REDOX

Reduction Oxidation Titration

ReductionOxidation
An application method of
InorganicPharmaceuticalAnalysis

Lecturer:Dr.TutusGusdinar
PharmacochemistryResearchGroup
SchoolofPharmacy
INSTITUTTEKNOLOGIBANDUNG
Inacidbasetitrations,thechangeinpHduringtitration
In acidbase titrations the change in pH during titration
maybecalculated,andthetitrationcurvesthus
obtained can be usedtoascertainthemostsuitable
obtainedcanbe used to ascertain the most suitable
indicatortobeusedinagiventitration, andto
determine the titration error
determinethetitrationerror.

Similarproceduresmaybecarriedout
Similar procedures may be carried out foroxidation
for oxidation
reductiontitrations.Considerfirstasimplecasewhich
involves onlychangeinioniccharge,andistheoretically
only change in ionic charge and is theoretically
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 sulphuricacid.
(IV)inthepresenceofdilute sulphuric acid
 EE=EEo +0.0591/n.log[Ox]/[Red]at25
0 0591/ l [O ]/[R d] t 25 oC

Standardpotentials Eo 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 onemoleeachof
experimentallyinasolutioncontaining one mole each of
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 thatispresent.
thenatureandconcentrationoftheacid that is present
Theformal potentialincorporatesinonevaluetheeffects
resulting fromvariationofactivitycoefficientswithionic
from variation of activity coefficients with ionic
strength,acidbasedissociation, complexation,liquid
junction potentials etc and thus has a real practical
junctionpotentials,etc.,andthushasarealpractical
value. Formal potentialsdonothavethetheoretical
significance of standard potentials buttheyareobserved
significanceofstandardpotentials, but they are observed
valuesinactualpotentiometric measurements.
100mL
100 mL of0.1Miron(II)with0.1M
of 0 1 M iron(II) with 0 1 M cerium (IV)inthe
(IV) in the
presenceofdilute sulphuricacid:

Thequantitycorrespondingto[H+]inacidbasetitration
istheratio [Ox]/[Red].Weareconcernedherewithtwo
systems : 1)theFe3+/Fe2+ ion electrode,and
2)theCe4+/Ce3+ ionelectrode.
For(1)at25oC:

Th
Theequilibriumconstantofthereactionisgivenby
ilib i f h i i i b
Duringtheadditionofthecerium(IV)solutionuptothe
During the addition of the cerium(IV) solution up to the
equivalencepoint, itsonlyeffectwillbetooxidisethe
iron(II) since K is large andconsequently
iron(II),sinceKislarge, and consequently changethe
change the
ratio[Fe3+]/[Fe2+].

When10mLoftheoxidisingagenthave beenadded,
[Fe3+]/[Fe2+]=10/90(approximately)and
] = 10/90 (approximately) and
E1 =0.75+0.0591log10/90=0.75 0.056=0.69volt

With50mLoftheoxidisingagent,E1 =Eo1=0.75volt
With 90 mL E1 =0.75+0.0591log90/10=0.81volt
With90mL,E = 0 75 + 0 0591 log 90/10 = 0 81 volt
With99mL,E1 =0.75=0.0591log99/1=0.87volt
With 99 9 mL E1 =0.75+0.0591log99.9/0.1=0.93volt
With99.9mL,E = 0 75 + 0 0591 log 99 9/0 1 = 0 93 volt
Attheequivalencepoint(100.0mL):
h l ( )
[Fe3+]=[Ce3+] and[Ce4+]=[Fe2+]
Theelectrodepotentialisgivenby
h l d i li i b :
(E1 +E2)/2=(0.75+1.45)/2=1.10volts

Thesubsequentadditionofcerium(IV)solutionwill
merelyincreasetheratio
l i h [C 4+]/[Ce
i [Ce ]/[C 3+].
]
Thus:
Wi h 100 1 L E1 =1.45+0.0591log0.1/100=1.27volts
With100.1mL,E 1 45 0 0591 l 0 1/100 1 27 l
With101mL,E1 =1.45+0.0591log1/100=1.33volts
Wi h 110 L E1 =1.45+0.0591log10/100=1.39volts
With110mL,E 1 45 0 0591 l 10/100 1 39 l
With190mL,E1 =1.45+0.0591log90/100=1.45volts
Titrationof100mL of0.1 Miron(II)with0.1 Mcerium(IV)sulphate
 Itisofinteresttocalculatetheiron(II)concentrationin
theneighbourhood
h i hb h d oftheequivalencepoint.When
f h i l i h
99.9mLofthecerium(IV)solutionhavebeen added,
[ 2+
[Fe 2 ]=0.1x0.1/199.9=5x
] / 1055 or pFe2+
2 =4.3.

The
h concentration
i attheequivalencepointisgivenby
h i l i i i b

Now[Fe3+]=0.05 M,hence[Fe2+]=5x102/8.4x105 =6
x 108 M,or
x10 M or pFe2+ =7.2
=72
Upontheadditionof100.1mLofcerium(IV)solution,the
reduction potential is 1 27 volts The [Fe3+]ispractically
reductionpotentialis1.27volts.The[Fe ] is practically
unchanged at5x102 M,andwemaycalculate[Fe2+]
with sufficient accuracy for our purposefromthe
withsufficientaccuracyforour purpose from the
equation:
 E =EEo1 +0.0591log[Fe
E + 0.0591 log [Fe3+]/[Fe
] /[Fe2+]

