ANALYTICAL CHEMISTRY

Redox titration

1. REDOX REACTION

Oxidation - Reduction reactions (Redox rxns)

involve the transfer of electrons from one
species of the reactants to another. This results
in an increase in oxidation number (O.N.) of a
specific species and a complementary decrease
in oxidation number of another species.
Example:
Ce4+ + Fe2+ D Ce3+ + Fe3+
The O.N. of cerium was decreased while that of
iron was increased. Cerium is reduced while
iron is oxidized. A process that involves an
increase in O.N. is an oxidation process and vice
versa
3

Usually, a Redox reaction can be separated

into two halves.
Ce4+ + e D Ce3+
Fe2+ D Fe3+ + e

Reduction
Oxidation

Electrons appear in each half reaction while

they do not show up in the overall
equations.

Identification of a Redox Reaction

It is a good practice to indicate the O.N. of each
species in a chemical reaction in order to check if it
is a Redox reaction or not. If the O.N. of any
species changes, then it is a definite indication of a
Redox reaction. Example,
2 KMnO4 + 5 H2C2O4 + 6 HCl D 2 MnCl2 + 2KCl + 10 CO2 + 8 H2O

It is observed that in the left-hand part of the equation,

manganese has an O.N. equals 7 and carbon has
an O.N. equals 3. In the right-hand part, the O.N. of
manganese is 2 and that of carbon is 4.
Therefore, permanganate is reduced while oxalic
acid is oxidized.
5

An example of a non-Redox reaction can be

written where no change in O.N. occurs,
Na2CO3 +

2 HCl = 2 NaCl + CO2 + H2O

+1 +4 -2

+1 -1

+1 -1 +4 -2

+1 -2

There is no change in O.N. of any species

involved in the reaction, which indicates
that this is not a Redox reaction.

Balancing Redox Equations

Simple reactions easy to balance
Complex reactions
Usually encountered in laboratory
Can include CrO42-, Cr2O72-, MnO4-, NO3- and
SO42 Follow balancing guidelines

Balancing Redox Reactions

Guidelines
Step 1: Write the unbalanced equation for the reaction in ionic
form.
Step 2: Separate the equation into two half-reactions
Step 3: Balance each half-reaction for number and type of atoms
and charges. (Look at medium)
Step 4: Add the two half-reactions together and balance the final
equation by inspection. The electrons on both sides must cancel.
(Be sure they are equal)
Step 5: Verify that the equation contains the same type and
numbers of atoms and the same charges on both sides of the
equation.

Balancing Redox Equations

The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution?
1. Write the unbalanced equation for the reaction ion ionic form.
Fe2+ + Cr2O72-

Fe3+ + Cr3+

2. Separate the equation into two half-reactions.

+2

Fe2+

Oxidation:
+6

+3

Fe3+
+3

Cr2O72Cr3+
Reduction:
3. Balance the atoms other than O and H in each half-reaction.
Cr2O722Cr3+

Balancing Redox Reactions

4. For reactions in acid, add H2O to balance O atoms and H+ to
balance H atoms.
Cr2O722Cr3+ + 7H2O
14H+ + Cr2O722Cr3+ + 7H2O
5. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+
Fe3+ + 1e6e- + 14H+ + Cr2O722Cr3+ + 7H2O
6. If necessary, equalize the number of electrons in the two halfreactions by multiplying the half-reactions by appropriate
coefficients.
6Fe2+
6Fe3+ + 6e6e- + 14H+ + Cr2O722Cr3+ + 7H2O

Balancing Redox Reactions

7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.
Oxidation:
6Fe2+
Reduction: 6e- + 14H+ + Cr2O7214H+ + Cr2O72- + 6Fe2+

6Fe3+ + 6e2Cr3+ + 7H2O

6Fe3+ + 2Cr3+ + 7H2O

8. Verify that the number of atoms and the charges are balanced.
14x1 2 + 6x2 = 24 = 6x3 + 2x3
9. For reactions in basic solutions, add OH- to both sides of the
equation for every H+ that appears in the final equation.

