REDOX REDOX

Reduction Oxidation Titration ReductionOxidation Titration

An application method of
InorganicPharmaceuticalAnalysis
Lecturer:Dr.TutusGusdinar
PharmacochemistryResearchGroup
SchoolofPharmacy
INSTITUTTEKNOLOGIBANDUNG
In acidbase titrations the change in pH during titration Inacidbasetitrations,thechangeinpHduringtitration
maybecalculated,andthetitrationcurvesthus
obtained can be used to ascertain the most suitable obtainedcanbe usedtoascertainthemostsuitable
indicatortobeusedinagiventitration, andto
determine the titration error determinethetitrationerror.
Similar procedures may be carried out for oxidation Similarproceduresmaybecarriedout foroxidation
reductiontitrations.Considerfirstasimplecasewhich
involves only change in ionic charge and is theoretically involves onlychangeinioniccharge,andistheoretically
independentofthehydrogenion concentration.
A suitable example for purposes of illustration is the Asuitableexample,forpurposesofillustration,isthe
titration of100mL of0.1Miron(II)with0.1M cerium
(IV) in the presence of dilute sulphuric acid (IV)inthepresenceofdilute sulphuricacid.
E E
o
0 0591/ l [O ]/[R d] t 25
o
C E=E
o
+0.0591/n.log[Ox]/[Red]at25
o
C
Standardpotentials E
o
areevaluatedwithfullregardto
activityeffectsand withall ionspresentinsimpleform :
theyarereallylimitingoridealvaluesand arerarely
observedinapotentiometric measurement.
In practice,thesolutions maybequiteconcentrated and
frequentlycontainotherelectrolytes;underthese
conditionstheactivitiesofthepertinentspeciesare
muchsmallerthanthe concentrations,and consequently
theuseofthelattermayleadtounreliable conclusions.
Also,theactualactivespeciespresentmay differfrom
thosetowhichtheidealstandardpotentialsapply.
Theformal potential Eoisthepotentialobserved
experimentally in a solution containing one mole each of experimentallyinasolutioncontaining onemoleeachof
theoxidised andreducedsubstancestogetherwithother
specified substances at specified concentrations It is specifiedsubstancesatspecifiedconcentrations.Itis
foundthatformal potentials vary appreciably,e.g. with
the nature and concentration of the acid that is present thenatureandconcentrationoftheacid thatispresent.
Theformal potentialincorporatesinonevaluetheeffects
resulting from variation of activity coefficients with ionic resulting fromvariationofactivitycoefficientswithionic
strength,acidbasedissociation, complexation,liquid
junction potentials etc and thus has a real practical junctionpotentials,etc.,andthushasarealpractical
value. Formal potentialsdonothavethetheoretical
significance of standard potentials but they are observed significanceofstandardpotentials, buttheyareobserved
valuesinactualpotentiometric measurements.
100 mL of 0 1 M iron(II) with 0 1 M cerium (IV) in the 100mL of0.1Miron(II)with0.1M cerium (IV)inthe
presenceofdilute sulphuricacid:
Thequantitycorrespondingto[H
+
]inacidbasetitration
istheratio [Ox]/[Red].Weareconcernedherewithtwo
systems : 1)theFe
3+
/Fe
2+
ion electrode,and
2)theCe
4+
/Ce
3+
ionelectrode.
For(1)at25
o
C:
Th ilib i f h i i i b Theequilibriumconstantofthereactionisgivenby
During the addition of the cerium(IV) solution up to the Duringtheadditionofthecerium(IV)solutionuptothe
equivalencepoint, itsonlyeffectwillbetooxidisethe
iron(II) since K is large and consequently change the iron(II),sinceKislarge, andconsequently changethe
ratio[Fe
3+
]/[Fe
2+
].
When10mLoftheoxidisingagenthave beenadded,
[Fe
3+
]/[Fe
2+
] = 10/90 (approximately) and [Fe ]/[Fe ]=10/90(approximately)and
E
1
=0.75+0.0591log10/90=0.75 0.056=0.69volt
With50mLoftheoxidisingagent,E
1
=E
o
1
=0.75volt
With 90 mL E = 0 75 + 0 0591 log 90/10 = 0 81 volt With90mL,E
1
=0.75+0.0591log90/10=0.81volt
With99mL,E
1
=0.75=0.0591log99/1=0.87volt
With 99 9 mL E = 0 75 + 0 0591 log 99 9/0 1 = 0 93 volt With99.9mL,E
1
=0.75+0.0591log99.9/0.1=0.93volt
h l ( ) Attheequivalencepoint(100.0mL):
[Fe
3+
]=[Ce
3+
] and[Ce
4+
]=[Fe
2+
]
h l d i l i i b Theelectrodepotentialisgivenby :
(E
1
+E
2
)/2=(0.75+1.45)/2=1.10volts
Thesubsequentadditionofcerium(IV)solutionwill
l i h i [C
4+
]/[C
3+
] merelyincreasetheratio [Ce
4+
]/[Ce
3+
].
Thus:
Wi h 100 1 L E 1 45 0 0591 l 0 1/100 1 27 l With100.1mL,E
1
=1.45+0.0591log0.1/100=1.27volts
With101mL,E
1
=1.45+0.0591log1/100=1.33volts
Wi h 110 L E 1 45 0 0591 l 10/100 1 39 l With110mL,E
1
=1.45+0.0591log10/100=1.39volts
With190mL,E
1
=1.45+0.0591log90/100=1.45volts
Titrationof100mL of0.1 Miron(II)with0.1 Mcerium(IV)sulphate
Itisofinteresttocalculatetheiron(II)concentrationin
h i hb h d f h i l i h theneighbourhood oftheequivalencepoint.When
99.9mLofthecerium(IV)solutionhavebeen added,
[
2
] /
5 2
[Fe
2+
]=0.1x0.1/199.9=5x 10
5
or pFe
2+
=4.3.
h i h i l i i i b The concentration attheequivalencepointisgivenby
Now[Fe
3+
]=0.05 M,hence[Fe
2+
]=5x10
2
/8.4x10
5
=6
x 10
8
M or pFe
2+
= 7 2 x10 M,or pFe =7.2
Upontheadditionof100.1mLofcerium(IV)solution,the
reduction potential is 1 27 volts The [Fe
3+
] is practically reductionpotentialis1.27volts.The[Fe ]ispractically
unchanged at5x10
2
M,andwemaycalculate[Fe
2+
]
with sufficient accuracy for our purpose from the withsufficientaccuracyforour purposefromthe
equation:
E = E
o
1
+ 0.0591 log [Fe
3+
] /[Fe
2+
] E E
1
+0.0591log[Fe ]/[Fe ]
ThuspFe
2+
changesfrom4.3to10between0.1percentbefore
d f h i hi i d i and 0.1percentafterthestoichiometricendpoint.
Thesequantitiesareofimportance inconnectionwiththeuseof
indicators for the detection of the equivalence point indicatorsforthedetectionoftheequivalencepoint.
Itisevidentthattheabruptchangeofthepotentialin
the neighbourhood of the equivalence point is theneighbourhood oftheequivalencepointis
dependentuponthestandardpotentialsofthetwo
oxidation reduction systems that are involved and oxidationreductionsystemsthatareinvolved,and
thereforeupontheequilibrium constantofthereaction;
it is independent of the concentrations unless these itisindependentoftheconcentrationsunlessthese
areextremelysmall.
Thechangeinredoxpotentialforanumberoftypical
oxidation reduction systems is exhibited graphically in oxidationreductionsystemsisexhibitedgraphicallyin
MnO
4
/Mn
2+
systemandotherswhicharedependent
upon the pH of the solution the hydrogen ion concen uponthepHofthesolution,thehydrogenionconcen
trationisassumedtobemolar :loweracidities give
lower potentials The value at 50% oxidised form will of lowerpotentials.Thevalueat50%oxidisedformwill,of
course, correspondtothestandardredoxpotential.
