DETERMINATIONOFSTANDARD

REDOXPOTENTIALSFROM
POTENTIOMETRIC TITRATIONS
POTENTIOMETRICTITRATIONS
Formalredox potentialofFe2+/Fe3+
andofCe3+/Ce4+ systemin1MH2SO4

IISC,Bangalore

Oxidationand
Oxidation
and
ReductionReactions
Oxidationistheprocessofthelossofelectronsfrom
anatomorion

Fe2+Fe3++e
Reductionistheprocessofthegainofelectronsfrom
anatomorion
3 +eFe2+
2
Fe3+

Electrode Potential
ElectrodePotential
Ifaplatinumwire(sourceofelectron)isdippedintoan
a p at u
e (sou ce o e ect o ) s d pped to a
aqueoussolutioncontaining,Fe3+andFe2+ions,witha
counteranionpresenttopreserveelectroneutrality.
Fe3+(aq)+e (metal)
Fe2+(aq)
Iftheequilibriumliestotheleft,favouring theformation
ofFe3+(aq),inelectrodeaslightnegativechargeand
insolutionaslightpositivecharge,andviceversa
(dynamic equilibrium) a charge separation and hence
(dynamicequilibrium)achargeseparation,andhence
apotentialdifference,betweenthemetalandthe
solutionwillbeobserved.

Nernst Equation
NernstEquation
Fe3++eFe
+ e
Fe2+
An electrode potential is established on the metal
wire relative to the solution phase. The
correlation of an electrode potential and redox
system composition (in our case Fe3+/Fe2+ system)
can be described by the Nernst equation:

E EFe3 / Fe2

Fe2
RT

ln 3
nF
Fe

Reference Electrode
ReferenceElectrode
Itisnotpossibletomeasurethepotentialofa
It
is not possible to measure the potential of a
singleelectrodedirectly.
Usingtheexampleabove,howcouldthepotential
i
h
l b
h
ld h
i l
oftheplatinumwiredippingintothesolutionbe
measured?
Electrode potentials must be measured relative to
Electrodepotentialsmustbemeasuredrelativeto
somereference.

ReferenceElectrodes
1. Standard
1
StandardHydrogenElectrode
Hydrogen Electrode
2. CalomelReferenceElectrode
Calomel Reference Electrode
3. Silver/SilverChlorideReference
Electrode

Standard Hydrogen Electrode

StandardHydrogenElectrode
Arbitrarily,astandardhydrogenreferenceelectrode(SHE)
y,
y g
(
)
isusedasauniversalstandardandallelectrodepotentials
arequotedrelativetothis.
ForexampleinthecaseoftheFe3+/Fe2+couple,
E0(Fe2+/Fe3+)=0.77V
implyingthatthecell,
Pt|H2(g)(p=1)|H+(a=1)||Fe2+(aq)(a=1),Fe3+(aq)
( 1) | Pt
(a=1)|Pt
hasanemf of0.77V,withtheplatinumelectrodedipping
into the Fe2+ / Fe3+ solution having a positive potential
intotheFe2+/Fe3+solutionhavingapositivepotential.

SHE
H+ + e- = H2
E = Eo 2.303RT/F log (PH2)1/2/aH+
Eo = 0
0.000
000 V
V. If PH2 = 1 atm.,
atm E = -2.303RT/F
2 303RT/F pH

Hydrogenelectrode.

Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Practical Reference Electrodes

PracticalReferenceElectrodes
InpracticetheSHEisinconvenientforeverydayuse.
p
y y
Saturated calomel reference electrode (SCE) which
comprises a mercury electrode coated in mercury
chloride in contact with a saturated potassium chloride
solution. The solution contains potassium chloride
crystals to ensure that saturation is maintained and the
system is connected to the solution in question by a
frit allowing ion exchange with this solution.
frit,
solution The
potential determining equilibrium is:
Cl(aq)
(aq)
Hg2Cl2(s) + e 2Hg(l) + Cl

SCE

The S.C.E. is a common reference electrode.