ThuspFe2+ changesfrom4.3to10between0.1percentbefore
and
d 0.1percentafterthestoichiometricendpoint.
f h i hi i d i
Thesequantitiesareofimportance inconnectionwiththeuseof
indicators for the detection of the equivalence point
indicatorsforthedetectionoftheequivalencepoint.
Itisevidentthattheabruptchangeofthepotentialin
the neighbourhood oftheequivalencepointis
theneighbourhood of the equivalence point is
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
MnO4/Mn2+ 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 Cr2O72/Cr3+ system :thepotentialat
thecurveforthe : the potential at
theequivalencepointcanbedetermined asalready
described.
described
Itispossibletotitratetwosubstancesbythesame
titrant provided that the standardpotentialsofthe
titrantprovidedthatthe standard potentials of the
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
anoxidationpotentialintermediatebetween
id i i li di b thatofthe
h f h
solutiontitrated(analyte)andthatofthetitrant,and
whichexhibitsasharp,readilydetectablecolourchange.
hi h hibi h dil d bl l h

Anredox
d indicator
i di i
isacompoundwhich
d hi h exhibits
hibi
differentcolours intheoxidised andreducedforms :

InOx +ne InRed

Theoxidationandreductionshouldbereversible.Ata
potentialEtheratioof
i lE h i f theconcentrationsofthetwo
h i f h
formsisgivenbytheNernstequation :
whereEo isthestandard(strictlytheformal)potentialof
the indicator If the colour intensitiesofthetwoforms
theindicator.Ifthe intensities of the two forms
arecomparableapracticalestimateofthe colourchange
interval corresponds to the change in the ratio
intervalcorrespondstothechangeintheratio
[InOx]/[InRed] from10to1/10,thisleadstoanintervalof
potential of :
potentialof
Ifthecolour
If the colour intensitiesofthetwoformsdiffer
intensities of the two forms differ
considerablytheintermediate colour isattainedat
potential somewhat removed from Eo,buttheerroris
potentialsomewhatremovedfromE but the error is
unlikelytoexceed0.06volt.

Forasharpcolour changeattheendpoint,Eo should

differ by about at least 0 15 volt from the standard
differbyaboutatleast0.15voltfromthestandard
(formal)potentials oftheothersystemsinvolvedinthe
reaction.
reaction
Oneofthebestoxidationreductionindicatorsisthe
1,10phenanthroline
1,10 phenanthroline iron(II)complex.Thebase1,10
iron(II) complex. The base 1,10
phenanthroline combinesreadilyinsolution with
iron(II) salts in the molecular ratio 3 base: 1 iron(II)ion
iron(II)saltsinthemolecularratio3base: iron(II) ion
formingthe intenselyred1,10phenanthrolineiron(II)
complex ion; with strong oxidising agentstheiron(III)
complexion;withstrongoxidising agents the iron(III)
complexionisformed,whichhasapalebluecolour.
The colour changeisaverystrikingone
change is a very striking one :
Thestandardredox potentialis1.14volts;theformal
potential is 1 06 volts in 1Mhydrochloricacidsolution.
potentialis1.06voltsin 1 M hydrochloric acid solution
Thecolour change,however,occursatabout 1.12volts,
because the colour ofthereducedform(deepred)isso
becausethecolour of the reduced form (deep red) is so
muchmore intensethanthatoftheoxidised form(pale
blue) The indicator is of great value inthetitrationof
blue).Theindicatorisofgreatvalue in the titration of
iron(II)saltsandothersubstanceswithcerium (IV)
sulphate solutions.Itispreparedbydissolving1,10
solutions It is prepared by dissolving 1 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 (knownasferroin).Onedropis
iron(II)complexsulphate (known as ferroin) One drop is
usuallysufficientinatitration :thisisequivalent toless
than 0 01 mL of0.05
than0.01mL of 0 05 Moxidising
M oxidising agent,and
agent and the indicator
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
oxidationfirstintocolourless
id i fi i l l di h lb idi (II),which
diphenylbenzidine (II) hi h isthe
i h
realindicatorandisreversiblyfurtheroxidised to diphenylbenzi
dine violet(III).
violet (III) Diphenylbenzidine violetundergoesfurther
violet undergoes further
oxidationifitisallowed tostandwithexcessofdichromate
solution;thisfurtheroxidationis irreversible, andredoryellow
productsofunknowncompositionareproduced.
Diphenylamine
RedoxTitrationMethods
Permanganometry
Dichromatometryy
Cerimetry
Iodometry&Iodimetry
Iodatometry
Bromatometry
 1.PermanganometricTitration
Thisvaluableandpowerfuloxidisingagentwasfirstintroducedintotitrimetric
analysisbyF.Margueritteforthetitrationofiron(II).Inacidsolutions,the
reduction can be represented by the following equation :
reductioncanberepresentedbythefollowingequation

Thestandardpotentialinacidsolution,E
h d d i li id l i o hasbeencalculatedtobe1.51volts;
h b l l d b l
hencethepermanganateioninacidsolutionisastrongoxidisingagent.
Sulphuricacidisthemostsuitableacid,asithasnoactionuponpermanganate
indilutesolution.Withhydrochloricacid,thereisalikelihoodofthereaction :