17B Calculating Redox Equilibrium

Constants
Ex 17-6: Calculate

the equilibrium constant for the

reaction
Sol:

2Fe3+ + 3I- 2Fe2+ + I3-

2Fe3+ + 2e- 2Fe2+

I3- + 2e- 3I-

E0 = 0.536 V

E Fe3 /Fe 2 E 0 Fe3 /Fe 2

E I /I E 0 I3 /I
3

E0 = 0.771 V

0.0592
[Fe 2 ]2

log
2
[Fe3 ]2

0.0592
[I ]3

log
2
[I3 ]

E Fe3 /Fe2 E I /I
3

E 0 Fe3 /Fe2

3
0.0592
[Fe 2 ]2
0
.
0592
[
I
]
0

log

log
I 3 /I

3 2
2
[Fe ]
2
[I3 ]

2(E 0 Fe3 /Fe 2 - E 0 I3- /I - )

[Fe 2 ]2
[I ]3
log
log
3 2
0.0592
[ Fe ]
[I3 ]

[Fe 2 ]2 [I 3 ]
log
[Fe3 ]2 [I ]3

[Fe 2 ]2 [I 3 ] 2(E 0 Fe3 /Fe2 E 0 I3 /I )

log

3 2 3
[Fe ] [I ]
0.0592

2(E 0 Fe3 /Fe2 E 0 I3 /I ) 2(0.771 0.536)

log K eq

7.94
0.0592
0.0592
K eq anti log 7.94 8.7 107

Example 17-7
Calculate the equilibrium constant for the reaction
2MnO4- + 3Mn2+ + 2H2O 5MnO2(s) + 4H+

Sol: 2MnO4- + 8H+ +6e- 2MnO2(s) + 4H2O

3MnO2(s) + 12H+ + 6e- 3Mn2+ + 6H2O
EMnO4-/MnO2 = EMnO2/Mn2+

E0 = +1.695 V
E0 = +1.23 V

0.0592
1
0.0592
[Mn 2 ]3
1.695
log
1.23
log
2
8
6
6
[H ]12
[MnO 4 ] [H ]

6(1.695 1.23)
1
[H ]12
log
log
2
8
0.0592
[Mn 2 ]3
[MnO 4 ] [H ]
6(1.695 1.23)
[H ]12
log

0.0592
[MnO 4 ]2 [Mn 2 ]3 [H ]8
[ H ]4
47.1 log
log K eq
2
2 3
[MnO 4 ] [Mn ]

K eq anti log 47.1 110 47

Calculating potentials of electrochemical cells

Ecell = Eright Eleft
Ex.

Cu Cu2+(0.0200M)

Ag+(0.0200M) Ag

Cu (s) + 2Ag+ = Cu2+(aq) + 2Ag(s)

Ag+ + e = Ag(s)

Eo = + 0.799 V

Cu2+ + 2e = Cu(s)

Eo = + 0.337 V

2Ag+ + 2e = 2Ag(s) Eo = + 0.799 V

0.6984 V

E = 0.799 (0.05916/1) log (1/0.0200) =

Cu2+ + 2e = Cu(s)
0.2867V

E = 0.337 (0.05916/2) log (1/0.0200) =

Eo = + 0.337 V

Cu (s) + 2Ag+ = Cu2+(aq) + 2Ag(s)

Eocell = + 0.799 V (+ 0.337 V)
= + 0.462 V

Ecell = Eright Eleft = 0.6984 0.2864

= + 0.412 V

G = nFE = 2 96485 C 0.412 V = 79,503 J (18.99 kcal)

EX
Calculate the potential of the following cell and indicate the reaction that would occur
spontaneously if the cell were short-circuited.
Pt U4+(0.200M), UO22+(0.0150M), H+(0.300M) Fe2+(0.0100M), Fe3+ (0.0250M) Pt

