is proportional to the square root of the

scan rate

RT
E p  E1 2  1.1 i p  kn AD cv
32 12 12

nF

44 VSMuralidharan 21/05/1439
 For Nernstian CV
 DEp = |Epa - Epc| = 59/n mV at 250C
 independent of n

 Eo = (Epa + Epc)/2

 Ipc/Ipa = 1

45 VSMuralidharan 21/05/1439
 For Nernstian Process
 Potential excitation controls [R]/[O] as in Nernst equation:
Eapp = E0- 0.059/n log [R]/[O]

 if Eapp > E0, [O] ___ [R] and ox occurs

 if Eapp < E0, [O] ___ [R] and red occurs
 i.e., potential excitation CONTROLS [R]/[O]

46 VSMuralidharan 21/05/1439
 Quasi-reversible or Irreversible
 Quasi-reversible:
 DEp > 59 mV and DEp increases with increasing n
 iR can mascarade as QR system
 Irreversible:
 chemically - no return wave
 slow ET - 2 waves do not overlap

47 VSMuralidharan 21/05/1439
 Criteria for Nernstian Process
 Ep independent of scan rate

 ip  n1/2 (diffusion controlled)

 Ipc/Ipa = 1 (chemically reversible)

48 VSMuralidharan
 Some schemes

E A+e=B
EE A + e = B; B + e = C; 2B = A + C
EC A1 + e = B1; B1 = B2
EC’ A + e = B; B + P = A + Q
EC2 A + e = B; 2B = B2
CE Y = A; A + e = B
ECE A1 + e = B1; B1 = B2; B2 + e = C2;
B1 + B2 = A1 + C2
v.s.muralidharan 2/6/2018
Adsorption Phenomena
 Non-specifically adsorbed
 No close-range interaction with electrode
 Chemical identity of species not important

 Specifically adsorbed
 Specific short-range interactions important
 Chemical identity of species important

VSMuralidharan 50
 Applications of CV
 Many functional group are not reducible so we can derivatize
these groups
 convert them into electroactive groups by chemical
modification

 EXAMPLES:
 alcohols + chromic acid = aldehyde group
 phenyl + nitration = nitro group

21/05/1439 VSMuralidharan 51
 CV and Adsorption
 If electroactive adsorbed species:
 Ep = Eo - (RT/nF) ln (bo/bR)
 ip = (n2F2/4RT) A o* n

90 mV  If ideal Nernstian,
I Epa = Epc and DEp/2 = 90.6 mV/n at
Eapp 250C

VSMuralidharan 52
UME’s Radial vs. Planar Diffusion
Radial Diffusion Planar Diffusion
 Redox wave:  Redox wave:
 sigmoidal shape  normal shape
 Iss = 4nFrDoCo*  Ip  n1/2  Do1/2 C
 Iss scan rate independent 
DoCo*

21/05/1439 VSMuralidharan 53
 EXAMPLE 1: UME’s
in Sol-Gels

 Learn Do from CA

 Obtain Co*from slow scan rate

CV (Iss)

21/05/1439 VSMuralidharan 54
20 mV/s EXAMPLE 2: No
Electrolyte!
20 mV/s  [S2Mo18O62]4- + e- = [S2Mo18O62]5-
+ e- = [S2Mo18O62]6-
 BAS 100-A
100 mV/s  3-electrode cell:
 GC macrodisk/Pt wire/ Pt wire
 ACN with no electrolyte

vsm VSMuralidharan 55
 Ultra micro electrodes
Fast scan rates Slow scan rates
30 V/s 5 mV/s
planar diffusion radial diffusion
Fe3+

0.1 mm 0.1 mm

21/05/1439 VSMuralidharan 56
 EXAMPLE 2: Oxidation
of Cysteine at BDD

21/05/1439 VSMuralidharan 57
Stripping Analysis or Stripping
Voltammetry
 Cathodic (CSV)
 Good for anions and oxyanions
 Anodic (ASV)
 Good for metal cations

21/05/1439 VSMuralidharan 58
 Stripping Voltammetry - Steps
1. Deposition
2. Concentration
3. Equilibration
4. Stripping

21/05/1439 VSMuralidharan 59
 Example of ASV: Determination of Pb
at HDME
 Deposition (cathodic) reduce Pb2+
 Stir (maximize convection)

Eapp  Concentrate analyte

I  Stop stirring = equilibration/rest period

 Scan E in anodic sense and record
Ip voltammogram
 oxidize analyte (so redissolution occurs)

Pb  Pb2+ + 2e-

21/05/1439 VSMuralidharan 60
Stripping Voltammetry - Quantitation
I p  Co *

Concentrations obtained using

either
Standard addition
Calibration curve

21/05/1439 VSMuralidharan 61
 HDME ASV
 Usually study M with Eo more negative than
Hg
 Ex: Cd2+, Cu2+, Zn2+, Pb2+
 Study M with Eo more positive than Hg at GC
 Ex: Ag+, Au+, Hg
 Can analyze mixture with DEo  100 mV

21/05/1439 VSMuralidharan 62
CSV
 Anodic deposition
 Form insoluble, oxidized Hg salt of analyte anion
 Stir (maximize convection)
 Equilibrate (stop stirring)
 Scan potential in opposite sense (cathodic)
 Reducing salt/film and forming soluble anion
 Record voltammogram

21/05/1439 VSMuralidharan 63
 Stripping Voltammetry
 For cations of amalgam-forming metals and anions of
sparingly soluble Hg salts
 First step is electrochemical deposition (preconcentration)
at the Hg electrode
 Second step is anodic or cathodic potential sweep, in which
peak currents are measured
 Extremely sensitive (nM or ppb range) depending on
preconcentration time

21/05/1439 VSMuralidharan 64
vsmuralidharan
Anodic Stripping Voltammagram

VSMuralidharan 66
vsmuralidharan
vsmuralidharan
audience

VSM