takingplace,andsomepermanganatemaybeconsumedintheformationof
chlorine.Thisreactionisparticularlyliabletooccurwithironsaltsunlessspecial
precautions are adopted. With a small excess of free acid, a very dilutesolution,
precautionsareadopted.Withasmallexcessoffreeacid,avery dilute solution,
lowtemperatureandslowtitrationwithconstantshaking,the dangerfromthis
causeisminimised.Thereare,however,sometitrations,such asthosewith
arsenic(III) oxide antimony(III) and hydrogen peroxide which canbecarriedout
arsenic(III)oxide,antimony(III),andhydrogenperoxide,which can be carried out
inthepresenceofhydrochloricacid.
Potassiumpermanganateinstronglyalkalinesolution
can take place two reactions :
cantakeplacetworeactions
(1)Inrapidreaction :
MnO4 +e
+e MnO42
(2)In slowreaction :
MnO42 +2H
+ 2H2O +2e
+ 2e + 4 OH
MnO2 +4
StandardpotentialEo ofreaction(1)is0.56voltandofreaction
(2) is0.60volt.Bycontrollingtheexperimentalconditions(e.g.by
additionofbariumions toformafinegranularprecipitateof
sparinglysolublebarium manganate)reaction(1)willbetheonly
occured.d
In moderatealkalinesolution,permanganatewillbe
red ced q antitati el to formmanganesedioxide
reducedquantitativelyto form manganese dio ide with
ith
a halfcell reaction :
MnO4 +2H
+ 2H2O +3e
+ 3e + 4 OH
MnO2 +4
StandardpotentialEo is0.59volt.
KMnO4 isnotaprimarystandard.Itisdifficulttoobtain the
substance perfectly pure and completely free from manganese
substanceperfectlypureandcompletelyfreefrommanganese
dioxide. Moreover,ordinarydistilledwaterislikelytocontain
reducingsubstances (tracesoforganicmatter,etc.)whichwill
reactwiththepotassiumpermanganate toformmanganese
dioxide.Thepresenceofthelatterisveryobjectionable becauseit
catalysestheautodecompositionofthepermanganatesolution
t l th t d iti f th t l ti
on standing:

4MnO4 +2H2O 4MnO2 +3O2 +4OH

Permanganateisinherentlyunstableinthepresenceof
manganese (II)ions:

2 MnO4 +3 Mn2+ +2 H2O 5 MnO2 +4 H+

Thisreactionisslowinacidsolution,butitisveryrapidinneutral
Thi ti i l i id l ti b t it i id i t l
solution.
For these reasons, potassium permanganate solution is rarely made
up by
b dissolving
di l i weighed
i h d amounts t off the
th purified
ifi d solid
lid in
i water;
t it is
i
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
sulphuric
l h i acidcleaning
id l i mixtureandthenthoroughlywithdistilled
i t d th th hl ith di till d
water.Acidicandalkalinesolutions arelessstablethanneutral
ones. Solutions of permanganate should be protected from
ones.Solutionsofpermanganateshouldbeprotected from
unnecessaryexposuretolight:adarkcoloured bottleisrecom
mended. Diffusedaylightcausesnoappreciable decomposition,
butbrightsunlightslowly decomposesevenpuresolutions.
 STANDARDIZATIONOFKMnO4

MethodA :Witharsenic(III)oxide.

Thisprocedure,whichutilises arsenic(III) oxideasaprimary

standardandpotassiumiodideorpotassiumiodate
d d d i i did i i d asa catalyst
l
forthereaction,isconvenientinpracticeandisa trustworthy
method for the standardisation ofpermanganatesolutions.
methodforthestandardisation of permanganate solutions
Analyticalgrade arsenic(III)oxidehasapurityofatleast99.8per
cent,andtheresultsbythis methodagreetowithin1partin3000
withthesodiumoxalateprocedure (MethodB,below).

4OH
As2O3 +4OH
A HA O32
2 HAsO 2 + H O
2
5H3AsO3 +2MnO4 +6H+ 5 H3AsO4 +2 Mn2+ +3 H2O
Method B :Withsodiumoxalate
MethodB With sodium oxalate.Thisreagentisreadilyobtained
hi i dil b i d
pureand anhydrous,andtheordinarymaterialhasapurityofatleast99.9per
cent.In theexperimentalprocedureoriginallyemployedasolutionofthe
oxalate, acidifiedwithdilutesulphuric acidandwarmedto8090OC,was
titratedwith thepermanganatesolutionslowly(1015mL min1)andwith
constant stirring untilthefirstpermanentfaintpinkcolour
constantstirring until the first permanent faint pink colour wasobtained;the
was obtained; the
temperaturenear theendpointwasnotallowedtofall below60oC.However
withthisprocedure theresultsmaybe0.10.45percenthigh;thetitre depends
upon the acidity the temperature,therateofadditionofthepermanganate
upontheacidity,the temperature the rate of addition of the permanganate
solution,andthespeed ofstirring.Becauseofthisitisbesttomakeamorerapid
additionof9095 percentofthepermanganatesolution(about2535mL min')
to a solution ofsodiumoxalatein1Msulphuric
toasolution of sodium oxalate in 1 M sulphuric acidat2530OC,thesolutionis
acid at 25 30 OC the solution is
thenwarmed to5560OCandthetitrationcompleted,thelast0.51mL portion
being addeddropwise.
DETERMINATIONOFHYDROGENPEROXIDE

