CHAPTER I

TITRATIONS INVOLVING
OXIDATION REDUCTION REACTIONS

/ reactions involve transfer of electrons from one reactant to

another.
The oxidaion of Fe2+ with Ce4+ is represented by the equation

Ce4+ + Fe2+ Ce3+ + Fe3+

Ce4+ has strong affinity for electrons (electron acceptor) and is

called an oxidizing agent or oxidant. Fe2+ is ready to donate electrons
(electron donor) and is called reducing agent or reductant. Fe2+ is
oxidized by Ce4+ while Ce4+ is reduced by Fe2+.
The oxidation-reduction equation is made up of two half reactions.
Ce4+ + e- Ce3+ (reduction of Ce4+)
Fe2+ Fe3+ + e- (oxidation of Fe2+)
A half reaction cannot occur alone. It must be accompanied by a
second half reaction.
If chemical evidence shows that the equilibrium of the reaction lies
to the right, it can be stated that Ce4+ is a better electron acceptor
(stronger oxidant) than Fe3+ and that Fe2+ is more effective electron donor
(better reductant) than Ce3+
or generally
Ox1 + Red2 Red1 + Ox2
To understand such tendency we have to study the electrochemical
cells and electrode potential.

ELECTROCHEMICAL CELLS
The electrochemical cell illustrates the fact that redox processes are
transfer of electrons.
The electrochemical cells include the galvanic (voltaic) and
electrolytic. In a voltaic cell, a spontaneous chemical reaction takes
place producing electricity. This occurs when the cell current is closed,
as when a flashlight appears. The cell voltage (e.g. in a battery) is
determined by the potential difference of the two half reactions. When
the reaction has gone to completion, the cell runs down, and the voltage is
zero (the battery is dead). In an electrolytic cell, however, the reaction is

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forced to the opposite direction by applying an external voltage greater
than and opposite to the spontaneous voltage. In both types, the electrode
at which oxidation occurs is the anode and that at which reduction occurs
is the cathode.
Voltaic cells are of importance on discussing potentiometry while
the electrolytic cells in methods such as voltammetry.
The cell potential :
Consider the following redox reaction in a voltaic cell
Fe2+ + Ce4+ Fe3+ + Ce3+
Now assume that Fe2+ solution and Ce4+ solution are placed in
separate beakers and connected by a salt bridge (it allows charge transfer
through the solution but prevents mixing of the solutions : i.e. maintains
electrical neutrality). Now put an inert Pt wire in each solution and
connect the two wires. The set up constitutes a voltaic cell. If a
microammeter is connected, current flow is indicated and the electron
directed from anode (at which Fe2+ is oxidized) to cathode (at which Ce4+
is reduced).
Therefore, each electrode will adopt an electrical potential
(tendency to give off or take on electrons) and is called electrode
potential. The larger the potential difference the greater the tendency for
the reactions between Fe2+ & Ce4+ to take place. This driving force
(potential difference) can be used to perform work such as lighting (e.g.
battery) or running motor (car). It should be noted that no half reaction
can occur by itself, but each will generate a definite potential.

-2-
HALF-REACTION POTENTIALS :
No way to measure individual electrode potentials (i.e. half
reaction potential), but the difference between two electrode potentials
can be measured. The electrode potential of the half-reaction.

H+ + e- H

has arbitrarily been assigned a value of 0.00 V at standard conditions of

[H+], PH, and T and is called NHE (normal hydrogen electrode) or SHE
(standard hydrogen electrode). All other electrode potentials are
measured relative to it and are arranged in a decreasing order. In the
Gibbs-Stockholm convention, adopted at the 17th conference of the
International Union of Pure & Applied chemistry in Stockholm 1953,
half-reactions are written as reduction reactions and the potential
increases as the tendency for reduction (of the oxidized form of the half-
reaction) increases.

Table : Some Standard Potentials

Half-Reaction Eo (V)
+ -
H2O2 + 2H + 2e = 2H2O 1.77
MnO4- + 4H+ + 3e- = MnO2 + 2H2O 1.695
Ce4+ + e- = Ce3+ 1.61
MnO4- + 8H+ + 5e- = Mn2+ + 4H2O 1.51
Cr2O72- + 14H+ + 6e- = 2Cr3+ + 7H2O 1.33
MnO2 + 4H+ + 2e- = Mn2+ + 2H2O 1.23
2IO3- + 12H+ + 10e- = I2 + 6H2O 1.20
H2O2 + 2e- = 2 OH- 0.88
Cu2 + I- + e- = CuI 0.86
Fe3+ + e- = Fe2+ 0.771
O2 + 2H+ + 2e- = H2O2 0.682
I2(aq) + 2e- = 2I- 0.6197
H3AsO4 + 2H+ + 2e- = H3AsO3 + H2O 0.559
I3- + 2e- = 3I- 0.5355
Sn4+ + 2e- = Sn2+ 0.154
S4O62- + 2e- = 2S2O32- 0.08
2H+ + 2e- = H2 0.000
Zn2+ + 2e- = Zn -0.763
2H2O + 2e- = H2 + 2OH- -0.828

-3-
 The general conclusions to be drawn are
(1) The more positive the electrode potential, the stronger the
oxidizing power.
(2) The more negative the electrode potential, the stronger the
reducing power.
Example :
a) Ce4+ (Eo = 1.61 V) is a good oxidizing agent but Ce3+ is a poor
reducing agent
b) Zn is a good reducing agent but Zn2+ (Eo = -0.763 V) is a poor
oxidant.
(3) The reduced form in a half-reaction is capable of reducing the
oxidized form in another half reaction with a more positive
potential

e.g. Fe3+ + e- = Fe2+ (Eo = 0.771 V)

