Redox Titrations

-the oxidation/reduction reaction between analyte and titrant

-titrants are commonly oxidizing agents, although reducing

titrants can be used

-the equivalence point is based upon:

Aox + Bred ! Ared + Box

Rx’n goes to completion after each addition of titrant –

Potentiometric Titration:

Titration reaction:

Ce4+ + Fe2+ ! Ce3+ + Fe3+ (1)

Reference half-reaction:

2Hg(l) + 2Cl- ! Hg2Cl2(s) + 2e-

At the Pt indicator electrode (Indicator half-reaction)

Fe3 + e- ! Fe2+ E0 = 0.767 V (2)

Ce4+ + e- ! Ce3+ E0 = 1.70V (3)

Cell reactions (in 1 M HClO4):

2Fe3+ + 2Hg(l) + 2Cl- ! 2Fe2+ + Hg2Cl2(s) (4)

2Ce4+ + 2Hg(l) + 2Cl- ! 2Ce3+ + Hg2Cl2(s) (5)

Relationships

- Cell reactions are not the same as the titration reaction

- May describe the cell voltage with either (4) or (5) or

both

Balancing Redox Reactions

Balance:
-atoms
-# of electrons transferred
Example:

Cr(s) + Ag+ ! Cr3+ + Ag(s)

1. Write the half reactions:

2. Balance the electrons:

3. Recombine

Equilibrium constants for oxidation-reduction reactions

Cu(s) + 2Ag ! Cu2+ + 2 Ag(s)

[Cu2+ ]
Keq =
[Ag+ ]2
Galvanic cell:
Ecell = Ecathode – Eanode = EAg+ - ECu2+

Under equilibrium conditions, the potential of the cell

becomes zero, thus can write:
 Ecell = O = Ecathode – Eanode = EAg+ - ECu2+

or
Ecathode = Eanode = EAg+ = ECu2+

-Also when in equilibrium, electrode potentials of all

systems are identical:

EOx1 = EOx2 = EOx3 = EOx4

Where EOx1…..are electrode potentials for the four half-

reactions

Calculating Equilibrium Constants

Cu(s) + 2Ag ! Cu2+ + 2 Ag(s)

E0Ag+ - log 1+ 2 =
0.0592
E0Cu2+- log 1 +
0.0592
2 [Ag ] 2 [Cu2 ]

0.0592 1 0.0592 1
E0Ag+ - E0Cu2+ = log 2
! log
2 [Ag+] 2 [Cu2+ ]
2(E 0 Ag+ ! E 0Cu2+ ) [Cu2+ ]
= = log = log K eq
0.0592 [Ag+]2

Ex: Calculate the equilibrium constant:

[Cu2+ ] 2(0.799
- 0.337)
logK eq = log 2
=
[Ag+] 0.0592
= 15.6
Keq = antilog 15.6 = 4.1 x 1015 = 4 x 1015
 Redox Titration Curves
Fe2+ + Ce4+ ! Fe3+ + Ce3+

ECe4+ = EFe3+ = Esystem

EIn = ECe4+ = EFe3+ = Esystem

Equivalence Point Potentials

Fe3 + e- ! Fe
2+
Ce4+ + e- ! Ce
3+

0 0.0592 [Ce3+ ]
1. Eeq = E ! log
Ce4+ 1 [Ce4+ ]

0 0.0592 [Fe2+ ]
2. Eeq = E ! log
Fe3+ 1 [Fe3+ ]

0 0 [Ce3+ ][Fe2+ ]
2 Eeq = E +E ! (1)
Ce4+ Fe3+ [Ce4+ ][Fe3+ ]

Definition of e.p. requires that:

[Fe3+] = [Ce3+]
[Fe2+] = [Ce4+]
 3+ 4+
0.0592 [Ce ][Ce ]
2 E eq = E 0 +E 0 ! log = E0 + E0
Ce4+ Fe3+ 1 4+ 3+ Ce4 + Fe3+
[Ce ][Ce ]

E0
E 0 3+
4+
Eeq= Ce Fe (2)
2

The Derivation of Titration Curves

Titration of 50.00 mL of 0.05000 M Fe2+ with 0.1000 M Ce4+ in a
solution that is 1.0 M in H2SO 4 at all times.

Ce4+ + e- ! Ce
3+
Ef = 1.44V
Fe3+ + e- ! Fe
2+
Ef = 0.68V

1. Initial potential – Ce and Fe3+ only present in very small amounts.

2. Potential after addition of 5.00 mL of Ce4+

0.500
[Fe3+]= 5.00x 0.1000" [Ce4+ ] !
50.00
+ 5.00 55.00

50.00x 0.0500
- 5.00x 0.1000 2.000
[Fe2+] = + [Ce4+ ] !
55.00 55.00

Substitution into Nernst equation:

= +0.68- 0.0592log 2.00/55.00 = 0.64V

E system
1 0.500/55.00

E.P. potential
 f f
ECe 4+
+E
Fe3+ 1.44+ 0.68
E eq = = = 1.06V
2 2

3. Potential after addition of 25.10 mL of Ce4+

[Fe2+] = amt of Ce4+ left unreacted, therefore added to CCe4+

calculated from the volumes of the two solutions and subtracted from
CCe3+

Conc of two cerium ion species:

[Ce3+]= 25.00x 0.1000" [Fe2+ ] ! 2.500

75.10 75.10

0.0592 [Ce3+ ] 2.500/75.00

E = +1.44! log =+1.44- 0.0592
log
1 [Ce4+ ] 1 0.010/75.10

= +1.30 V

Effect of system variables on redox titration curves

Concentration – independent of analyte and reagent concentrations.