Hydrogenperoxideisusuallyencounteredintheformofan
d id i ll di h f f
aqueoussolution containingabout6percent,12percentor
30 per cent hydrogen peroxide and frequentlyreferredtoas
30percenthydrogenperoxide,and frequently referred to as
'20volume','40volume',and'100volume'hydrogen
peroxiderespectively;thisterminologyisbaseduponthe
volumeofoxygen liberatedwhenthesolutionisdecomposed
byboiling.Thus1mL of'100volume'hydrogenperoxidewill
yield100mL
i ld 100 L ofoxygenmeasuredatstandard
f d d d temperature
andpressure.
DETERMINATIONOFNITRITES
Nitritesreactinwarmacidsolution(ca
Ni i i id l i ( 40 40 oC)withpermanganate
C) i h
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
potassiumpermanganatesolution,acidifiedwithdilutesulphuric
t i t l ti idifi d ith dil t l h i
acid,istreated withthenitritesolution,addedfromaburette,
until the permanganate is just decolorised,resultsaccurateto
untilthepermanganateisjust decolorised results accurate to
0.51percentmaybeobtained.Thisisdueto thefactthat
nitrousaciddoesnotreactinstantaneouslywiththe
permanganate. Thismethodmaybeusedtodeterminethepurity
ofcommercialpotassium nitrite.
 2.Di(orBi)chromatometricTitration
Potassiumdichromateisnotsuchapowerfuloxidising agentas
potassium permanganate,but
permanganate but ithasseveraladvantagesoverthe
it has several advantages over the
lattersubstance.Itcanbeobtainedpure,it isstableuptoitsfusion
point,anditisthereforeanexcellentprimarystandard. Standard
solutionsofexactlyknownconcentrationcanbepreparedby
weighing outthepuredrysaltanddissolvingitintheproper
volumeofwater.
l f t Furthermore,theaqueoussolutionsarestable
F th th l ti t bl
indefinitelyifadequately protectedfromevaporation.Potassium
dichromate is used only in acid solution, andisreducedrapidlyat
dichromateisusedonlyinacidsolution, and is reduced rapidly at
theordinarytemperaturetoagreenchromium(III) salt.
In acid solution :
Thegreencolour
The due to the Cr3+ ionsformedbythe
green colour duetotheCr ions formed by the
reductionofpotassium dichromatemakesitimpossible
to ascertain the end point of a dichromate titrationby
toascertaintheendpointofadichromate titration by
simplevisualinspectionofthesolutionandsoaredox
indicator mustbeemployedwhichgivesastrongand
must be employed which gives a strong and
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 sodiumdiphenylaminesulphonate
0.005MNaOH)and sodium diphenylamine sulphonate
(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,
mgL1.
Theanalysisoftheimpurewatersampleiscarriedoutin
parallelwithablank determinationonpure,double
distilledwater.
Procedure.
Placea50mL
Place a 50 mL volumeofthewatersampleina250mL
volume of the water sample in a 250 mL conical flaskwitha
flask with a
groundglassneckwhichcanbefittedwithawatercondenserfor refluxing.
Add1gofmercury(II)sulphate,followedby80mL ofasilver sulphate/
sulphuric acidsolution.Thenadd10mL
acid solution Then add 10 mL ofapproximately
of approximately 0.00833
0 00833 M standard
standard
potassiumdichromatesolution,fittheflaskwith therefluxcondenserand
boilthemixturefor15minutes.Oncoolingrinsethe insideofthecondenser
with50mL
ih ofwaterintotheflaskcontents.Addeither
f i h fl k dd i h diphenylamine
di h l i
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)x0.2x20mgL1

asa1mL
as a 1 mL differencebetweenthetitrationscorrespondsto0.2mgofoxygen
difference between the titrations corresponds to 0 2 mg of oxygen
requiredbythe50mL sample(acorrectionmust,ofcourse,bemadeif
solutions ofslightlydifferentmolaritiesareemployed).
 3. Ce et c t at o
3.CerimetricTitration

Cerium(IV)sulphate isapowerfuloxidising agent;itsreduction

potential in 0.54.0Msulphuric
potentialin acid at 25 oCis1.43
0 5 4 0 M sulphuric acidat25 C is 1 43 +0.05volts.
+ 0 05 volts
Itcanbeusedonlyin acidsolution,bestin0.5 Morhigher
concentrations ::asthesolutionis
as the solution is neutralised,
neutralised,cerium(IV)
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
evenbeboiledforashort
b b il d f h timewithoutappreciablechangein
i ih i bl h i
concentration.Thestabilityofsulphuric acidsolutionscoversthe
wide range of 1040 mL ofconcentratedsulphuric
widerangeof1040mL of concentrated sulphuric acidperlitre.Itis
acid per litre It is
evident,therefore,thatanacidsolutionofcerium(IV) sulphate
surpassesapermanganatesolutioninstability.
2.Cerium(IV)sulphate maybeemployedinthedeterminationof
reducing agentsinthepresenceofahighconcentrationofHCl.
3 C i (IV) l i
3.Cerium(IV)solutionsin0.1Msolutionarenottoohighly
i 01M l i hi hl
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
slowattheambienttemperature;itisnecessaryto
l t th bi t t t it i t addatraceof
dd t f
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
solutiontothefirstsharpcolour
l ti t th fi t h l change
h :orangeredto
d t verypale
l
blueoryellowishgreentopurplerespectively.
MethodB :Standardisation withsodiumoxalate.

Standardisation mayalsobe carriedoutwithsodiumoxalate;in

thiscase,anindirectproceduremustbe
this case, an indirect procedure must be used
usedastheredox
as the redox
indicatorsarethemselvesoxidised attheelevatedtemperatures
whicharenecessary.Theprocedure,therefore,istoaddan
excessofthe cerium(IV)solution,andthen,aftercooling,the
excessisdeterminedby backtitrationwithaniron(II)solution.

Itispossibletocarryoutadirect titrationofthesodiumoxalate
ifapotentiometric
p procedureisused.
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. The solution, after reduction, is collected in a solution of
state.Thesolution,afterreduction,iscollectedinasolutionof
ammonium iron(III)sulphate,andtheFe2+ ionformedistitrated
withstandardcerium(IV) sulphate solutionusingferroin orN
phenylanthranilic acidasindicator.