Sn4+ + 2e- = Sn2+ (Eo = 0.154 V)
Therefore 2Fe3+ + Sn2+ = 2Fe2+ + Sn4+

Obviously no reaction possibility between two oxidants (Sn4+ & Fe3+)

or between two reductants (Sn2+ & Fe2+). But the reduced form of the
more negative potential (Sn2+) is reacting with the oxidized form of
the more positive potential (Fe3+). Note that the number of electrons
given from one Sn2+ must go to two Fe3+ ions. If the two potentials
are substracted and a positive value is given, the reaction goes
spontaneously as written above i.e. 0.771 V – 0.154 V = 0.617 V. If it
is negative, the reaction will occur in the reverse direction*.
Example : List the oxidizing power in decreasing order and the
reducing capability in decreasing order among the following

MnO4-, Ce3+, Cr3+, IO3-, Fe3+, I-, H+, Zn2+

*
This is the result of the convention that, for a spontaneous reaction, the free energy
change is negative. At standard conditions
∆ Go = nF ∆ Eo
For example, for
o o
E 4+ 3+ = 1.61 V and E 3+ 2+ = 0.771 V
Ce /Ce Fe /Fe
o
∆G for the former is more negative than the latter giving a negative value.

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Solution :
Referring to standard potentials table
- The most positive to least positive :
MnO4-, IO3-, Fe3+, H+, Zn2+ (MnO4-, most powerful and Zn2+, very poor).
- The remainder are reductants in order I-, Cr3+, Ce3+, (I- is a reasonably
good reductant, Ce3+ is poor)

The Anode and the Cathode :

Anode/solution/cathode

By convention, the anode is written on the left, the single lines

represent boundary lines. In the above Figure the cell is written as
Pt / Fe2+ (C1), Fe3+ (C2) // Ce4+ (C3), Ce3+ (C4) / Pt

C1, C2, C3 and C4 represent the concentrations of the different species, the
double line represents the salt bridge.
Since oxidation occurs at the anode and reduction occurs at the
cathode, the stronger reducing agent is placed on the left and the stronger
oxidizing agent is placed on the right.
The potential is given by

Ecell = Eright – Eleft = Ecathode - Eanode

= E(+) - E(-)

When the cell is set up properly, the calculated voltage will always
be positive, otherwise the reaction is proceeding in the reverse direction.
At standard conditions, in the above cell
o o _ o
Ecell = E E = 1.61 - 0.77
Ce 4+ / Ce 3+ Fe 3+/ Fe 2+

= 0.84 V
For a reaction to be complete enough to obtain a sharp end point in
a titration, there should be at least 0.2-0.3 V difference between the two
electrode potentials.
Example :
Determine the reaction between the following half reactions and
calculate the corresponding cell voltage.
Fe3+ + e- = Fe2+ Eo = 0.771 V
- - -
I3 + 2e = 3I Eo = 0.5355 V

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Solution :
1st is more +ve than 2nd, Fe3+ is a stronger oxidizing agent than I3-
and Fe3+ oxidizes I-.
∴ 2 Fe3+ + 3I- = 2 Fe2+ + I3- & Ecell = 0.771 – 0.536 = 0.235 V.
Note that multiplying a half-reaction by any number does not
change its potential.
The Nernst Equation*
(Potential as a function of concentration)
Eo listed in the table are determined when the [Ox] and [Red] and
all other species were at unit activity and they are called standard
potentials. Concentration rather than activity is used here because
titrations deal with large potential changes and errors are small by doing
so.
The potential dependence on concentration is described by the
Nernst equation. This equation is used to calculate the cell potential or
the electrode potential at concentrations other than 1.0 M.
aOx + ne- b Red

2.303 RT [Ox]a
E = Eo + ____________________
log ____________

nF [Red]b
Eo = standard electrode potential.
E = reduction potential under non-standard conditions.
n = number of electrons involved in the half-reaction.
R = gas constant (8.3145 JK-1 mol-1).
T = absolute temp in Kelvins.
F = Faraday const (96485 coul eq-1)
- At 25oC the above constant is 0.05916, while at 30oC it is equal to 0.06.
- The concentration of pure substances such as precipitates and liquids is
taken as unity.
Example :
A solution of 10-3 M Cr2O72- & 10-2 M Cr3+.
If pH is 2.0 what is the potential of the half reaction ?

*
Walther Herman Nernst (1841-1941) : German physical chemist, Noble Prize 1920; The passage of
1 Faraday in a solution produces a chemical change of 1 eq wt of substance.

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Solution :
Cr2O72- + 14 H+ + 6e- 2Cr3+ + 7H2O
0.06 (10-3) (10-2)14
E = Eo + _____________
log ________________________

6 (10-2)2

0.06
_____________
= 1.33 – 27 ( )
6
= 1.06 V

Theoretically, E would be infinity if there were no Cr3+ at all in

solution. Actually, the E is always finite, either there will be a small
amount of impurity (oxidized/reduced) or more probably the potential
will be limited by another half-reaction such as oxidation/reduction of
H2O that prevents it from going to infinity.

Remarks on Nernst Equation :

(1) In the following half reaction
aA + bB + ne- cC + dD

[C]c [D]d
________________
Keq =
[A]a [B]b

0.06 1
o ___________ ___________
E=E + log
n Keq

(2) [ ] = C = a , since a = fC & f = 1 for dilute solutions.