The cell half-reaction is: Hg2Cl2 + e- = Hg + Cl-.
E = Eo 0.0592 log 1/aCl- = 0.242 V for saturated KCl.

Gary Christian,
G
Ch i ti
Analytical Chemistry,
6th Ed. (Wiley)

Commercial saturated calomel electrode.

SCE
It can be seen that the potential of the
calomel electrode is dependent only on the
chloride ion activity. This is constant as the
solution is saturated with chloride ions. The
potential of a calomel electrode relative to a
standard
d d hydrogen
h d
electrode
l
d is
i +0.242V,
0 242V so if
measurements are made using a calomel
electrode rather than a hydrogen electrode,
electrode
this value must be added to the measured
voltage.
voltage

Ag/AgCl
/
Ref.Electrode
A A Cl (satd),KCl (satd)
AgAgCl

AgCl(s)+e
( ) Ag(s)+Cl
( ) (aq)
( )

E =0.199V

ElectrodesandPotentiometry
Potentiometry
UseofElectrodestoMeasureVoltagesthatProvideChemical
i f
information
ti
- Variouselectrodeshavebeendesignedtorespond
selectivelytospecificanalytes

IndicatorElectrode:electrode
thatrespondstoanalyte and
donates/acceptselectrons
/

ReferenceElectrode:second
cellataconstantpotential

Cellvoltageisdifference
Cell
voltage is difference
betweentheindicatorand
referenceelectrode

ComponentsofaPotentiometric Cell
1.
2
2.
3.
4.

Referenceelectrode
Salt bridge
Saltbridge
Analyte
Indicatorelectrode

Ecell=EindicatorEreference
Formostelectrochemicalmeasurementsjunctionpotentialissmallenoughtoignore

Potentiometric Analysis
Reference electrode A halfcell with an accurately known
electrode potential, Eref, that is independent of the
concentration of the analyte or any other ions in the solution
Always treated as the lefthand electrode
Indicator electrode which is immersed in a solution of the
analyte, develops a potential, Eind, that depends on the
activity of the analyte. Is selective in its response
Salt bridge Preventing components of the analyte solution
from mixing with those of the reference electrode A
potential develops across the liquid junctions at each end of
the salt bridge. Potassium chloride is a nearly ideal
electrolyte for the salt bridge because the mobilities of the
K i and
K+ion
d the
th Cl
Cl ion
i are nearly
l

ElectrodesandPotentiometry
Overview
O
i

Potentialchangeonlydependentononecell
concentrations

Referenceelectrode isfixedorsaturated doesnt

change!

[ Fe 2 ]
0.05916
0.222 0.05916 log[ Cl ]
E cell 0.771
log
[ Fe 3 ]
1

Potentialofthecell
onlydependson[Fe2+]&
[Fe3+]

Unknownsolutionof
[Fe2+]&[Fe3+]

Referenceelectrode,[Cl]
isconstant

Ptwireisindicator
electrodewhose
potentialrespondsto
[Fe2+]/[Fe3+]

Potentiometric Titrations
A potentiometric titration involves measurement of

the potential of a suitable indicator electrode as a

function of titrant volume.
The measurement is base on the titrant volume
that causes a rapid change in potential near the
equivalence point.
Potentiometric titrations provide
d data
d
that
h are
more reliable than data from titrations that use
particularlyy useful
chemical indicators. Theyy are p
with colored or turbid solutions and for detecting
the presence of unsuspected species.