Asanindicationoftheapplication ofthecurves,
consider the titration of iron(II) with potassium considerthetitrationofiron(II)withpotassium
dichromate.The titrationcurvewouldfollowthatof
the Fe(II)/Fe(III) system until the end point was theFe(II)/Fe(III)systemuntiltheendpoint was
reached,thenitwouldrisesteeplyandcontinuealong
the curve for the Cr O
2
/Cr
3+
system : the potential at thecurveforthe Cr
2
O
7
2
/Cr
3+
system :thepotentialat
theequivalencepointcanbedetermined asalready
described described.
Itispossibletotitratetwosubstancesbythesame
titrant provided that the standard potentials of the titrantprovidedthatthe standardpotentialsofthe
substancesbeingtitrated,andtheiroxidationor
reduction products differ by about 0 2 V Stepwise reductionproducts,differbyabout0.2V.Stepwise
titrationcurvesareobtained inthetitrationof
mixtures or of substances having several oxidation mixturesorofsubstanceshavingseveraloxidation
states.
RedoxIndicators
Theidealoxidationreductionindicatorwillbeonewith
id i i l i di b h f h anoxidationpotentialintermediatebetween thatofthe
solutiontitrated(analyte)andthatofthetitrant,and
hi h hibi h dil d bl l h whichexhibitsasharp,readilydetectablecolourchange.
d i di i d hi h hibi Anredox indicator isacompoundwhich exhibits
differentcolours intheoxidised andreducedforms :
In
Ox
+ne In
Red
Theoxidationandreductionshouldbereversible.Ata
i l E h i f h i f h potentialEtheratioof theconcentrationsofthetwo
formsisgivenbytheNernstequation :
whereE
o
isthestandard(strictlytheformal)potentialof
the indicator If the colour intensities of the two forms theindicator.Ifthe colour intensitiesofthetwoforms
arecomparableapracticalestimateofthe colourchange
interval corresponds to the change in the ratio intervalcorrespondstothechangeintheratio
[In
Ox
]/[In
Red
] from10to1/10,thisleadstoanintervalof
potential of : potentialof :
If the colour intensities of the two forms differ Ifthecolour intensitiesofthetwoformsdiffer
considerablytheintermediate colour isattainedat
potential somewhat removed from E
o
but the error is potentialsomewhatremovedfromE ,buttheerroris
unlikelytoexceed0.06volt.
Forasharpcolour changeattheendpoint,E
o
should
differ by about at least 0 15 volt from the standard differbyaboutatleast0.15voltfromthestandard
(formal)potentials oftheothersystemsinvolvedinthe
reaction reaction.
Oneofthebestoxidationreductionindicatorsisthe
1,10phenanthroline iron(II) complex. The base 1,10 1,10 phenanthroline iron(II)complex.Thebase1,10
phenanthroline combinesreadilyinsolution with
iron(II) salts in the molecular ratio 3 base: 1 iron(II) ion iron(II)saltsinthemolecularratio3base: 1 iron(II)ion
formingthe intenselyred1,10phenanthrolineiron(II)
complex ion; with strong oxidising agents the iron(III) complexion;withstrongoxidising agentstheiron(III)
complexionisformed,whichhasapalebluecolour.
The colour change is a very striking one : The colour changeisaverystrikingone :
Thestandardredox potentialis1.14volts;theformal
potential is 1 06 volts in 1 M hydrochloric acid solution potentialis1.06voltsin 1Mhydrochloricacidsolution.
Thecolour change,however,occursatabout 1.12volts,
because the colour of the reduced form (deep red) is so becausethecolour ofthereducedform(deepred)isso
muchmore intensethanthatoftheoxidised form(pale
blue) The indicator is of great value in the titration of blue).Theindicatorisofgreatvalue inthetitrationof
iron(II)saltsandothersubstanceswithcerium (IV)
sulphate solutions It is prepared by dissolving 1 10 sulphate solutions.Itispreparedbydissolving1,10
phenanthroline hydrate(relative molecularmass=
198 1) in the calculated quantity of 0 02 M acid free 198.1)inthecalculatedquantityof0.02Macidfree
iron(II) sulphate,andistherefore1,10phenanthroline
iron(II) complex sulphate (known as ferroin) One drop is iron(II)complexsulphate (knownasferroin).Onedropis
usuallysufficientinatitration :thisisequivalent toless
than 0 01 mL of 0 05 M oxidising agent and the indicator than0.01mL of0.05 Moxidising agent,and the indicator
blank isnegligibleatthisorhigher concentrations.
Theearliestinternal indicatorsisa 1percentsolutionof
diphenylamineinconcentratedsulphuric acid,andwas
introducedforthetitrationofiron(II)withpotassium
dichromatesolution.An intensebluevioletcolorationis
producedattheendpoint.Theadditionof phosphoric (V)
acidisdesirable,foritlowerstheformal potentialofthe
Fe(III)Fe(II)systemsothattheequivalencepoint
potentialcoincidesmore nearlywiththatoftheindicator.
Theactionofdiphenylamine (I)asanindicator dependsuponits
id i fi i l l di h lb idi (II) hi h i h oxidationfirstintocolourless diphenylbenzidine (II),which isthe
realindicatorandisreversiblyfurtheroxidised to diphenylbenzi
dine violet (III) Diphenylbenzidine violet undergoes further dine violet(III). Diphenylbenzidine violetundergoesfurther
oxidationifitisallowed tostandwithexcessofdichromate
solution;thisfurtheroxidationis irreversible, andredoryellow
productsofunknowncompositionareproduced.
Diphenylamine
RedoxTitrationMethods
Permanganometry Permanganometry
Dichromatometryy
Cerimetry
Iodometry&Iodimetry
Iodatometry Iodatometry
Bromatometry Bromatometry
1.PermanganometricTitration
Thisvaluableandpowerfuloxidisingagentwasfirstintroducedintotitrimetric
analysisbyF.Margueritteforthetitrationofiron(II).Inacidsolutions,the
reduction can be represented by the following equation : reductioncanberepresentedbythefollowingequation :
h d d i l i id l i h b l l d b l Thestandardpotentialinacidsolution,E
o
hasbeencalculatedtobe1.51volts;
hencethepermanganateioninacidsolutionisastrongoxidisingagent.
Sulphuricacidisthemostsuitableacid,asithasnoactionuponpermanganate
indilutesolution.Withhydrochloricacid,thereisalikelihoodofthereaction :
takingplace,andsomepermanganatemaybeconsumedintheformationof
chlorine.Thisreactionisparticularlyliabletooccurwithironsaltsunlessspecial
precautions are adopted. With a small excess of free acid, a very dilute solution, precautionsareadopted.Withasmallexcessoffreeacid,avery dilutesolution,
lowtemperatureandslowtitrationwithconstantshaking,the dangerfromthis
causeisminimised.Thereare,however,sometitrations,such asthosewith
arsenic(III) oxide antimony(III) and hydrogen peroxide which can be carried out arsenic(III)oxide,antimony(III),andhydrogenperoxide,which canbecarriedout
inthepresenceofhydrochloricacid.
Potassiumpermanganateinstronglyalkalinesolution
can take place two reactions : cantakeplacetworeactions :
(1)Inrapidreaction :
MnO
4