(3) ppt, solid and pure solvent have [ ] = 1
(4) E = Eo + 0 when [Ox] = [Red] or at unit activity.
(5) E is more +ve when [Ox] is high and vice versa E is more negative
when [Red] is high.
(6) In constructing a titration curve, we are interested in the equilibrium
electrode potential, Ecathode = Eanode and Ecell = 0, at which the titrant is
quantitatively reacted with the analyte (This happens when a battery
runs down).

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e.g. : 2Fe3+ + Sn2+ Sn4+ + 2Fe2+
Ox1 + Red2 Ox2 + Red1
[Ecathode = Eanode]

0.06 [Ox1] 0.06 [Ox2]

Eo1 + ________
log ___________
= Eo2 + _________
log ____________

n [Red1] n [Red2]

Rearrangement
n
___________
. ∆Eo = log Keq
0.06
OR

0.06
o ___________
∆E = log Keq
n

for the previous reaction

2
________
( 0.77 – 0.15) = log Keq
0.06

Keq = 1021

Problem
Calculate Keq for the reaction Cr2O72- (Eo = 1.33 V) and Fe2+ (Eo2 =
0.77 V)
Note that :
(i) log Keq = +ve → Keq > 1 → reaction is spontaneous as written
(ii) log Keq = -ve → Keq < 1 → reaction should be reversed (non-
spontaneous as written).
(iii) Keq ≥ 106 or ∆E ≥ n means that the reaction is quantitative.
(iv) The above reaction at equilibrium
2Fe3+ + Sn2+ Sn4+ + 2Fe2+
a Ox1 + b Red2 b Ox2 + a Red1
Ecathode = Eanode = E

-8-
 [Fe3+]
E = Eo1 + 0.06 log ____________

[Fe2+]

0.06 [Sn4+]
E = Eo2 + _______
log ____________
, multiply by 2
2+
2 [Sn ]

[Sn4+]
2E = 2Eo2 + 0.06 log ____________

[Sn2+]
____________________________________________________________

[Fe3+] [Sn4+]
3E = Eo1 + 2Eo2 + 0.06 log _____________________

[Fe2+] [Sn2+]

Since [Sn4+] = [Fe2+] & [Fe3+] = [Sn2+] at equivalence.

Eo1 + 2E2o
___________________
E =
3
or generally

bEo1 + aE2o
___________________
E =
b+a

2 x 0.77 + 1 x 0.15
____________________________
∴E =
3

= 0.563 V

Formal potential :
Formal potential is designated as Eo`. It is the standard potential of
a redox couple at 1 M concentrations and with solution conditions
specified.
e.g. Eo` for Ce4+/Ce3+ couple in 1 M HCl is 1.28 V (note that Eo = 1.61 V);
in this case HCl complexes with cerium (IV and III) with different Kf.
The formal potential is used when not all species are known and the
Nernst equation is written as usual using Eo` instead of Eo.

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Limitations for Eo uses :
(1) pH effect :
Many redox reactions involve protons and their potentials are
influenced by pH.
Ox + m H+ + ne- Red + m/2 H2O
(write equations for the couples Cr2O72-/Cr3+; MnO4-/Mn2+; IO3-/I-;
H3AsO4/H3 AsO3).

0.06 [Ox] [H+]m

E = Eo + ____________
log _________________

ne [Red]

m 0.06 [Ox]
or E = Eo + 0.06 _________
log [H+] + ___________
log _________
n n [Red]

m
o _____
The term E + 0.06 log [H+] = E0` = formal potential
n

Example :
H3AsO4 + 2H+ + 2e- H3AsO3 + H2O

0.06 [H3AsO4] [H+]2

E = Eo + _____________
log _____________________

2 [H3AsO3]

0.06 [H3AsO4]
∴E o
= E + 0.06 log [H ] + + __________
log ________________

2 [H3AsO3]

0.06 [H3AsO4]
o __________ ________________
or E = E - 0.06 pH + log
2 [H3AsO3]

The term (Eo –0.06 pH), where Eo is the standard potential, is

considered as Formal potential (Eo`). In neutral solution it is Eo – 0.06 (7)
= Eo – 0.42 = 0.559 – 0.42 = 0.139 V.
Therefore, in strongly acid medium H3AsO4, Eo = 0.559 V will
oxidize I-, but in neutral medium Eo` = 0.139 V less than (I3-/3I- = 0.535

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V) the reaction goes in the reverse direction and I2 oxidizes H3AsO3.
The pH effect may be through secondary reactions as illustrated
here
(i) S + 2e- S2-
H+

H2S

i.e. Acidity favors reduction and the reduced form is eliminated

increasing E measured or Eo`
(ii) I2 + 2e 2I-
-
+ OH

IO-

i.e. Alkalinity favors oxidation and eliminates the oxidant decreasing E

measured or Eo`.
In Fe(CN)63-/Fe(CN)64- couple; H+ addition eliminates Fe(CN)64-
through weak acid formation, increasing thereby Eo`.