Determinationofnitrites:
Determination of nitrites :
Satisfactoryresultsareobtainedbyaddingthenitritesolutionto
excessofstandard0.1Mcerium(IV)sulphate,anddetermining
( ) p , g
theexcessof cerium(IV)sulphate withastandardiron(II)
solution.

Forpractice,determinethepercentageofNO;inpotassium
nitrite or the purityofsodiumnitrite,preferablyofanalytical
nitrite,orthe purity of sodium nitrite preferably of analytical
gradequality.
 4.IodiometricTitration
Thedirectiodometric titrationmethod(sometimestermed
y)
iodimetry)refersto titrationswithastandardsolutionofiodine.
Theindirectiodometric titration method(sometimestermed
iodometry)dealswiththetitrationofiodineliberated inchemical
reactions.

The normal reduction potential of the reversible system:

Thenormalreductionpotentialofthereversiblesystem:

I2 (solid)
(solid) +2e 2I is0.5345volt.

Theaboveequationreferstoasaturatedaqueoussolutioninthe
presenceofsolidiodine;thishalfce11reactionwilloccur,for
example,towards theendofatitrationofiodidewithan
oxidising agentsuchaspotassium
agent such as potassium permanganate,whenthe
permanganate when the
iodideionconcentrationbecomesrelativelylow.
Nearthebeginning,orinmostiodometric titrations,whenan
excess of iodide ion is present,thetriiodideionisformed
excessofiodideionis present the tri iodide ion is formed

sinceiodineisreadilysolubleinasolutionofiodide.Thehalf
ce11reactionis betterwritten:

andthestandardreductionpotentialis0.5355volt.Iodineor
and the standard reduction potential is 0 5355 volt Iodine or
thetriiodideion isthereforeamuchweakeroxidising agent
thanpotassiumpermanganate,
p p g ,ppotassiumdichromate,and
,
cerium(IV)sulphate.
Inmostdirecttitrationswithiodine(iodimetry)asolutionof
iodinein potassiumiodideisemployed,andthereactivespecies
isthereforethetriiodide ionI3.Strictlyspeaking,all equations
involvingreactionsofiodineshouldbe written with I3 rather
involving reactions of iodine should be writtenwithI rather
thanwithI2 e.g.
Inmostdirecttitrationswithiodine(iodimetry)asolutionof
i di i potassiumiodideisemployed,andthereactivespecies
iodinein i i did i l d d h i i
isthereforethetriiodide ionI3.Strictlyspeaking,all equations
involvingreactionsofiodineshouldbe written with I3 rather
involving reactions of iodine should be writtenwithI rather
thanwithI2 e.g.

ismoreaccuratethan

Strongreducingagents(substanceswithamuchlowerreductionpotential),
Strong reducing agents (substances with a much lower reduction potential),
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
minimum,oritsreducingpowerisamaximum.
i i it d i i i
Twoimportantsourcesoferrorintitrationsinvolvingiodineare :
(a) lossof
loss of iodineowingtoitsappreciablevolatility;and
iodine owing to its appreciable volatility; and
(b)acidsolutionsofiodideare oxidised byoxygenfromtheair.

Inthepresenceofexcessofiodide,thevolatilityisdecreased
markedlythrough
k dl th h theformationofthetriiodideion;atroom
th f ti f th t i i did i t
temperaturethelossofiodineby volatilisation fromasolution
containing at least 4 per cent of potassium iodide isnegligible
containingatleast4percentofpotassiumiodide is negligible
providedthetitrationisnotprolongedunduly.
Titrationsshould beperformedincoldsolutionsinconicalflasks
andnotinopenbeakers.Ifa solutionistostanditshouldbekept
inaglassstoppered vessel. Theatmosphericoxidationofiodideis
negligibleinneutralsolutionintheabsenceofcatalysts,
li ibl i t l l ti i th b f t l t butthe
b t th
rateofoxidationincreasesrapidlywithdecreasingpH.
The reactionis
reaction is catalysed bycertainmetalionsofvariablecharge
by certain metal ions of variable charge
value(particularlycopper),by nitriteion,andalsobystronglight.
Itseemsappropriatetoreferatthispointtotheusesofa standard
solution containingpotassiumiodideandpotassiumiodate.
containing potassium iodide and potassium iodate
Thissolutionisquitestable andyieldsiodinewhentreatedwith
acid :

Thestandardsolutionispreparedbydissolvingaweighedamount
ofpure potassiumiodate inasolutioncontainingaslightexcessof
pure potassium iodide,anddilutingtoadefinitevolume.
purepotassium iodide and diluting to a definite volume

Thissolutionhastwoimportantuses
p :
Thefirstisasasourceofaknownquantityofiodineintitrations;it
mustbeaddedtoasolutioncontainingstrongacid;it cannotbe
employedinamediumwhichisneutralorpossessesalowacidity.
Theseconduseisinthedeterminationoftheacidcontentof
solutions iodometrically orinthestandardisation
or in the standardisation ofsolutionsof
of solutions of
strongacids.
 DetectionoftheEndPoint
Asolutionofiodineinaqueousiodidehasanintenseyellowto
browncolour. Onedropof0.05 Miodinesolutionimpartsa
perceptiblepaleyellowcolour
bl l ll l to100mL ofwater,sothatin
f h
otherwisecolourless solutionsiodinecanserve asitsown
indicator The test is made much more sensitive by the use of a
indicator.Thetestismademuchmoresensitivebytheuseofa
solutionofstarchasindicator.Starchreactswithiodineinthe
presenceofiodide toformanintenselybluecoloured
p y complex,
p
whichisvisibleatverylow concentrationsofiodine.Thesensitivity
ofthecolour reactionissuchthata bluecolour isvisiblewhenthe
i di i i 2 10 Mandtheiodide
iodineconcentrationis2x10 d h i did concentrationis
i i
greaterthan4x104 Mat20C.