+ e MnO
4
2
MnO
4
+e MnO
4
(2)In slowreaction :
MnO
4
2
+ 2H
2
O + 2e MnO
2
+ 4 OH

MnO
4
+2H
2
O +2e MnO
2
+4 OH
StandardpotentialE
o
ofreaction(1)is0.56voltandofreaction
(2) is0.60volt.Bycontrollingtheexperimentalconditions(e.g.by
additionofbariumions toformafinegranularprecipitateof
sparinglysolublebarium manganate)reaction(1)willbetheonly
d occured.
In moderatealkalinesolution,permanganatewillbe
red ced q antitati el to form manganese dio ide ith reducedquantitativelyto formmanganesedioxide with
a halfcell reaction :
MnO

+ 2H O + 3e MnO + 4 OH

MnO
4

+2H
2
O +3e MnO
2
+4 OH

StandardpotentialE
o
is0.59volt.
KMnO
4
isnotaprimarystandard.Itisdifficulttoobtain the
substance perfectly pure and completely free from manganese substanceperfectlypureandcompletelyfreefrommanganese
dioxide. Moreover,ordinarydistilledwaterislikelytocontain
reducingsubstances (tracesoforganicmatter,etc.)whichwill
reactwiththepotassiumpermanganate toformmanganese
dioxide.Thepresenceofthelatterisveryobjectionable becauseit
t l th t d iti f th t l ti catalysestheautodecompositionofthepermanganatesolution
on standing:
4MnO
4
+2H
2
O 4MnO
2
+3O
2
+4OH
Permanganateisinherentlyunstableinthepresenceof
manganese (II)ions:
2 MnO
4
+3 Mn
2+
+2 H
2
O 5 MnO
2
+4 H
+
Thi ti i l i id l ti b t it i id i t l Thisreactionisslowinacidsolution,butitisveryrapidinneutral
solution.
For these reasons, potassium permanganate solution is rarely made
b di l i i h d t f th ifi d lid i t it i up by dissolving weighed amounts of the purified solid in water; it is
more usual to heat a freshly prepared solution to boiling and keep it
on the steam bath for an hour or so, and then filter the solution
through a non-reducing filtering medium, such as purified glass wool
or a sintered-glass filtering crucible (porosity No. 4).
Alternatively,thesolutionmaybeallowedtostandfor 23daysat
roomtemperaturebeforefiltration.Theglassstoppered bottleor
flaskshouldbecarefullyfreedfromgreaseandpriordepositsof
manganese dioxide:thismaybedonebyrinsingwithdichromate
l h i id l i i t d th th hl ith di till d sulphuric acidcleaning mixtureandthenthoroughlywithdistilled
water.Acidicandalkalinesolutions arelessstablethanneutral
ones. Solutions of permanganate should be protected from ones.Solutionsofpermanganateshouldbeprotected from
unnecessaryexposuretolight:adarkcoloured bottleisrecom
mended. Diffusedaylightcausesnoappreciable decomposition,
butbrightsunlightslowly decomposesevenpuresolutions.
STANDARDIZATIONOFKMnO
4
MethodA :Witharsenic(III)oxide.
Thisprocedure,whichutilises arsenic(III) oxideasaprimary
d d d i i did i i d l standardandpotassiumiodideorpotassiumiodate asa catalyst
forthereaction,isconvenientinpracticeandisa trustworthy
method for the standardisation of permanganate solutions methodforthestandardisation ofpermanganatesolutions.
Analyticalgrade arsenic(III)oxidehasapurityofatleast99.8per
cent,andtheresultsbythis methodagreetowithin1partin3000
withthesodiumoxalateprocedure (MethodB,below).
A O 4OH 2 HA O
2
H O As
2
O
3
+4OH