(2) Precipitation :
Ag+ + e- Ag Eo = 0.799 V
E = E + 0.06 log [Ag+];
o
X- addition
Ag+ + X- AgX
Ksp
[Ag+] = ____________
[X-]

Substitution gives:
Ksp
o __________
E = E + 0.06 log
[X-]

= Eo + 0.06 log Ksp – 0.06 log [X-]

Eo`

i.e. Eo` is going parallel to Ksp value

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 Eo` for AgCl/Ag = 0.222 V, for AgI/Ag = -0.151 V and the
measured
E is inversely proportional to [X-]
Example: Calculate E for Ag electrode immersed in 0.05 M NaCl
solution (Ksp = 1.8 x 10-10)
(a) EoAg+/Ag = 0.799 V (b) Eo`AgCl/Ag = 0.222 V

Solution :
(a) Ag+ + e- Ag Eo` = 0.799
E = E + 0.06 log [Ag+]
o

Ksp
___________
= 0.799 + 0.06 log = 0.299 V
-
[Cl ]
(b) AgCl + e- Ag + Cl- Eo` = 0.222 V
1
__________
E = 0.222 + 0.06 log = 0.299 V
0.05
* Other situations
- Addition of Zn2+ to Fe(CN)63-/Fe(CN)64- increases E due to
pptation of ferrocyanide.
- ECu2+/Cu+ is increased also by addition of I- or NCS- through
Cu+ removal.

(3) Complexation :
Ag+ + e- Ago
Ag + 2X = Ag X2-
+ -

[Ag X2-]
_______________
and Kf =
[Ag+] [X-]2
E = EoAg+/Ag + 0.06 log [Ag+]
[Ag X2-]
= E Ag+/Ag + 0.06 log _______________
o

Kf [X-]2
[Ag X2-]
E = EoAg+/Ag - 0.06 log Kf + 0.06 log _______________

[X-]2
Eo`

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 [Ag X2-]
o` _____________
E = E + 0.06 log
[X-]2

Example :
Calculate E for Ag electrode in 1.0 M KCN to which sufficient Ag+
is added to give Ag(CN)2- complex of 0.01 M using
Eo = 0.799 V or Eo` = -0.46 V (Answer = -0.58 V)
- Another situation is the F addition to Fe3+/Fe2+ where its
-

potential decreases through FeF63- formation.

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 Titration Curves
100 ml of 0.1 M Fe2+ is titrated with 0.1 M Ce4+ in dil H2SO4
Ce4+ + Fe2+ = Ce3+ + Fe3+
(1) (2) E01 = 1.45 V; Eo2 = 0.75 V

Solution :
1
____________
log Keq = (1.45 – 0.75); and Keq = 7 x 1011
0.06

0.36
___________
& ∆E > ∴ Reaction is quantitative (refer p. 8)
1

(a) Before e.p. change will be in Fe3+/Fe2+ ratio

* with 10 ml Ce4+
10
E = 0.75 + 0.06 log _____ = 0.69 V
90
4+
* with 50 ml Ce E = 0.75 V
* with 90 ml Ce4+ E = 0.81 V
* with 99 ml Ce4+ E = 0.87 V

1Eo1 + 1Eo2
_________________
(b) At e.p. E = ⇒ 1.10 V
1+1

(c) After e.p. change in Ce4+ / Ce3+ ratio

[Ce4+]
4+ ___________
* with 100.1 ml Ce E = 1.45 + 0.06 log
[Ce3+]
E = 1.27 V
* with 110 ml Ce4+ E = 1.39 V

End point detection :

(1) Self indicator : MnO4- and I2 titrations.
(2) External indicator :
Use of ferricyanide in Fe2+ titration with Cr2O72-

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(3) Internal indicator :
Inox + ne In red

Requirements :
(a) Inox and In red are of different distinctive colors.
(b) The reaction should be reversible, so that back titration is possible.
(c) Soluble in H2O to give stable solution and should not undergo side
reactions.
(d) The Transition Potential Range (TPR) E = Eo ± 0.06 should be
between Eo of sample and Eo titrant; note that (±1) from
Inox 10 1
___________ _____ ______
log ( to ) ∴ i.e. +1 to –1.
In red 1 10

(e) TPR should not be affected by pH change otherwise a buffer is used

e.g. (i) (Ph)3 Fe3+ + e- (Ph)3 Fe2+ Fe2+

blue red
N

3
Ferroin
or (1,10-phenanthroline)
(ii) Diphenylamine for Fe2+ vs Cr2O72-

H H
NH N N + 2H+ + 2e-

Diphenylamine Diphenylbenzidine
colorless colorless

N N + 2H+ + 2e-

Violet
Diphenylbenzidine violet
o
E = 0.76 V

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 CHAPTER II
Applications of Redox Titrations

Permanganate Titrations
[A] Reactions : Mn7+ is reduced to +2, +3, +4 and +6 states.
• Strong acid medium (+2 state)
MnO4- + 8H+ + 5e- Mn2+ + 4H2O (Eo = 1.51 V)
• Moderate acidic medium (+3 state)
H2P2O72-
- + -
* MnO4 + 8H + 4e Mn(H2P2O7)33- + 4H2O (Eo = 1.7 V)
(H2P2O72- stabilizes Mn3+, otherwise 2Mn3+ Mn2+ + Mn4+)
• Neutral (pH 4-7) medium (+4 state)
MnO4- + 4H+ + 3e- MnO2 + 2H2O (Eo = 1.69 V)
• Alkaline medium (+ 6 state)
(1 M OH-)
MnO4- + e- MnO42- (Eo = 0.55 V)

[B] Stability : It is a SECONDARY STANDARD and should be

standardized
- Unstable in presence of Mn2+
2 MnO4- + 3Mn2+ + 2H2O 5 MnO2 + 4H+
So addition of H+ favors the appearance of MnO4- color towards the
end point.
- Tends to oxidize H2O
4MnO4- + 2H2O 4MnO2 + 3O2 + 4OH-
- Standardized by H2C2O4, 2 MnO2, As2O3 every 3 weeks

[C] Applications :
(1) Direct titration :
Standard MnO4- is used to determine H2O2; Fe2+ & Fe3+
mixture, reduced iron (Fe2O3 + Feo), iron protoxalate (FeC2O4 &
H2C2O4); oxalic and oxalate mixture; Ferrocyanide and Ferricyanide
mixture.
(2) Back titration :
NO2- & HCOO-
(3) Indirect titration
Ca2+; Pb subacetate & persulfate.