The two half-reactions are

Fe3+ + e_ Fe2+
Eo = + 0.771V
UO22+ + 4H+ + 2e- U4+ + 2H2O Eo = + 0.334V
The electrode potential for the right-hand electrode is
Eright = 0.771 0.05916 log [Fe 2+]/[Fe 3+]
= 0.771 0.05916 log 0.0100/0.0250 = 0.771 ( 0.0236) = 0.7946 V
The electrode potential for the left-hand electrode is
ELeft = 0.334 (0.0592 / 2) log [U4+ ] / [UO22+][ H+]4
= 0.334 (0.0592 / 2) log 0.200 / (0.0150) (0.0300) 4
= 0.334 0.2136 = 0.1204 V
And
E cell = E right E left = 0.7946 0.2136 = 0.674V
The positive sign means that the spontaneous reaction is the oxidation of U 4+ on the
left and the reduction of Fe 3+ on the right, or
U4+ +2 Fe 3+ + 2H2O UO22+ +Fe 2+ + 4H+

EX
Calculate the cell potential for
Ag AgCl (satd), HCl (0.0200M) H2(0.800atm ), Pt

Cell without liquid junction

Note that this cell does not require two compartments (nor a salt bridge) because
molecular H2 has little tendency to react directly with the low concentration of Ag + in
the electrolyte solution. This is an example of a cell without liquid junction.
The two half- reactions and their corresponding standard electrode potentials are
2H+ + 2e - H2
AgCl(s) + e - Ag (s) + Cl

EoH+/H2 = 0.000V
EoAgCl/Ag = 0.222V

The two electrode potentials are

Eright = 0.000 (0.0592/2)log pH2 / [H+]2
= (0.0592/2) log 0.800 / (0.0200) 3 = 0.0977 V
Eleft = 0.222 0.0592log [Cl-] = 0.222 0.0592 log 0.0200 = 0.3226V
The cell potential is thus
E cell = E right E left = -0.0977 0.3226 = 0.420V
The negative sign indicates that the cell reaction as considered
2H+ + 2 Ag(s) H2 + 2AgCl(s)
is nonspontaneous. To get this reaction to occur, we would have to apply an external
voltage and construct an electrolytic cell.

Ex
Calculate the potential for the following cell using (a) concentration and (b) activities:
Zn ZnSO4(5.00 104 M), PbSO4 (satd) Pb
(a) [SO42] = CZnSO4 = 5.00 104
PbSO4(s) + 2e Pb (s) + SO42

Eo = 0.350 V

Zn2+ + 2e Zn (s)

Eo = 0.763 V

Eright = Eo (0.05916 / 2) log [SO42] = 0.350 (0.05916 / 2) log (5.00 104)

= 0.252 V
Eleft = Eo (0.05916 / 2) log (1 / [Zn2+]
= 0.763 (0.05916 / 2) log {1 / (5.00 104)} = 0.860 V
Ecell = Eright Eleft = 0.252 ( 0.860) = 0.608 V

(b) Ionic strength for 5.00 104 M ZnSO4 :

= (1/2) {(5.00 104) (+2)2 + (5.00 104) ( 2)2 } = 2.00 103

Debye-Huckel Eq. :

log = (0.51 Z2 ) / ( 1+ 3.3 )

SO42 = 0.4 nm , Zn2+ = 0.4 nm

SO42 = 0.820,

Zn2+ = 0.825

Activity = [C]
Eright = Eo (0.05916 / 2) log { SO42 [SO42] }
= 0.350 (0.05916 / 2) log (0.820 5.00 104) = 0.250 V
Eleft = Eo (0.05916 / 2) log {1 / ( Zn2+ [Zn2+])}
= 0.763 (0.05916 / 2) log {1 / (0.825 5.00 104)} = 0.863 V
Ecell = Eright Eleft = 0.250 ( 0.863) = 0.613 V

Redox systems in the respiratory chain, P=phosphate ion.

(From P.Karlson, Introduction to modern Biochemistry.)