2 HAsO
3
2
+ H
2
O
5H
3
AsO
3
+2MnO
4

+6H
+
5 H
3
AsO
4
+2 Mn
2+
+3 H
2
O
Method B With sodium oxalate hi i dil b i d MethodB :Withsodiumoxalate.Thisreagentisreadilyobtained
pureand anhydrous,andtheordinarymaterialhasapurityofatleast99.9per
cent.In theexperimentalprocedureoriginallyemployedasolutionofthe
oxalate, acidifiedwithdilutesulphuric acidandwarmedto8090OC,was
titratedwith thepermanganatesolutionslowly(1015mL min
1
)andwith
constant stirring until the first permanent faint pink colour was obtained; the constantstirring untilthefirstpermanentfaintpinkcolour wasobtained;the
temperaturenear theendpointwasnotallowedtofall below60
o
C.However
withthisprocedure theresultsmaybe0.10.45percenthigh;thetitre depends
upon the acidity the temperature the rate of addition of the permanganate upontheacidity,the temperature,therateofadditionofthepermanganate
solution,andthespeed ofstirring.Becauseofthisitisbesttomakeamorerapid
additionof9095 percentofthepermanganatesolution(about2535mL min')
to a solution of sodium oxalate in 1 M sulphuric acid at 25 30 OC the solution is toasolution ofsodiumoxalatein1Msulphuric acidat2530OC,thesolutionis
thenwarmed to5560OCandthetitrationcompleted,thelast0.51mL portion
being addeddropwise.
DETERMINATIONOFHYDROGENPEROXIDE
d id i ll d i h f f Hydrogenperoxideisusuallyencounteredintheformofan
aqueoussolution containingabout6percent,12percentor
30 per cent hydrogen peroxide and frequently referred to as 30percenthydrogenperoxide,and frequentlyreferredtoas
'20volume','40volume',and'100volume'hydrogen
peroxiderespectively;thisterminologyisbaseduponthe
volumeofoxygen liberatedwhenthesolutionisdecomposed
byboiling.Thus1mL of'100volume'hydrogenperoxidewill
i ld 100 L f d d d yield100mL ofoxygenmeasuredatstandard temperature
andpressure.
DETERMINATIONOFNITRITES
Ni i i id l i ( 40
o
C) i h Nitritesreactinwarmacidsolution(ca 40
o
C)withpermanganate
solutioninaccordancewiththeequation :
If a solution of a nitrite is titrated in the ordinary way with Ifasolutionofanitriteistitratedintheordinarywaywith
potassium permanganate,poorresultsareobtained,becausethe
nitritesolutionhasfirst tobeacidifiedwithdilutesulphuric acid.
Nitrousacidisliberated,whichbeing volatileandunstable,is
partiallylost.If,however,ameasuredvolumeofstandard
t i t l ti idifi d ith dil t l h i potassiumpermanganatesolution,acidifiedwithdilutesulphuric
acid,istreated withthenitritesolution,addedfromaburette,
until the permanganate is just decolorised results accurate to untilthepermanganateisjust decolorised,resultsaccurateto
0.51percentmaybeobtained.Thisisdueto thefactthat
nitrousaciddoesnotreactinstantaneouslywiththe
permanganate. Thismethodmaybeusedtodeterminethepurity
ofcommercialpotassium nitrite.
2.Di(orBi)chromatometricTitration
Potassiumdichromateisnotsuchapowerfuloxidising agentas
potassium permanganate but it has several advantages over the potassium permanganate,but ithasseveraladvantagesoverthe
lattersubstance.Itcanbeobtainedpure,it isstableuptoitsfusion
point,anditisthereforeanexcellentprimarystandard. Standard
solutionsofexactlyknownconcentrationcanbepreparedby
weighing outthepuredrysaltanddissolvingitintheproper
l f t F th th l ti t bl volumeofwater. Furthermore,theaqueoussolutionsarestable
indefinitelyifadequately protectedfromevaporation.Potassium
dichromate is used only in acid solution, and is reduced rapidly at dichromateisusedonlyinacidsolution, andisreducedrapidlyat
theordinarytemperaturetoagreenchromium(III) salt.
In acid solution :
The green colour due to the Cr
3+
ions formed by the Thegreencolour duetotheCr
3+
ionsformedbythe
reductionofpotassium dichromatemakesitimpossible
to ascertain the end point of a dichromate titration by toascertaintheendpointofadichromate titrationby
simplevisualinspectionofthesolutionandsoaredox
indicator must be employed which gives a strong and indicator mustbeemployedwhichgivesastrongand
unmistakablecolour change;this procedurehas
rendered obsolete the external indicator method which renderedobsoletetheexternalindicatormethodwhich
was formerlywidelyused.
Suitable indicators for use with dichromate titrations Suitableindicatorsforusewithdichromatetitrations
includeNphenylanthranilic acid(0.1percentsolutionin
0 005 M NaOH) and sodium diphenylamine sulphonate 0.005MNaOH)and sodiumdiphenylaminesulphonate
(0.2percentaqueous solution);thelatter mustbeused
in presence of phosphoric (V) acid inpresenceofphosphoric (V)acid.
DETERMINATIONOFC.O.D
Oneveryimportantapplicationofpotassium
dichromateisina backtitrationfortheenvironmental
determinationoftheamountofoxygen requiredto
oxidise all theorganicmaterialinasampleofimpure
water,such assewageeffluent.Thisisknownasthe
chemicaloxygendemand(C.O.D.)and isexpressedin
termsofmilligramsofoxygenrequiredperlitre ofwater,
mgL
1
.
Theanalysisoftheimpurewatersampleiscarriedoutin
parallelwithablank determinationonpure,double
distilledwater.
Procedure.
Place a 50 mL volume of the water sample in a 250 mL conical flask with a Placea50mL volumeofthewatersampleina250mL conical flaskwitha
groundglassneckwhichcanbefittedwithawatercondenserfor refluxing.
Add1gofmercury(II)sulphate,followedby80mL ofasilver sulphate/
sulphuric acid solution Then add 10 mL of approximately 0 00833 M standard sulphuric acidsolution.Thenadd10mL ofapproximately 0.00833 M standard
potassiumdichromatesolution,fittheflaskwith therefluxcondenserand
boilthemixturefor15minutes.Oncoolingrinsethe insideofthecondenser
i h f i h fl k dd i h di h l i with50mL ofwaterintotheflaskcontents.Addeither diphenylamine
indicator(1mL)orferroin indicatorandtitratewith0.025 M ammonium
iron(II)sulphatesolution.Diphenylaminegivesacolourchangefromblueto
greenattheendpoint,whilstthatforferroin isbluegreen toredbrown.Call
thistitrationAmL. Repeatthebacktitrationfortheblank(titrationB mL).The
differencebetweenthetwovaluesistheamountof potassiumdichromate p
usedupintheoxidation.
TheC.O.D.iscalculatedfrom therelationship:
C.O.D.=(A B)x0.2x20mgL
1
as a 1 mL difference between the titrations corresponds to 0 2 mg of oxygen asa1mL differencebetweenthetitrationscorrespondsto0.2mgofoxygen
requiredbythe50mL sample(acorrectionmust,ofcourse,bemadeif
solutions ofslightlydifferentmolaritiesareemployed).
3.CerimetricTitration 3. Ce et c t at o
Cerium(IV)sulphate isapowerfuloxidising agent;itsreduction
potential in 0 5 4 0 M sulphuric acid at 25
o
C is 1 43 + 0 05 volts potentialin 0.54.0Msulphuric acidat25
o
Cis1.43 +0.05volts.
Itcanbeusedonlyin acidsolution,bestin0.5 Morhigher
concentrations :asthesolutionis neutralised,cerium(IV) concentrations : as the solution is neutralised, cerium(IV)
hydroxide[hydratedcerium(IV)oxide]orbasicsalts precipitate.
Thesolutionhasanintenseyellowcolour,andinhotsolutions
whicharenottoodilutetheendpointmaybedetectedwithout
an indicator anindicator.
Thisprocedure,however,necessitatesthapplication ofablank
correction,and itisthereforepreferabletoaddasuitable , p
indicator.
Theadvantagesofcerium(IV)sulphate asastandardoxidising
agentare : g
1.Cerium(IV)sulphate solutionsareremarkablystableover
prolongedperiods. Theyneednotbeprotectedfromlight,andmay
b b il d f h i i h i bl h i evenbeboiledforashort timewithoutappreciablechangein
concentration.Thestabilityofsulphuric acidsolutionscoversthe
wide range of 1040 mL of concentrated sulphuric acid per litre It is widerangeof1040mL ofconcentratedsulphuric acidperlitre.Itis
evident,therefore,thatanacidsolutionofcerium(IV) sulphate
surpassesapermanganatesolutioninstability.
2.Cerium(IV)sulphate maybeemployedinthedeterminationof
reducing agentsinthepresenceofahighconcentrationofHCl.
3 C i (IV) l i i 0 1 M l i hi hl 3.Cerium(IV)solutionsin0.1Msolutionarenottoohighly
coloured toobstruct visionwhenreadingthemeniscusinburettes
and other titrimetric apparatus andothertitrimetric apparatus.
4.Inthereactionofcerium(IV)saltsinacidsolutionwithreducing
agents,the simplechangeisassumedtotakeplace.With
permanganate,ofcourse,anumberofreduction productsare
producedaccordingtotheexperimentalconditions.
StandardizationofCerium(IV)sulphate
MethodA :Standardisation witharsenic(III)oxide.
Themost trustworthymethodforstandardising cerium(IV)
sulphate solutionsiswith purearsenic(III)oxide.Thereaction
betweencerium(IV)sulphate solutionand arsenic(III)oxideisvery
l t th bi t t t it i t dd t f slowattheambienttemperature;itisnecessaryto addatraceof
osmiumtetroxide ascatalyst.Thearsenic(III)oxideisdissolved in
sodium hydroxide solution, the solution acidified with dilute sodiumhydroxidesolution,thesolutionacidifiedwithdilute
sulphuric acid, andafteradding2dropsofan'osmic acid'solution
preparedbydissolving 0.1gosmiumtetroxide in40mL of0.05M
sulphuric acid,andtheindicator (12dropsferroin or0.5mL N
phenylanthranilic acid),itistitratedwiththe cerium(IV)sulphate
l ti t th fi t h l h d t l solutiontothefirstsharpcolour change :orangeredto verypale
blueoryellowishgreentopurplerespectively.
MethodB :Standardisation withsodiumoxalate.
Standardisation mayalsobe carriedoutwithsodiumoxalate;in
thiscase,anindirectproceduremustbe usedastheredox this case, an indirect procedure must be used as the redox
indicatorsarethemselvesoxidised attheelevatedtemperatures
whicharenecessary.Theprocedure,therefore,istoaddan
excessofthe cerium(IV)solution,andthen,aftercooling,the
excessisdeterminedby backtitrationwithaniron(II)solution.
Itispossibletocarryoutadirect titrationofthesodiumoxalate
ifapotentiometric procedureisused. p p
Practicallyall thedeterminationsdescribedunderpotassiumpermanganate
and potassium dichromate may be carried out with cerium(IV) sulphate Use andpotassiumdichromatemaybecarriedoutwithcerium(IV)sulphate.Use
ismadeofthevariousindicatorsalreadydetailedandalso,insomecases
where greataccuracyisnotrequired,ofthepaleyellowcolour producedby
the cerium(IV)sulphate itself.Onlyafewdeterminationswill,therefore,be
consideredinsomedetail.
Determinationofcopper:
Copper(II) ions are quantitatively reduced in 2M hydrochloric Copper(II)ionsarequantitativelyreducedin2Mhydrochloric
acidsolutionbymeansofthesilverreductor tothecopper(I)
state.Thesolution,afterreduction,iscollectedinasolutionof state. The solution, after reduction, is collected in a solution of
ammonium iron(III)sulphate,andtheFe
2+
ionformedistitrated
withstandardcerium(IV) sulphate solutionusingferroin orN
phenylanthranilic acidasindicator.
Determination of nitrites : Determinationofnitrites:
Satisfactoryresultsareobtainedbyaddingthenitritesolutionto
excessofstandard0.1Mcerium(IV)sulphate,anddetermining ( ) p , g
theexcessof cerium(IV)sulphate withastandardiron(II)
solution.
Forpractice,determinethepercentageofNO;inpotassium
nitrite or the purity of sodium nitrite preferably of analytical nitrite,orthe purityofsodiumnitrite,preferablyofanalytical
gradequality.
4.IodiometricTitration
Thedirectiodometric titrationmethod(sometimestermed
iodimetry)refersto titrationswithastandardsolutionofiodine. y)
Theindirectiodometric titration method(sometimestermed
iodometry)dealswiththetitrationofiodineliberated inchemical
reactions.
The normal reduction potential of the reversible system: Thenormalreductionpotentialofthereversiblesystem:
I
2 (solid)
+2e 2I