Exception: Electrode potentials dependent upon dilution

I 3! +2e- ! 3 I-

0.0592 [I -]3
E = E0! log
2 [I 3- ]

num-mol/L3, denom-mol/L
Completeness of reaction – the change in Esystem in the e.p. region
becomes larger as the reaction becomes more concentrated.
Redox indicators

a. specific indicators – react with one of the participants in the

titration to produce a color, e.g. thiocyanate

b. Oxidation-reduction indicators- respond to the potential of the

system rather than to the appearance or disappearance of some
species during the course of the titration, e.g. methylene blue

Color changes will occur over the range:

0.05916
E = (E 0 ± )Volts
n
where n= # of electrons in the indicator half-reaction

-larger diff in std potential between titrant and analyte, the sharper the
break in the titration curve at the e.p.

≥0.2 V, best detected potentiometrically

Gran plot
- more accurate way to use potentiometric data
- uses data well before e.p. (Ve) to locate Ve

For the oxidation of Fe2+ to Fe3+, the potential prior to Ve is:

0' [Fe2+ ]
E = [E ! 0.05916
log( )! E
3+ ref
[Fe ]

where, E 0'= formal potential for Fe3+ Fe2+ and Eref is the potential of the
reference electrode.

If vol of analyte = V0 and the vol of titrant = V, and if reaction goes to

completion with each addition of titrant:

[Fe2+] / [Fe3+] = (Ve-V)

V 10-nE/0.05916 = Ve10-n(Eref –E0’)/0.05916 - V 10-n(Eref –E0’)/0.05916

y b x m

Adjustment of Analyte Oxidation State

-before titration, e.g. Mn2+ preoxidized to MnO4-

-excess preadjustement reagent must be destroyed so that it will not

interfere in subsequent titration

Preoxidation
-powerful oxidants can be removed after preoxidation, e.g.
peroxydisulfate (S2O 8 2-) – requires Ag+ as a catalyst.

S2O82- + Ag+ ! SO24- + SO-4 + Ag2+

Excess reagent destroyed:

boiling
2S2O82- + 2H O !! ! !!" 4SO24- + O + 4H+
2 2

Prereduction
-Stannous chloride (SnCl2) will reduce Fe3+ to Fe2+ in hot HCl

Excess reductant is then destroyed:

Sn2+ + 2HgCl2 ! Sn4+ + HgCl2 + 2 Cl-

Oxidation with Potassium Permanganate

-strong oxidant, violet color

In strongly acidic solutions, reduced to colorless Mn2+:

MnO4- + 8H + + 5e- ! Mn
2+
+ 4 H 20
In neutral or alkaline solution, the product is the brown solid, MnO2:

MnO4- + 4H + + 3e- ! MnO2(s) + 2H 2 O

In strongly alkaline solution (2 M NaOH), green manganate is

produced:

MnO4- + e- ! MnO4 2-

Tales 16.3……..see below

Note: permanganate solutions are unstable, therefore not a primary

standard.
4MnO4- + 2H 2 O > 4MnO2 + 4OH- + 3O 2 (MnO2 catalyses this
reaction)
Permanganate must be standardized for example with oxalate;
H 2 C2 O 4 > 2H + + CO 2 + 2e-
Overall:
. 2MnO4- + 5H 2C2 O 4 + 16H + > 2Mn2+ + 10CO 2 + 8H 2 O
Initially the reaction is slow but is catalyzed by Mn2+ so becomes
more rapid.
Can also standardize with arsenic (III) oxide
As(III) > As(V) + 2e-
The reaction of As (III) with permanganate ion takes place without
complications in acidic medium if a trace of an iodine compound (for
example potassium iodate) is added as a catalyst.
The reaction generally carried out in HCl rather than H2SO 4
.... in the latter a brown green coloration occurs due to formation of a
manganese arsenate compound
KMnO4 can serve as own indicator, since product Mn2+ is colorless.
Cerium(IV)
Strong oxidant > Ce(III)
Ce4+ [Yellow ]+ e- > Ce3+ [Colorless]
Note however that the color change not good enough for it to act as
self indicator.
Ce(IV) not found in acid solution as simple aqua ion .. forms
complexes.
Dichromate reactions
Dichromate ion is an oxidizing agent
Cr2 O 7 2- + 14H + + 6e- > 2Cr3+ + 7H 2 O E = +1.33V
Dichromate has replace permanganate in many analyses ... notably
iron (II)... it can be prepared as a standard solution and so avoids the
need to standardize as is the case with permanganate.
Iodine Methods
I2 + 2e- > 2I- E = +0.54V
Value for E is intermediate can therefore be reduced or
oxidized...iodine can be reduced to iodide by for example As(III),
Sn(II) whilst iodide can be oxidized to iodine by for example
permanganate. Use of iodide as titrant..practical problems ..so add
excess potassium iodide and titrate the liberated iodine with for
example standard thiosulphate solution

Miscellaneous Oxidizing agents

Sodium bismuthate and lead (IV) oxide are strong oxidizing agents.
NaBiO 3 + 6H + + 2e- > Na + + Bi3+ + 3H 2 O E = +1.6V
PbO 2 + 4H + + 2e- > Pb2+ + 2H 2 O E = +1.5V

Hydrogen peroxide
... strong oxidant even in alkaline conditions.
H 2 O 2 + 2H + + 2e- > 2H 2 O E = +1.77V
Excess peroxide may be removed by boiling...decomposes

Ex: Derive a titration curve for the titration of 50.00 mL of 0.02500

M U4+ with 0.1000 M Ce4+