Thecoloursensitivitydecreaseswithincreasingtemperatureofthesolution;
thusat50oCitisabout tentimeslesssensitivethanat25oC.Thesensitivity
decreases upon the addition ofsolvents,suchasethanol
decreasesupontheaddition of solvents such as ethanol :nocolour
: no colour isobtained
is obtained
insolutionscontaining 50%ethanolormore.Itcannotbeusedinastronglyacid
medium becausehydrolysisofthestarchoccurs.
Thecoloursensitivitydecreaseswithincreasingtemperatureof
the solution; thus at 50 oCitisabout
thesolution;thusat50 C it is about tentimeslesssensitivethan
ten times less sensitive than
at25oC.Thesensitivitydecreasesupontheaddition ofsolvents,
suchasethanol :nocolour isobtainedinsolutionscontaining
50percentethanolormore.Itcannotbeusedinastronglyacid
medium becausehydrolysisofthestarchoccurs.

Starchescanbeseparatedintotwomajorcomponents,amylose
and amylopectin,whichexistindifferentproportionsinvarious
amylopectin, which exist in different proportions in various
plants.

Amylose, whichisastraightchaincompoundandisabundantin
potatostarch,givesa bluecolour withiodineandthechain
assumesaspiralform.
i lf

Amylopectin,which
Amylopectin, which hasabranched
has a branchedchain
chainstructure,formsared
structure, forms a red
purpleproduct,probablyby adsorption.
Thegreatmeritofstarch isthatitisinexpensive.Itpossessesthe
following disadvantages :
(1) insolubilityincoldwater;
(2) instabilityofsuspensionsin water;
(3) itgivesawaterinsolublecomplexwithiodine,theformation
ofwhich precludestheadditionoftheindicatorearlyinthe
tit ti (f thi
titration(forthisreason,in
i titrationsofiodine,thestarch
tit ti f i di th t h
solutionshouldnotbeaddeduntiljustpriorto theendpoint
when the colour beginstofade);and
whenthecolour begins to fade); and
(4) thereissometimesa 'drift'endpoint,whichismarkedwhen
thesolutionsaredilute.

Mostoftheshortcomingsofstarchasanindicatorareabsentinsodium starch
gglycollate.Thisisawhite,nonhygroscopicpowder,readilysolublein
y , yg p p , y hot
watertogiveafaintlyopalescentsolution,whichisstableformanymonths; it
doesnotformawaterinsolublecomplexwithiodine,andhencetheindicator
may be added at any stage of the reaction
maybeaddedatanystageofthereaction.
Carbontetrachloridehasbeenusedincertainreactionsinstead
of starch solution.Onelitre
ofstarch solution One litre ofwaterat25OCwilldissolve0.335
of water at 25 OC will dissolve 0 335
gofiodine,butthesame volumeofcarbontetrachloridewill
dissolveabout28.5g.Iodineistherefore about85timesas
solubleincarbontetrachlorideasitisinwater,andthe
carbontetrachloride solutionishighlycoloured.Whenalittle
carbontetrachlorideis
b t t hl id i addedtoanaqueoussolutioncontaining
dd d t l ti t i i
iodineandthesolutionwellshaken, thegreatpartoftheiodine
will dissolve in the carbon tetrachloride; the latter willfall
willdissolveinthecarbontetrachloride;thelatter will fall tothe
to the
bottomsinceitisimmisciblewithwater,andthecolour ofthe
organiclayerwillbemuchdeeperthanthatoftheoriginal
aqueoussolution.
Thereddishvioletcolour ofiodineincarbontetrachlorideis
visibleinverylow
i ibl i l concentrationsofiodine;thusonshaking10
t ti f i di th h ki 10
mL ofcarbontetrachloridewith 50mL of105 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)oxidewhichhasbeendriedat105 110oCfortwo
Arsenic(II1) oxide which has been dried at 105110 C for two
hoursisan excellentprimarystandard.Thereactionbetweenthis
substanceandiodineis areversibleone:

andonlyproceedsquantitativelyfromlefttorightifthehydrogen
d l d tit ti l f l ft t i ht if th h d
iodideis removedfromthesolutionasfastasitisformed.
This may be done by theadditionofsodiumhydrogencarbonate
Thismaybedoneby the addition of sodium hydrogencarbonate : :
sodiumcarbonateandsodium hydroxidecannotbeused,since
theyreactwiththeiodine,formingiodide,hypoiodite,andiodate.
Actuallyithasbeenshownthatcompleteoxidationof thearsenite
occurswhenthepHofthesolutionliesbetween4and9,thebest
valuebeing6.5,whichisveryclosetotheneutralpoint.Buffer
l b i 6 5 hi h i l t th t l i t B ff
solutions areemployedtomaintainthecorrectpH.
(B)Withstandardsodiumthiosulphate solution.
Sodiumthiosulphate
di hi l h solution,
l i whichhasbeenrecently
hi h h b l
standardised,preferablyagainstpurepotassiumiodate, is
employed Transfer 25 mL oftheiodinesolutiontoa250mL
employed.Transfer25mL of the iodine solution to a 250 mL
conicalflask, diluteto100mL andaddthestandardthiosulphate
solutionfromaburette untilthesolutionhasapaleyellow
colour.Add2mL ofstarchsolution,and continuetheadditionof
thethiosulphate solutionslowlyuntilthesolutionis just
colourless.
l l