is0.5345volt.
2 (solid)
Theaboveequationreferstoasaturatedaqueoussolutioninthe
presenceofsolidiodine;thishalfce11reactionwilloccur,for
example,towards theendofatitrationofiodidewithan
oxidising agent such as potassium permanganate when the oxidising agentsuchaspotassium permanganate,whenthe
iodideionconcentrationbecomesrelativelylow.
Nearthebeginning,orinmostiodometric titrations,whenan
excess of iodide ion is present the tri iodide ion is formed excessofiodideionis present,thetriiodideionisformed
sinceiodineisreadilysolubleinasolutionofiodide.Thehalf
ce11reactionis betterwritten:
and the standard reduction potential is 0 5355 volt Iodine or andthestandardreductionpotentialis0.5355volt.Iodineor
thetriiodideion isthereforeamuchweakeroxidising agent
thanpotassiumpermanganate, potassiumdichromate,and p p g , p ,
cerium(IV)sulphate.
Inmostdirecttitrationswithiodine(iodimetry)asolutionof
iodinein potassiumiodideisemployed,andthereactivespecies
isthereforethetriiodide ionI
3

.Strictlyspeaking,all equations
involving reactions of iodine should be written with I

rather involvingreactionsofiodineshouldbe writtenwithI
3
rather
thanwithI
2
e.g.
Inmostdirecttitrationswithiodine(iodimetry)asolutionof
i di i i i did i l d d h i i iodinein potassiumiodideisemployed,andthereactivespecies
isthereforethetriiodide ionI
3

.Strictlyspeaking,all equations
involving reactions of iodine should be written with I