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Applications :
I- Direct Titration
(1) H2O2
5 H2O2 + 6H+ + 2MnO4- = 2Mn2+ + 8H2O + 5O2
2MnO4- ≡ 5H2O2 = 10e-
Note : 2H2O2 = 2H2O + O2
2 x 34.02 → 22400 ml
1 g → 329.2 ml O2
(2) Fe2+ & Fe3+
MnO4- + 5Fe2+ + 8H+ = 5Fe3+ + 4H2O
MnO4- ≡ 5Fe2+ ≡ 5e-
In total, Fe3+ is reduced by Sn2+ followed by HgCl2 addition & then
Zimmermann Reinhardt Reagent
(MnSO4, H3PO4, H2SO4) why ?

(3) Reduced Iron (Fe2O3 + Feo) contains not less than 80% Fe
through reduction of Fe2O3 by H2 gas.
Fe2O3 + Fe + Cu2+ = Fe2O3 + Cuo + Fe2+
↓ Filter
2+
Fe , determined as above

(4) Iron protoxalate : (FeC2O4 & H2C2O4)

- 5H2C2O4 + 2MnO4- + 6H+ = 10CO2 + 2Mn2+ + 8H2O
V1 = Total
{ - 5FeC2O4 + 3MnO4- + 24H+ = 5Fe3+ 10CO2 + 3Mn2+ + 12H2O
↓ Zn powder
filter
V2 ≡ Fe3+ ← 5Fe2+
MnO4-
∴ 3V2 ≡ FeC2O4
and V1 – 3V2 = H2C2O4

(5) H2C2O4 & Na2C2O4 : Acid by base; Total by MnO4-.

(6) Fe(CN)64- & Fe(CN)63-
2Fe(CN)63- + H2O2 = 2Fe(CN)64- + 2H+ + O2
then 5Fe(CN)64- + MnO4- + 8H+ = 5Fe(CN)63- + Mn2+ + 4H2O
(Total); New portion with MnO4-; V2 ≡ Ferrocyanide & ∆V ≡
Ferricyanide.
∴ V1 = total

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II- Back Titration :
(7) NO2-
V2 MnO4-

NO2-
V1 MnO4- MnO4-
C2O42- Vox
[(V1 + V2) MnO4- - VOX] = MnO4- corresponding to NO2-
∆
- - +
5NO2 + 2MnO4 + 6H 5NO3- + 2Mn2+ + 3H2O
50oC
(8) HCOO- Same procedure like (7)
5HCOO- + 2MnO4- + 11H+ = 5CO2 + 2Mn2+ + 8H2O
HCOO-
1 ml 0.1 N MnO4- = ____________________
2 x 10 x 1000
III- Indirect Determination :
(9) Ca2+ :
Ca2+ + C2O42- = CaC2O4 ↓
↓ H+
H2C2O4

Then Free oxalic is titrated with 0.1 N MnO4-

Ca2+
- _____________________
1 ml 0.1 N MnO4 =
2 x 10 x 1000
(10) PbAc and PbO (Pb subacetate)
- -
PbA + H2C2O4 = PbC2O4 + 2HA MnO4-
PbO + H2C2O4 = PbC2O4 + H2O
Portion ≠ NaOH → alkalinity H2C2O4
Portion ≠ MnO4- → total PbO PbAc OH-
2 HA
Base
(11) S2O82-
C2O42- + S2O82- = 2SO42- + 2CO2
5C2O42- + 2MnO4- + 16H+ = 10CO2 + 2Mn2+ + 8H2O
H2C2O4
S2O82-
MnO4-

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Dichromate titrations :
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O (Eo = 1.33 V)

a- PRIMARY STANDARD Why ? Its solution is stable indefinitely

others?
b- Due to its lower Eo; compared with MnO4-; cannot oxidize H2C2O4,
HCl and Fe(CN)64- quantitatively and therefore it is of limited use.
c- Cannot be used as self-indicator.
Ferroin is used as indicator for Fe2+ in Cr2O72- titration.
d- Used in the determination of
(i) reducing agents as glycerol
(ii) oxidants by addition of excess Fe2+ and back-titrate Fe2+

Cerric titrations :
Ce4+ + e- Ce3+ Eo (V)

More stable complexes [Ce(ClO4)63-] 1.70 in HClO4

Less stable complexes [Ce(NO3)63-] 1.61 in HNO3
1.45 in H2SO4
1.23 in HCl

Remarks :
(a) has different Eo on variation of acids, may be due to complexation of
Ce3+ species.
(b) oxidizing power ranges from stronger than MnO4- (Eo = 1.51 V) to
slightly less than Cr2O72- (Eo = 1.33 V).
(c) cannot be used in alkaline/neutral medium otherwise Ce(OH)3 ↓ will
precipitate.

(d) Compared with MnO4- & Cr2O72-

(1) Solutions are stable even on boiling.
(2) No intermediate product, it is a one-step reaction
Ce4+ + e- Ce3+
3+
(3) Ce is colorless (i.e. does not obscure end point).
(4) Ce4+ does not oxidize Cl- even in 2M H+.
(5) It is available in high purity and is used as a PRIMARY
STANDARD.
(6) Indicator used is Ferroin.