Potentiometric Titration
Fe2+ is titrated against Ce4+. The potential developed on
a platinum electrode immersed in the solution
(
(measured
d against
i t the
th RE) is
i plotted
l tt d as a function
f ti off
the volume of Ce4+ added
The half equations for this redox reaction are as follows:
Fe3+ (aq)+e
Fe2+(aq)
Ce4+ ((aq)+e
q)
Ce3+ ((aq)
q)
The redox potential of the Ce4+ / Ce3+ couple is much
more positive than that of the Fe3+ / Fe2+ couple, so if
Ce4+ is added to a solution containing Fe2+,
Fe2+ effectively
all of the Ce4+ reacts to oxidize Fe2+ to Fe3+ and the
overall reaction is as follows.
Fe2+ (aq)+Ce4+ (aq)Ce3+(aq)+Fe3+ (aq)

Potentiometric Titration
In
Inredox
redox titrations,theconcentrationofthe
titrations the concentration of the
substancesorionsinvolvedinthereaction
continuously keeps changing in the course of
continuouslykeepschanginginthecourseof
thetitration.Hence,theredox potentialofthe
solution must also change Measurements of
solutionmustalsochange.Measurementsof
thepotentialofthecellasafunctionofthe
volume of Ce4+ addedduringatitrationofCe
volumeofCe
added during a titration of Ce4+
againstFe2+ willthenleadtoaplotwiththree
distinct sections
distinctsections.

Potentiometric Titration
Region
RegionII Beforeequivalencepoint
Before equivalence point
Inthefirst,alltheCe4+ addedoxidizesFe2+ to
Fe3+ sonoCe
so no Ce4+ ispresentinthecellin
is present in the cell in
significantquantity,whilebothFe3+ andFe2+
are present Thus measurements of the emf
arepresent.Thus,measurementsoftheemf
aremadeontheFe3+/Fe2+ couple,basedon
the cell: Ag AgCl |KCl
thecell:Ag,AgCl
| KCl ||Fe
|| Fe3+,Fe
Fe2+ |Pt.
| Pt

E EFe

E
3
ref
/ Fe2

Fe2
RT

lln 3
nF
Fe

Potentiometric Titration
Athalfneutralizationpoint
At half neutralization point
Athalfneutralizationpoint,[Fe2+]=[Fe3+];then
Henceonecancalculatetheformalpotential
fromthehalfneutralizationpointofthe
titrationcurve,ifEref0 isknown

E EFe
E
F 3 / Fe
F 2

ref

Potentiometric Titration
Region
RegionII
II Atequivalencepoint
At equivalence point
thepointatwhichalltheFe2+ hasbeen
oxidized to Fe3+ byCe
oxidizedtoFe
by Ce4+.Bydefinitionthe
By definition the
equivalencepointoccurswhen:[Fe3+]=[Ce3+]
and [Fe2+]=[Ce
and[Fe
] = [Ce4+].Thepotentialofthesystem
] The potential of the system
canbegivenbyboth:

Eeq ECe4 / Ce3 E

Eeq EFe3 /F e2 E

ref

ref

Ce3
RT

log 4
nF
Ce
Fe 2
RT

log 3
nF
Fe

Potentiometric Titration
Adding
Addingandrearrangingthesetwoexpressions
and rearranging these two expressions
andsubstituting[Fe3+]=[Ce3+]and[Fe2+]=
[Ce4+],weget:
] we get:
Eeq

EFe

E
3
/F e 2
Ce 4 / Ce3

ref

Potentiometric Titration
RegionIII
Region III Afterequivalencepoint
After equivalence point
Inthethirdsection,noFe2+ remainstobe
oxidized by the Ce4+,someasurementsare
oxidizedbytheCe
so measurements are
madeontheCe4+/Ce3+ couplebasedonthe
cell Ag AgCl |KCl
cellAg,AgCl
| KCl ||Ce
|| Ce4+,Ce
Ce3+ |Pt.
| Pt
TheNernstequationforthiscellis:

Eeq ECe
E
C 4 / C
Ce3

ref

Ce 3
RT

log
g 4
nF
Ce

Potentiometric Titration
By
Byplottingtheredox
plotting the redox potentialcorresponding
potential corresponding
todifferentpointsinthetitration,atitration
curve similar to the curve obtained in an acid
curvesimilartothecurveobtainedinanacid
basemethodisobtainedandthisgraphcan
be used to detect different stages of titration
beusedtodetectdifferentstagesoftitration
andfinallytheformalredox potentialsof
Fe2+/Fe3+ andofCe
and of Ce3+/Ce4+ system.
system