rather involvingreactionsofiodineshouldbe writtenwithI
3
rather
thanwithI
2
e.g.
ismoreaccuratethan
Strong reducing agents (substances with a much lower reduction potential), Strongreducingagents(substanceswithamuchlowerreductionpotential),
suchastin(II)chloride,sulphurousacid,hydrogensulphide,andsodium
thiosulphate,reactcompletelyandrapidlywithiodineeveninacidsolution.
With somewhat weaker reducing agents e g arsenic(III) or antimony(III) Withsomewhatweakerreducingagents,e.g.arsenic(III),orantimony(III),
completereactionoccursonlywhenthesolutioniskeptneutralorveryfaintly
acid;undertheseconditionsthereductionpotentialofthereducingagentisa
i i it d i i i minimum,oritsreducingpowerisamaximum.
Twoimportantsourcesoferrorintitrationsinvolvingiodineare :
(a) loss of iodine owing to its appreciable volatility; and (a) lossof iodineowingtoitsappreciablevolatility;and
(b)acidsolutionsofiodideare oxidised byoxygenfromtheair.
Inthepresenceofexcessofiodide,thevolatilityisdecreased
k dl th h th f ti f th t i i did i t markedlythrough theformationofthetriiodideion;atroom
temperaturethelossofiodineby volatilisation fromasolution
containing at least 4 per cent of potassium iodide is negligible containingatleast4percentofpotassiumiodide isnegligible
providedthetitrationisnotprolongedunduly.
Titrationsshould beperformedincoldsolutionsinconicalflasks
andnotinopenbeakers.Ifa solutionistostanditshouldbekept
inaglassstoppered vessel. Theatmosphericoxidationofiodideis
li ibl i t l l ti i th b f t l t b t th negligibleinneutralsolutionintheabsenceofcatalysts, butthe
rateofoxidationincreasesrapidlywithdecreasingpH.
The reaction is catalysed by certain metal ions of variable charge The reactionis catalysed bycertainmetalionsofvariablecharge
value(particularlycopper),by nitriteion,andalsobystronglight.
Itseemsappropriatetoreferatthispointtotheusesofa standard
solution containing potassium iodide and potassium iodate solution containingpotassiumiodideandpotassiumiodate.
Thissolutionisquitestable andyieldsiodinewhentreatedwith
acid : acid :
Thestandardsolutionispreparedbydissolvingaweighedamount
ofpure potassiumiodate inasolutioncontainingaslightexcessof
pure potassium iodide and diluting to a definite volume purepotassium iodide,anddilutingtoadefinitevolume.
Thissolutionhastwoimportantuses : p
Thefirstisasasourceofaknownquantityofiodineintitrations;it
mustbeaddedtoasolutioncontainingstrongacid;it cannotbe
employedinamediumwhichisneutralorpossessesalowacidity.
Theseconduseisinthedeterminationoftheacidcontentof
solutions iodometrically or in the standardisation of solutions of solutions iodometrically orinthestandardisation ofsolutionsof
strongacids.
DetectionoftheEndPoint
Asolutionofiodineinaqueousiodidehasanintenseyellowto
browncolour. Onedropof0.05 Miodinesolutionimpartsa
bl l ll l f h perceptiblepaleyellowcolour to100mL ofwater,sothatin
otherwisecolourless solutionsiodinecanserve asitsown
indicator The test is made much more sensitive by the use of a indicator.Thetestismademuchmoresensitivebytheuseofa
solutionofstarchasindicator.Starchreactswithiodineinthe
presenceofiodide toformanintenselybluecoloured complex, p y p
whichisvisibleatverylow concentrationsofiodine.Thesensitivity
ofthecolour reactionissuchthata bluecolour isvisiblewhenthe
i di i i 2 10 d h i did i i iodineconcentrationis2x10