-19-
Applications :
Direct titration :
Fe(CN)64- , Fe2+ , H2O2, I- using Ferroin as indicator
Back titration :
Polyhydroxyalcohols (glycerol), aldehydes, hydroxy acids.
The excess is titrated with oxalate or AsO33-
2Ce4+ + C2O42- = 2Ce3+ + 2CO2
I Cl is catalyst, ferroin indicator

C2O42- + I+ = 2CO2 + I-
2Ce4+ + I- = I+ + 2Ce3+
____________________________________________

C2O42- + 2Ce4+ = 2CO2 = 2Ce3+

or 2Ce4+ + (H3 AsO3) As3+ = 2Ce3 + As5+

I Cl catalyst and ferroin indicator

As3+ + I+ = As5+ + I-
2Ce4+ + I- = 2Ce3+ + I+
_____________________________________________

2Ce4+ + As3+ = 2Ce3+ + As5+

-20-
 IODINE TITRATIONS
The intermediate Eo is behind the wide use of iodine titration

I2 + 2e- 2I- (Eo = 0.54 V)

Two Types are known

(A)Direct (Iodimetry) B) Indirect (Iodometry)
Sample :
Reducing agents Oxidizing agents
(S2-, S2O32-, SO32- … etc) (MnO4-, Ce4+, Fe3+ … etc)

Titrant I2 S2O32-
Indicator appearance of disappearance of
blue starch complex blue starch complex

Reaction I2 + 2e- 2I- 2I- 2e- + I2

(A) (B)

Example (A) * I2 + 2S2O32- = S4O62- + 2I- ;

(B) * 6I- + BrO3- + 6H+ = Br- + 3I2 + 3H2O

Factors affecting Eo of the system. These are

(1) pH effect : as described earlier under AsO43-/AsO33- system (P 10).
(2) Precipitating agent :
(a) Although EoCu2+/Cu+ = 0.17 V, is less than EoI2/I-, yet it oxidizes I-.
Cu2+ + 2I- CuI + I
Ksp = 10-11
Applying Nernst Eo = 0.83 V > EoI2/I- system

(b) Fe(CN)63- + e- Fe(CN)64- (Eo = 0.36 V)

Nevertheless, it oxidizes I- in presence of Zn2+ ion. The latter
removes Fe(CN)64- increasing its potential.

(3) Complexing agent :

- Hg2+ addition increases I2/I- potential through removal of I-
as HgI42-. The Eo for I2/I- is increased to 1.0 V. So it is easy
to oxidize AsO33- in the presence of Hg2+ (or as before in
neutral medium, HCO3-).
- EDTA or H2P2O72- complexes Fe3+ decreasing thereby its
potential and, therefore, Fe2+ could be titrated with I2 in
presence of any stated complexing agent.

-21-
End point detection
(a) Starch solution :
Colloidal dispersed starch particles form a dark blue adsorbate that
appears at the end point of direct titration (iodimetry) and disappears at
the end point of indirect titration.

Remarks :
(1) Starch solution is added towards the end point in
iodometry. The reversibility in colour appearance is
attained when iodine concentration is low.
(2) The color stability is decreased at high temperature.
(3) Starch should not be used in high acid medium. Why?
(4) Starch is unstable on storage due to bacterial
decomposition.

(b) Extraction method :

CCl4 or HCCl3 dissolves iodine giving pink color. It is less
convenient and more time consuming than starch solution. But
sometimes both methods give excellent results.

ERROR SOURCES :
1- Due to pH consideration :
(a) pH and I2
I2 + 2OH- = I- + IO- + H2O
3IO- = 2I- + IO3-
Therefore I2 titration cannot be used satisfactorily in alkaline
medium.
(b) pH & S2O32-
H+ + S2O32- = HS2O3- = HSO3- + S
xss = SO2 + H2O + S

The reaction is not rapid, so S2O32- could be used safely in

moderate acid medium as long as there is –at any time – insignificant
excess of S2O32-.
I2 reaction with thiosulphate is not quantitative in alkaline medium
since S2O32- is partially converted to SO42-.
(c) pH & I-
4I- + 4H+ + O2 = 2I2 + 2H2O
Therefore considerable O2 error is introduced giving in iodometry
positive error.

-22-
2- Due to I2 (Secondary standard) :
- Volatilizes easily at high temperature and low I-
concentration giving positive error.
- Its concentration changing with time as it reacts with
reducing agents (organic matter, SO2, H2S) giving positive
error.
- Disproportionates with H2O.
(I2 + H2O = HIO + I- + H+) giving positive error.

3- Due to starch :
Easily decomposable with bacteria or high acidity.

SELECTED APPLICATIONS
(I) IODIMETRY
(A) Direct titration :
* (1) As2O3 / Sb2O3
As2O3 + 2I2 + 2H2O = As2O5 + 4I- + 4H+
N.B. : * using OH-/CO32- gives positive error due to side reactions
6 OH- (CO32-) + 3I2 = 5I- + IO3- + 3H2O (CO2)
Therefore, use of HCO3- is appropriate to make the reaction
quantitative.