Sodiumthiosulphate
Sodium thiosulphate (Na2S2O4.5H5H20)isreadilyobtainableina
0) is readily obtainable in a
stateofhighpurity,butthereisalwayssomeuncertaintyasto
theexactwater contentbecauseoftheefflorescentnatureof
thesaltandforotherreasons.The substanceistherefore
unsuitableasaprimarystandard.Itisareducingagent byvirtue
ofthehalfcell
f th h lf ll reaction
ti :
Itisnecessarytoreferbrieflytothestabilityof thiosulphate
solutions Solutions prepared with conductivity (equilibrium)
solutions.Solutionspreparedwithconductivity(equilibrium)
water areperfectlystable.However,ordinarydistilledwater
usuallycontainsanexcess
usually contains an excess of
ofcarbondioxide;thismaycausea
carbon dioxide; this may cause a
slowdecompositiontotakeplacewiththe formationofsulphur:

Moreover,decompositionmayalsobecausedbybacterialaction
(e g Thiobacillus thioparus),particularlyifthesolutionhasbeen
(e.g. thioparus) particularly if the solution has been
standingforsome time.Forthesereasons,thefollowing
recommendationsaremade:
1.Preparethesolutionwithrecentlyboileddistilledwater.
2.Add3dropsofchloroformor10mgL1 ofmercury(II)iodide;
these compoundsimprovethekeepingqualitiesofthesolution.
BacterialactivityisleastwhenthepHliesbetween9and10.The
of a small amount 0 1 g L11,ofsodiumcarbonateis
addition ofasmallamount,0.1gL of sodium carbonate is
advantageoustoensure thecorrectpH.
Ingeneral,alkalihydroxides,sodiumcarbonate(>0.1gL1),
and sodium tetraborate shouldnotbeadded,sincetheytendto
andsodiumtetraborate should not be added since they tend to
accelerate thedecomposition:

3.Avoidexposuretolight,asthistendstohastenthe
d
decomposition.
iti

Thestandardisation
The standardisation ofthiosulphate
of thiosulphate solutionsmaybeeffected
solutions may be effected
withpotassium iodate,potassiumdichromate,copperandiodine
asprimarystandards,orwith potassiumpermanganateor
cerium(IV)sulphate assecondarystandards.
Owing tothevolatilityofiodineandthedifficultyofpreparation
ofperfectlypure
f f tl i di
iodine,thismethodisnotasuitableonefor
thi th d i t it bl f
beginners.If,however,astandard solutionofiodineisavailable,
this may be used forthestandardisation
thismaybeused for the standardisation ofthiosulphate
of thiosulphate
solutions.
Standardizationofsodiumthiosulphatesolution
(A) Withpotassiumiodate.

Potassiumiodate hasapurityofatleast99.9percent :
itcanbedriedat120oC.Thisreactswithpotassiumiodidein
acidsolutionto liberateiodine:

Itsrelativemolecularmassis214.00;a0.02 Msolutiontherefore
contains 4.28 g ofpotassiumiodateperlitre.
contains4.28g of potassium iodate per litre.
(B)Withpotassiumdichromate.

Potassiumdichromateisreducedbyanacid solutionof
potassium iodide and iodine is set free :
potassiumiodide,andiodineissetfree

Thisreactionissubjecttoanumberoferrors :
(1) thehydriodic acid(from excessofiodideandacid)isreadily
oxidised
idi d byair,especiallyinthepresence
b i i ll i h ofchromium(III)
f h i (III)
salts,and
(2) itisnotinstantaneous.Itisaccordinglybestto
(2) it is not instantaneous It is accordingly best to passa
pass a
currentofcarbondioxidethroughthereactionflaskbefore
andduring thetitration(amoreconvenientbutless
efficientmethodistoaddsomesolid sodium hydrogen
carbonatetotheacidsolution,andtokeeptheflask
covered d asmuchaspossible),andtoallow5minutesforits
h ibl ) d t ll 5 i t f it
completion.
DeterminationofArsenic(V)
Thereactionisthereverseofthatemployedinthe standardi
sation ofiodine withsodiumarsenite solution:

Forgoodresults,thefollowing experimentalconditionsmustbe
observed :
(1) The hydrochloricacid concentrationinthefinalsolution
shouldbeatleast4 M;
(2) Air
Ai shouldbedisplacedfromthetitrationmixturebyaddinga
h ld b di l d f h i i i b ddi
littlesolidsodium hydrogencarbonate;
(3) Thesolutionmustbeallowedtostandforatleast
The solution must be allowed to stand for at least 5minutes
5 minutes
beforetheliberatediodineistitrated;and
(4) Constantstirringis essentialduringthetitrationtoprevent
decompositionofthethiosulphate in thestronglyacid
solution.
 5 Iodatometric Titration
5.IodatometricTitration
Potassiumiodate isapowerfuloxidising
p g agent,butthecourseof
g ,
thereaction isgovernedbytheconditionsunderwhichitis
employed.Thereactionbetween potassiumiodate andreducing
agentssuchasiodideionorarsenic(III)oxide insolutionsof
moderateacidity(0.12.0Mhydrochloricacid)stopsatthestage
when the iodate isreducedtoiodine
whentheiodate is reduced to iodine :

Asalreadyindicated,thefirstofthesereactionsisveryusefulfor
l d i di d h fi f h i i f lf
thegeneration ofknownamountsofiodine,anditalsoservesas
the basis of a method for standardising solutionsofacids.
thebasisofamethodfor solutions of acids
Withamorepowerfulreductant,e.g.titanium(III)chloride,the
iodate is reducedtoiodide:

Inmorestronglyacidsolutions(36
l id l i ( Mhydrochloricacid)reduction
h d hl i id) d i
occursto iodinemonochloride,anditisundertheseconditions
that it is most widely used.
thatitismostwidely used

Inhydrochloricacidsolution,iodinemonochloride formsastable
complexion withchlorideion:

The overall halfcell reactionmaythereforebewrittenas:

Theoverallhalfcell reaction may therefore be written as:

Thereductionpotentialis1.23volts;henceundertheseconditions
potassium iodate actsasaverypowerfuloxidising agent.
Oxidationbyiodate ioninastronghydrochloricacidmedium
proceeds throughseveralstages:
through several stages :

Intheinitialstagesofthereactionfreeiodineisliberated :as
more titrant is added,oxidationproceedstoiodinemonochloride,
moretitrant added oxidation proceeds to iodine monochloride
andthedarkcolour ofthe solutiongraduallydisappears.
Theoverallreactionmaybewrittenas
y :

Thereactionhasbeenusedforthedeterminationofmany
reducingagents.
Undertheseconditions(2.5
Under these conditions (2 59 9.0MofHCl)starchcannotbeused
0 M of HCl) starch cannot be used
asindicatorbecausethe characteristicbluecolour ofthest arch
iodinecomplexisnotformedathigh concentrationsof acid.
Intheoriginalprocedure,afewmillilitres of animmiscible
solvent(carbontetrachlorideorchloroform)wereaddedtothe
solutionbeing
l ti b i titratedcontainedinaglassstoppered
tit t d t i di l t d bottleor
b ttl
conicalflask.
The end point is markedbythedisappearanceofthelasttrace
Theendpointis marked by the disappearance of the last trace
ofvioletcolour,duetoiodine, fromthesolvent:iodine
monochloride isnotextractedandimpartsapale yellowish
colour totheaqueousphase.Theextractionendpointisvery
sharp.
Th
Themaindisadvantageistheinconvenienceofvigorousshaking
i di d t i th i i f i h ki
withthe extractionsolventinastoppered vesselaftereach
addition of the reagent near theendpoint.
additionofthereagentnear the end point.
Preparationof0.025MPotassiumIodateSolution

Drysomepotassiumiodate at120oCfor1hourandallowittocool
inaa covered
in coveredvesselinadesiccator.Weighoutexactly5.350gofthe
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,ideallythesolutionthenrequires4.28gL1
potassium iodate;themethodofpreparationwillbeasdescribed
iodate; the method of preparation will be as described
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 givesexcellentresults.
theendpoint;amaranth,however, gives excellent results
 6.BromatometricTitration
Potassiumbromate isapowerfuloxidising agentwhichisreduced
smoothly to bromide:
smoothlyto bromide :

Therelativemolecularmassis167.00,anda0.02 Msolution
contains3.34gL1potassiumbromate.Attheendofthetitration
f
freebromineappears
b i :

Thepresenceoffreebromine,andconsequentlytheendpoint,
canbedetected byitsyellowcolour,butitisbettertouse
indicatorssuchasmethylorange, methylred,naphthaleneblack
12B,xylidineponceau,andfuchsine.Theseindicatorshavetheir
usualcolour
l l i
inacidsolution,butaredestroyedbythe
id l ti b t d t d b th firstexcess
fi t
ofbromine.
Withall irreversibleoxidationindicatorsthedestruction ofthe
indicatorisoftenprematuretoaslightextent :alittleadditional
indicator isusuallyrequiredneartheendpoint.Thequantityof
is usually required near the end point The quantity of
bromate solution consumedbytheindicatorisexceedingly
small, and the 'blank'
small,andthe blank canbeneglected
can be neglected for0.02
for 0.02 Msolutions.
M solutions.
Directtitrationswithbromate solutioninthepresenceof
irreversibledyestuffindicatorsareusuallymadeinhydrochloric
acidsolution, theconcentrationofwhichshouldbeatleast
1.52 M.
At the end of the titration somechlorinemayappearbyvirtueof
Attheendofthetitration some chlorine may appear by virtue of
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 solution
byaddingacidandanexcessofbromide :

Inthisreaction1moleofbromate yieldssixatomsofbromine.
Bromineisvery
Bromine is very volatile,andhencesuchoperationsshouldbe
volatile and hence such operations should be
conductedataslowatemperature aspossibleandinconicalflasks
fittedwithgroundglassstoppers.Theexcess
fitted with ground glass stoppers. The excess of
ofbrominemaybe
bromine may be
determinediodometrically bytheadditionofexcessof potassium
iodideandtitrationoftheliberatediodinewithstandard
thiosulphate solution:

Potassiumbromate isreadilyavailableinahighstateofpurity;the
product hasanassayvalueofatleast99.9percent.Thesubstance
p y p
canbedriedat 120150oC,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:

Thepresenceoftinandofconsiderablequantitiesofironand
Th f ti d f id bl titi fi d
copperinterfere withthedeterminations.
Determinationofphenol

Anumberofphenolscanbesubstitutedrapidlyand
quantitatively withbromineproducedfrombromate
with bromine produced from bromate andand
bromideinacidsolution.Thedeterminationinvolvestreating
phenolwithanexcessofpotassiumbromate andpotassium
bromide;whenbromination ofthe phenoliscompletethe
unreacted bromineisthendeterminedbyaddingexcess
potassiumiodideandbacktitratingtheliberatediodinewith
t i i did d b k tit ti th lib t d i di ith
standardsodium thiosulphate.
End