Mandtheiodide concentrationis
greaterthan4x10
4
Mat20C.
Thecoloursensitivitydecreaseswithincreasingtemperatureofthesolution;
thusat50
o
Citisabout tentimeslesssensitivethanat25
o
C.Thesensitivity
decreases upon the addition of solvents such as ethanol : no colour is obtained decreasesupontheaddition ofsolvents,suchasethanol :nocolour isobtained
insolutionscontaining 50%ethanolormore.Itcannotbeusedinastronglyacid
medium becausehydrolysisofthestarchoccurs.
Thecoloursensitivitydecreaseswithincreasingtemperatureof
the solution; thus at 50
o
C it is about ten times less sensitive than thesolution;thusat50 Citisabout tentimeslesssensitivethan
at25
o
C.Thesensitivitydecreasesupontheaddition ofsolvents,
suchasethanol :nocolour isobtainedinsolutionscontaining
50percentethanolormore.Itcannotbeusedinastronglyacid
medium becausehydrolysisofthestarchoccurs.
Starchescanbeseparatedintotwomajorcomponents,amylose
and amylopectin, which exist in different proportions in various and amylopectin,whichexistindifferentproportionsinvarious
plants.
Amylose, whichisastraightchaincompoundandisabundantin
potatostarch,givesa bluecolour withiodineandthechain
i l f assumesaspiralform.
Amylopectin, which has a branchedchain structure, forms a red Amylopectin,which hasabranched chainstructure,formsared
purpleproduct,probablyby adsorption.
Thegreatmeritofstarch isthatitisinexpensive.Itpossessesthe
following disadvantages : following disadvantages :
(1) insolubilityincoldwater;
(2) instabilityofsuspensionsin water;
(3) itgivesawaterinsolublecomplexwithiodine,theformation
ofwhich precludestheadditionoftheindicatorearlyinthe
tit ti (f thi i tit ti f i di th t h titration(forthisreason,in titrationsofiodine,thestarch
solutionshouldnotbeaddeduntiljustpriorto theendpoint
when the colour begins to fade); and whenthecolour beginstofade);and
(4) thereissometimesa 'drift'endpoint,whichismarkedwhen
thesolutionsaredilute.
Mostoftheshortcomingsofstarchasanindicatorareabsentinsodium starch
glycollate.Thisisawhite,nonhygroscopicpowder,readilysolublein hot g y , yg p p , y
watertogiveafaintlyopalescentsolution,whichisstableformanymonths; it
doesnotformawaterinsolublecomplexwithiodine,andhencetheindicator
may be added at any stage of the reaction maybeaddedatanystageofthereaction.
Carbontetrachloridehasbeenusedincertainreactionsinstead
of starch solution One litre of water at 25 OC will dissolve 0 335 ofstarch solution.Onelitre ofwaterat25OCwilldissolve0.335
gofiodine,butthesame volumeofcarbontetrachloridewill
dissolveabout28.5g.Iodineistherefore about85timesas
solubleincarbontetrachlorideasitisinwater,andthe
carbontetrachloride solutionishighlycoloured.Whenalittle
b t t hl id i dd d t l ti t i i carbontetrachlorideis addedtoanaqueoussolutioncontaining
iodineandthesolutionwellshaken, thegreatpartoftheiodine
will dissolve in the carbon tetrachloride; the latter will fall to the willdissolveinthecarbontetrachloride;thelatter willfall tothe
bottomsinceitisimmisciblewithwater,andthecolour ofthe
organiclayerwillbemuchdeeperthanthatoftheoriginal
aqueoussolution.
Thereddishvioletcolour ofiodineincarbontetrachlorideis
i ibl i l t ti f i di th h ki 10 visibleinverylow concentrationsofiodine;thusonshaking10
mL ofcarbontetrachloridewith 50mL of10
5
Miodine,a
distinct violet coloration is produced in the organic layer. This distinctvioletcolorationisproducedintheorganic layer.This
enablesmanyiodometric determinationstobecarriedoutwith
comparativeease.
StandardizationofIodineSolution
(A) Witharsenic(III)oxide :
Arsenic(II1) oxide which has been dried at 105110
o
C for two Arsenic(II1)oxidewhichhasbeendriedat105 110 Cfortwo
hoursisan excellentprimarystandard.Thereactionbetweenthis
substanceandiodineis areversibleone:
d l d tit ti l f l ft t i ht if th h d andonlyproceedsquantitativelyfromlefttorightifthehydrogen
iodideis removedfromthesolutionasfastasitisformed.
This may be done by the addition of sodium hydrogencarbonate : Thismaybedoneby theadditionofsodiumhydrogencarbonate :
sodiumcarbonateandsodium hydroxidecannotbeused,since
theyreactwiththeiodine,formingiodide,hypoiodite,andiodate.
Actuallyithasbeenshownthatcompleteoxidationof thearsenite
occurswhenthepHofthesolutionliesbetween4and9,thebest
l b i 6 5 hi h i l t th t l i t B ff valuebeing6.5,whichisveryclosetotheneutralpoint.Buffer
solutions areemployedtomaintainthecorrectpH.
(B)Withstandardsodiumthiosulphate solution.
di hi l h l i hi h h b l Sodiumthiosulphate solution, whichhasbeenrecently
standardised,preferablyagainstpurepotassiumiodate, is
employed Transfer 25 mL of the iodine solution to a 250 mL employed.Transfer25mL oftheiodinesolutiontoa250mL
conicalflask, diluteto100mL andaddthestandardthiosulphate
solutionfromaburette untilthesolutionhasapaleyellow
colour.Add2mL ofstarchsolution,and continuetheadditionof
thethiosulphate solutionslowlyuntilthesolutionis just
l l colourless.
Sodium thiosulphate (Na S O 5H 0) is readily obtainable in a Sodiumthiosulphate (Na
2
S
2
O
4
.5H
2
0)isreadilyobtainableina
stateofhighpurity,butthereisalwayssomeuncertaintyasto
theexactwater contentbecauseoftheefflorescentnatureof
thesaltandforotherreasons.The substanceistherefore
unsuitableasaprimarystandard.Itisareducingagent byvirtue
f th h lf ll ti ofthehalfcell reaction :
Itisnecessarytoreferbrieflytothestabilityof thiosulphate
solutions Solutions prepared with conductivity (equilibrium) solutions.Solutionspreparedwithconductivity(equilibrium)
water areperfectlystable.However,ordinarydistilledwater
usuallycontainsanexcess ofcarbondioxide;thismaycausea usually contains an excess of carbon dioxide; this may cause a
slowdecompositiontotakeplacewiththe formationofsulphur:
Moreover,decompositionmayalsobecausedbybacterialaction
(e g Thiobacillus thioparus) particularly if the solution has been (e.g. Thiobacillus thioparus),particularlyifthesolutionhasbeen
standingforsome time.Forthesereasons,thefollowing
recommendationsaremade:
1.Preparethesolutionwithrecentlyboileddistilledwater.
2.Add3dropsofchloroformor10mgL
1
ofmercury(II)iodide;
these compoundsimprovethekeepingqualitiesofthesolution.
BacterialactivityisleastwhenthepHliesbetween9and10.The
addition of a small amount 0 1 g L
1
of sodium carbonate is addition ofasmallamount,0.1gL
1
,ofsodiumcarbonateis
advantageoustoensure thecorrectpH.
Ingeneral,alkalihydroxides,sodiumcarbonate(>0.1gL
1
),
and sodium tetraborate should not be added since they tend to andsodiumtetraborate shouldnotbeadded,sincetheytendto
accelerate thedecomposition:
3.Avoidexposuretolight,asthistendstohastenthe
d iti decomposition.
The standardisation of thiosulphate solutions may be effected Thestandardisation ofthiosulphate solutionsmaybeeffected
withpotassium iodate,potassiumdichromate,copperandiodine
asprimarystandards,orwith potassiumpermanganateor
cerium(IV)sulphate assecondarystandards.
Owing tothevolatilityofiodineandthedifficultyofpreparation
f f tl i di thi th d i t it bl f ofperfectlypure iodine,thismethodisnotasuitableonefor
beginners.If,however,astandard solutionofiodineisavailable,
this may be used for the standardisation of thiosulphate thismaybeused forthestandardisation ofthiosulphate
solutions.
Standardizationofsodiumthiosulphatesolution
(A) Withpotassiumiodate.
Potassiumiodate hasapurityofatleast99.9percent :
itcanbedriedat120
o
C.Thisreactswithpotassiumiodidein
acidsolutionto liberateiodine:
Itsrelativemolecularmassis214.00;a0.02 Msolutiontherefore
contains 4.28 g of potassium iodate per litre. contains4.28g ofpotassiumiodateperlitre.
(B)Withpotassiumdichromate.
Potassiumdichromateisreducedbyanacid solutionof
potassium iodide and iodine is set free : potassiumiodide,andiodineissetfree :
Thisreactionissubjecttoanumberoferrors :
(1) thehydriodic acid(from excessofiodideandacid)isreadily
idi d b i i ll i h f h i (III) oxidised byair,especiallyinthepresence ofchromium(III)
salts,and
(2) it is not instantaneous It is accordingly best to pass a (2) itisnotinstantaneous.Itisaccordinglybestto passa
currentofcarbondioxidethroughthereactionflaskbefore
andduring thetitration(amoreconvenientbutless
efficientmethodistoaddsomesolid sodium hydrogen
carbonatetotheacidsolution,andtokeeptheflask
d h ibl ) d t ll 5 i t f it covered asmuchaspossible),andtoallow5minutesforits