(B) Back titration of excess I2 :

OH- H+
* (2) 2 Ampicillin sod : → 2 penicilloic acid →
I2
2(CH3)2 C – CHCOOH → (CH3)2 C – CHCOOH
| | | |
SH NH2 S NH2
(D-penicillamine) |
S + 2HI
|
(CH3)2 C – CH COOH + 2HI
|
NH2
Disulphide

Excess I2 is back titrated with S2O32-

(∴ 2 ampicillin + I2 ≡ 2e-)

-23-
* (3) HgCl2
a. HgCl2 + HCHO + 3NaOH → Hg + 2NaCl + HCOONa + 2H2O
b. Hg + I2 = HgI2
c. HgI2 + 2KI = K2HgI4 soluble (∴ HgCl2 ≡ I2 ≡ 2e-)

* (4) SO32- + I2 + H2O = SO42- + 2H+ + 2I-

II- IODOMETRY
(5) Chlorinated lime : ( % of Cl2 available)
CaCl (OCl) + 2CH3COOH = Ca (CH3COO)2 + HCl + HClO
HCl + HClO = H2O + Cl2
2HI + Cl2 = 2HCl + I2
I2 + 2S2O32- = 2I- + S4O62-
(∴ ClO- ≡ Cl2 ≡ I2 ≡ 2e- )
(6) CuSO4
2Cu2+ + 4I- = Cu2I2 + I2
(∴ 2Cu2+ ≡ I2 ≡ 2e- )

(7) Phenol salicylic acid, Aspirin, phenylepherine (any of them gives the
same reaction)
OH
OH
O - COCH3
Br Br
COOH
COOH
H+ Br2

aspirin Br
- -
Br2 + 2I = 2Br + I2
(∴ Aspirin ≡ 3Br2 ≡ 6e-)
(8) Glycerol
CH2OH
|
3 CHOH + 7 Cr2O72- + 56H+ = 14Cr3+ + 9CO2 + 40H2O
|
CH2OH

Cr2O72- 3 glycerol glycerol

_________________ ___________________ _______________
(∴ ≡ ≡ ≡ 1e-)
6 7x2 14

-24-
(9) Organically combined I :
SO3

fuse
a. NaI
Na2CO3
I N

OH
* I- + 3Br2 + 3H2O = IO3- + 6HBr (remove excess Br2)
* IO3- + 5I- + 6H+ = 3I2 + 3H2O

(∴ Org I ≡ IO3- ≡ 6e-; increasing sensitivity)

(10) Polyhydroxy Alcohols / Aldehydes / Aldoses

(a) e.g. Mannitol

CH2OH (CHOH)n CH2OH consumes n + 1 HIO4

(mannitol consumes 5 HIO4)

2CH2O + 4 HCOOH + 5HIO3 + H2O

(from terminal OH) (from 2 ry OH)
Both IO3- & IO4- react with I- to give I2
IO3- + 5I- + 6H+ = 4I2 + 4H2O
IO4- + 7I- + 6H+ = 3I2 + 4H2O
VBlank – VExp. = Vmannitol
(∴ I M IO4- = Mannitol)
(b) Aldehydes and Aldoses (e.g. glucose)
(i) I2 + OH- = OI- + I-
RCHO + OI- = RCOOH + I-
(ii) OI- + I- + 2H+ = I2 + H2O
∴ RCHO ≡ IO- ≡ I2 ≡ 2e-
(11) Karl Fischer Reagent : (for H2O determination)
KFR is a mixture of pyridine, I2, SO2 & CH3OH and has a brown
color. Methanol is present in excess to prevent side reactions. It is
secondary standard and should be frequently standardized using dist H2O.

-25-
Main Reaction :
End point from yellow (product) to brown color excess titrant

+ I2 + 2

N H H N N
+ O
+

+ SO2 + N O3S N

excess CH3OH

CH3SO4
yellow

(side reaction) NSO3 + H2O

HSO4; prevented by additon of more CH3OH

This side reaction consumes more H2O, thereby giving negative

error.

KIO3 Titrations
(i) Primary standard, (ii) prepared in molar solution, (iii) solution
has different Eq. Wt according to the reaction involved.
1 N H+
Reaction 1: IO3- + 6H+ + 5e- I + 3H2O [Eo = 1.178 V)

4 N H+
Reaction 2: IO3- + Cl- + 6H+ + 4e- ICl + 3H2O (Eo = 1.24 V)

-26-
 • In Andrew’s reaction (reaction 2) the HCl normality should
be more than 4N, otherwise I+ will hydrolyze to give free I2
which consumes more IO3- , (i.e. positive error)

I+ + H2O HOI + H+

• Lang’s modification
In HCN solution, lower acidity (1-2 N HCl) is sufficient for
quantitation because ICN is more stable than ICl.

IO3- + 2I- + 3CN- + 6H+ = 3ICN + 3H2O

• End point detection :

Lang’s vs Andrew’s; in HCN starch can be used, while in 4N HCl
it cannot be used. Why ?

KBrO3 Titrations
It is a primary standard
BrO3- + 6H+ + 6e- = Br- + 3H2O (Eo = 1.44 V)

The end point could be detected by irreversible indicator Methyl-

orange (Methyl Red) which is bleached by xss Br2.

Applications : It is used in the following determinations

(1) Strong reductants :
As3+ in 2-3 N HCl
(2) Weak reductants
Ions (Mn2+, Cr3+, H2C2O4) reduce BrO3- partly to Br- and partly to Br2.

BrO3- + 6H+ + 5e- ½ Br2 + 3H2O

Addition of Hg2+ removes Br- as HgBr2, thus increasing the

tendency for reduction to Br- only.

-27-
(3) Indirect determination
(a) Phenol, Salicylic acid, Aspirin.
(b) Cations e.g. Mg2+, Al3+

chelate (ppt)
Mg2+ +

N H+

free ligand
OH
(8-hydroxyquinoline)

2
r
Br

2B
2HBr +

N Br

OH
(∴ 1 Mg2+ = 2 ligand = 4Br = 4e-)

-28-
 PRIOR OXIDATION and PRIOR REDUCTION

• This is carried out before the actual analysis to change the

sample component to the desired oxidation state. Iron salts,
for example, usually contain both Fe(II) & Fe(III). These
should quantitatively be converted to either Fe(II) through
prereductant addition or Fe(III) by preoxidant addition.
• Limitations :
1- Reaction should be quantitative and reasonably rapid.
2- Reaction must not interfere with other sample components.
3- Easy to remove the excess completely through
a- boiling (e.g. H2S, H2O2, S2O82-)
b- changing condition (e.g. HClO4 is oxidant when
hot, but not on cold).
c- 2nd phase use (e.g. metal, amalgam, BiO3-)

I- PREOXIDATIONS :
A. Gases :
(1) (Ozone) :
O3 + 2H+ + 2e- O2 + H2O (Eo = 2.07 V)
2H+ + O3 + Ag+ Ag3+ + O2 + H2O
3Ag3+ + 2Cr3+ 3Ag+ + 2Cr6+
Used : In acid medium (Ce3+, Cr3+, Mn2+) and in alkaline medium (NO2-,
I-, PO33-) to increase oxidation state. Excess O3 is removed by boiling or
by passing CO2. Ag+ is used as catalyst.

(2) (Bromine) :
Br2 + 2e- 2Br- (Eo = 1.07 V)
Used : I- → I2, remove excess by adding phenol or passing inert gas

B. Homogenous (HClO4, S2O82-, H2O2)

(3) HClO4 : ∆
HCIO4 + 7H + 7e → ½ Cl2 + 4H2O (Eo = 2.0 V)
+ -

- Used for Fe2+, Cr3+, org. S, org. As oxidation

- Removed through dilution or cooling.

-29-
(4) (NH4)2 S2O8 : (strong in acid medium and in presence of Ag+ as
catalyst)
S2O82- + 2e- 2SO42- (Eo = 2.01 V)
S2O82- + Ag+ 2SO42- + Ag3+ (slow)
3Ag3+ + 2Cr3+ 3Ag+ + 2Cr6+ (fast)
Excess Ag+ is removed as AgCl & S2O82- by boiling
2S2O82- + 2H2O = 2SO42- + 4H+ + O2

(5) H2O2 :
H2O2 + 2H+ + 2e- 2H2O (Eo = 1.77 V)
Used in acid medium (Fe2+, Sn2+ oxidation) or in alkaline medium
(Mn2+, Cr3+) and removed by boiling
2H2O2 H2O + O2

C. Solid peroxidant
(6) Na BiO3
BiO3- + 6H+ + 2e- = Bi3+ + 3H2O (Eo = 1.7 V)
Used for Mn2+ & Cr3+ oxidation and removed by filtration through
sintered glass filter.
II- PREREDUCTANTS
A. Gases :
(1) H2S :
2H+ + S + 2e- H2S (Eo = 0.14 V)
Used for Fe3+ reduction; removed by boiling or bubbling CO2. Its
drawback is the precipitation of cations.

(2) SO2 : pH dependent

SO42- + 4H+ + 2e- = H2SO3 + H2O (Eo = 0.17 V)
S2O62- + 4H+ + 2e- = 2H2SO3 (Eo = 0.15 V)
Used for Fe3+, As5+, Sb5+, Cr6+; Cu2+ (in SCN); removed by boiling
or CO2 bubbling.

B. Homogenous :
Sn4+ + 2e- Sn2+ (Eo = 0.154 V)
Used for Fe(III) reduction, keeping slight Sn2+ excess and high
[Cl-]. Excess Sn2+ is destroyed by Hg2+ addition giving Hg2Cl2. Large
[Sn2+] gives Hgo, the latter consumes more titrant producing positive
error.

-30-
C. Metallic :
* Jones Reductor : contains Zn-Hg packed into a column 36-cm
long, prepared through Zn/HgCl2 boiling.
Used : Reduction of Fe(III), Ti(IV), Ce(IV), Mn(VII) and Cr(VI).

Limitations :
(1) Its reducing action is non-selective.
(2) Cannot be used for solutions, containing NO3-. This is
converted to NH3, exhibiting interference.
(3) Air is reduced, therefore vacuum must be drawn into
column.
(4) H2SO4
2Zn + O2 + 2H2O = H2O + 2Zn (OH)2
is the appropriate acid used since HCl liberates H2 reacting with Zn.

* Walden Reductor : Less powerful but more selective reductant

Ag metal is used.
Ag+ + e- Ag (Eo = 0.77 V)
or AgCl + e- Ag + Cl- (Eo = 0.222 V)

Therefore, it is possible to decrease the reductant power on

changing [Cl-]; AgCl ppt on Ag metal could be washed out with NH3.
Again air could be reduced to H2O2.
Used : for Fe(III), Ce(IV), Mn(VII) and Cr(VI) reduction.
Standard Solutions :
* Oxidants :
Permanganate, Dichromate, Bromate, Ceric, Iodine and Iodate.

* Reductants :
Oxalates, thiosulphates, asrenite, ferrous ammonium sulphate.
Questions :
1- Calculate the equivalent weight for each.
2- Which is used as primary standard, and which as secondary
standard ?
3- How can you standardize the secondary standard solution ?

-31-