completion.
DeterminationofArsenic(V)
Thereactionisthereverseofthatemployedinthe standardi
sation ofiodine withsodiumarsenite solution:
Forgoodresults,thefollowing experimentalconditionsmustbe
observed :
(1) The hydrochloricacid concentrationinthefinalsolution
shouldbeatleast4 M;
(2) Ai h ld b di l d f h i i i b ddi (2) Air shouldbedisplacedfromthetitrationmixturebyaddinga
littlesolidsodium hydrogencarbonate;
(3) The solution must be allowed to stand for at least 5 minutes (3) Thesolutionmustbeallowedtostandforatleast 5minutes
beforetheliberatediodineistitrated;and
(4) Constantstirringis essentialduringthetitrationtoprevent
decompositionofthethiosulphate in thestronglyacid
solution.
5 Iodatometric Titration 5.IodatometricTitration
Potassiumiodate isapowerfuloxidising agent,butthecourseof p g g ,
thereaction isgovernedbytheconditionsunderwhichitis
employed.Thereactionbetween potassiumiodate andreducing
agentssuchasiodideionorarsenic(III)oxide insolutionsof
moderateacidity(0.12.0Mhydrochloricacid)stopsatthestage
when the iodate is reduced to iodine : whentheiodate isreducedtoiodine :
l d i di d h fi f h i i f l f Asalreadyindicated,thefirstofthesereactionsisveryusefulfor
thegeneration ofknownamountsofiodine,anditalsoservesas
the basis of a method for standardising solutions of acids thebasisofamethodfor standardising solutionsofacids.
Withamorepowerfulreductant,e.g.titanium(III)chloride,the
iodate is reducedtoiodide:
l id l i ( h d hl i id) d i Inmorestronglyacidsolutions(36 Mhydrochloricacid)reduction
occursto iodinemonochloride,anditisundertheseconditions
that it is most widely used thatitismostwidely used.
Inhydrochloricacidsolution,iodinemonochloride formsastable
complexion withchlorideion:
The overall halfcell reaction may therefore be written as: Theoverallhalfcell reactionmaythereforebewrittenas:
Thereductionpotentialis1.23volts;henceundertheseconditions
potassium iodate actsasaverypowerfuloxidising agent.
Oxidationbyiodate ioninastronghydrochloricacidmedium
proceeds through several stages : proceeds throughseveralstages:
Intheinitialstagesofthereactionfreeiodineisliberated :as
more titrant is added oxidation proceeds to iodine monochloride moretitrant is added,oxidationproceedstoiodinemonochloride,
andthedarkcolour ofthe solutiongraduallydisappears.
Theoverallreactionmaybewrittenas : y
Thereactionhasbeenusedforthedeterminationofmany
reducingagents.
Under these conditions (2 59 0 M of HCl) starch cannot be used Undertheseconditions(2.5 9.0MofHCl)starchcannotbeused
asindicatorbecausethe characteristicbluecolour ofthest arch
iodinecomplexisnotformedathigh concentrationsof acid.
Intheoriginalprocedure,afewmillilitres of animmiscible
solvent(carbontetrachlorideorchloroform)wereaddedtothe
l ti b i tit t d t i d i l t d b ttl solutionbeing titratedcontainedinaglassstoppered bottleor
conicalflask.
The end point is marked by the disappearance of the last trace Theendpointis markedbythedisappearanceofthelasttrace
ofvioletcolour,duetoiodine, fromthesolvent:iodine
monochloride isnotextractedandimpartsapale yellowish
colour totheaqueousphase.Theextractionendpointisvery
sharp.
Th i di d t i th i i f i h ki Themaindisadvantageistheinconvenienceofvigorousshaking
withthe extractionsolventinastoppered vesselaftereach
addition of the reagent near the end point. additionofthereagentnear theendpoint.
Preparationof0.025MPotassiumIodateSolution
Drysomepotassiumiodate at120
o
Cfor1hourandallowittocool
ina coveredvesselinadesiccator.Weighoutexactly5.350gofthe in a covered vessel in a desiccator. Weigh out exactly 5.350 g of the
finelypowdered potassiumiodate onawatchglass,andtransferit
bymeansofacleancamelhair brushdirectlyintoadry1L
graduatedflask.Addabout400500mL ofwater, andgentlyrotate
theflaskuntilthesaltiscompletelydissolved.Makeupto themark
with distilled water Shake well The solution will keep indefinitely withdistilledwater.Shakewell.Thesolutionwillkeepindefinitely.
Itmustbeemphasised thatthis0.025 Msolutionisintendedfor
thereaction:
butwhenusedinsolutionsofmoderateacidityleadingtothe
liberationoffree iodine,ideallythesolutionthenrequires4.28gL
1
potassium iodate; the method of preparation will be as described potassium iodate;themethodofpreparationwillbeasdescribed
abovewithsuitable adjustmentoftheweightofsalttaken.
DeterminationofArsenicandofAntimony
Thedeterminationofarsenicinarsenic(III)compoundsisbased
upon the following reaction : uponthefollowingreaction:
Asimilarreactionoccurswithantimony(III)compounds.The
determination ofantimony(III)inthepresenceoftartrate isnot
verysatisfactorywithan immisciblesolventtoassistinindicating
the end point; amaranth however gives excellent results theendpoint;amaranth,however, givesexcellentresults.
6.BromatometricTitration
Potassiumbromate isapowerfuloxidising agentwhichisreduced
smoothly to bromide : smoothlyto bromide:
Therelativemolecularmassis167.00,anda0.02 Msolution
contains3.34gL
1
potassiumbromate.Attheendofthetitration
f b i freebromineappears :
Thepresenceoffreebromine,andconsequentlytheendpoint,
canbedetected byitsyellowcolour,butitisbettertouse
indicatorssuchasmethylorange, methylred,naphthaleneblack
12B,xylidineponceau,andfuchsine.Theseindicatorshavetheir
l l i id l ti b t d t d b th fi t usualcolour inacidsolution,butaredestroyedbythe firstexcess
ofbromine.
Withall irreversibleoxidationindicatorsthedestruction ofthe
indicatorisoftenprematuretoaslightextent :alittleadditional
indicator is usually required near the end point The quantity of indicator isusuallyrequiredneartheendpoint.Thequantityof
bromate solution consumedbytheindicatorisexceedingly
small, and the 'blank' can be neglected for 0.02 M solutions. small,andthe blank canbeneglected for0.02 Msolutions.
Directtitrationswithbromate solutioninthepresenceof
irreversibledyestuffindicatorsareusuallymadeinhydrochloric
acidsolution, theconcentrationofwhichshouldbeatleast
1.52 M.
At the end of the titration some chlorine may appear by virtue of Attheendofthetitration somechlorinemayappearbyvirtueof
thereaction :
Thisimmediatelybleachestheindicator.
Examplesofdeterminationsutilising directtitrationwith
bromate solutions areexpressedinthefollowingequations : p g q
Varioussubstancescannotbeoxidised directlywithpotassium
bromate,but reactquantitativelywithanexcessofbromine.
Acidsolutionsofbromineof exactlyknownconcentrationare
readily obtainable from a standard potassium bromate solution readilyobtainablefromastandardpotassium bromate solution
byaddingacidandanexcessofbromide :
Inthisreaction1moleofbromate yieldssixatomsofbromine.
Bromine is very volatile and hence such operations should be Bromineisvery volatile,andhencesuchoperationsshouldbe
conductedataslowatemperature aspossibleandinconicalflasks
fittedwithgroundglassstoppers.Theexcess ofbrominemaybe fitted with ground glass stoppers. The excess of bromine may be
determinediodometrically bytheadditionofexcessof potassium
iodideandtitrationoftheliberatediodinewithstandard
thiosulphate solution:
Potassiumbromate isreadilyavailableinahighstateofpurity;the
product hasanassayvalueofatleast99.9percent.Thesubstance p y p
canbedriedat 120150
o
C,isanhydrous,andtheaqueoussolution
keepsindefinitely.Itcan thereforebeemployedasaprimary
standard.Itsonlydisadvantageisthat onesixthoftherelative
molecularmassisacomparativelysmallquantity.
DeterminationofArsenicandofAntimony
Theantimonyorthearsenicmustbepresentasantimony(III)or
arsenic(III) The reaction of arsenic(III) or antimony(III) with arsenic(III).Thereactionofarsenic(III)orantimony(III)with
potassium bromatemaybewritten:
Th f ti d f id bl titi f i d Thepresenceoftinandofconsiderablequantitiesofironand
copperinterfere withthedeterminations.
Determinationofphenol
Anumberofphenolscanbesubstitutedrapidlyand
quantitatively with bromine produced from bromate and quantitatively withbromineproducedfrombromate and
bromideinacidsolution.Thedeterminationinvolvestreating
phenolwithanexcessofpotassiumbromate andpotassium
bromide;whenbromination ofthe phenoliscompletethe
unreacted bromineisthendeterminedbyaddingexcess
t i i did d b k tit ti th lib t d i di ith potassiumiodideandbacktitratingtheliberatediodinewith
standardsodium thiosulphate.
End End