Calculation Redox Equilibrium Constant

Cu

Cu2+(x M) Ag+(y M) Ag

Cu (s) + 2Ag+ = Cu2+(aq) + 2Ag(s)

Keq = [Cu2+] / [Ag+]2
2Ag+ + 2e = 2Ag(s) Eo = + 0.799 V
Cu2+ + 2e = Cu(s)

Eo = + 0.337 V

Ecell = Eright Eleft = EAg ECu = 0

or

Eright = Eleft = EAg = ECu

EoAg (0.05916/2) log (1/[Ag+]2) = EoCu (0.05916/2) log (1/[Cu2+])

EoAg EoCu = (0.05916/2) log (1/[Ag+]2) (0.05916/2) log (1/[Cu2+])
EoAg EoCu = (0.05916/2) log (1/[Ag+]2) + (0.05916/2) log ([Cu2+]/1)
2 (EoAg EoCu ) / 0.05916 = log ([Cu2+]/[Ag+]2 ) = log Keq
ln Keq = Go/RT= nFEocell / RT
ln Keq = nEocell / 0.05916 = n (Eoright Eoleft ) / 0.05916

<At 25oC >

REDOX TITRATION

Redox titrations
The methods of acid-base volumetric analysis
can be applied to redox titrations
A redox titration involves a controlled reaction
between a solution containing an oxidising agent
and another solution containing a reducing
agent
The equivalence point occurs when the oxidising
agent and reducing agent have reacted
chemically equivalent amounts
The end point is found using suitable indicators

Common Primary Standards

In redox titrations two common primary
standards used are:
Ammonium iron(II) sulfate (NH4)2Fe(SO4)2
Active species Fe2+(aq)
Fe2+(aq)
Fe3+ + e-

Oxalic acid H2C2O42H2O

Active species H2C2O4(aq)
H2C2O4(aq)

2CO2(g) + 2H+ + 2e-

Redox Titrations
Titration: A procedure for determining the concentration
of a solution by allowing a carefully measured volume to
react with a solution of another substance (the standard
solution) whose concentration is known.
5H2C2O4(aq) + 2MnO41-(aq) + 6H1+(aq)
10CO2(g) + 2Mn2+(aq) + 8H2O(l)
If the unknown concentration is the potassium
permanganate solution, MnO41-, it can be slowly added to
a known amount of oxalic acid, H2C2O4, until a faint
purple color persists.
Copyright 2008
Pearson Prentice Hall,

Chapter 4/28

Redox Titrations
A solution is prepared with 0.2585 g of oxalic acid,
H2C2O4. 22.35 mL of an unknown solution of potassium
permanganate are needed to titrate the solution. What is
the concentration of the potassium permanganate
solution?
5H2C2O4(aq) + 2MnO41-(aq) + 6H1+(aq)
10CO2(g) + 2Mn2+(aq) + 8H2O(l)
Mass of
H2C2O4
Molar Mass of
H2C2O4
Copyright 2008
Pearson Prentice Hall,

Moles of
H2C2O4
Mole Ratio
Chapter 4/32

Moles of
KMnO4
Molarity of
KMnO4

Molarity of
KMnO4

Redox Titrations
5H2C2O4(aq) + 2MnO41-(aq) + 6H1+(aq)
10CO2(g) + 2Mn2+(aq) + 8H2O(l)
Moles of H2C2O4 available:
0.2585 g H2C2O4 x

1 mol
90.04 g

= 0.002871 mol H2C2O4

Moles of KMnO4 reacted:

2 mol KMnO4
0.002871 mol H2C2O4 x
= 0.001148 mol KMnO4
5 mol H2C2O4
Copyright 2008
Pearson Prentice Hall,

Chapter 4/33

Redox Titrations
5H2C2O4(aq) + 2MnO41-(aq) + 6H1+(aq)
10CO2(g) + 2Mn2+(aq) + 8H2O(l)
Concentration of KMnO4 solution:
0.001148 mol KMnO4
22.35 mL

Copyright 2008
Pearson Prentice Hall,

1000 mL
1L

Chapter 4/34

= 0.05136 M KMnO4

18B Reducing Agents

Thiosulfate: stable to air oxidation
Iron(II): E0 = 0.771V
for titration of cerium(IV), chromium(VI),
vanadium(V)
indicator:
ferroin or diphenylamine sulfonate.

18C Oxidizing Agents

Potassium permanganate (KMnO4)
E0=1.51
In neutral solution: MnO4-MnO2
In acid solution: MnO4-Mn2+

Autocatalytic decomposition:
Standardization: Na2C2O4
5H2C2O4+2MnO4-+6H+
10CO2+2Mn2++8H2O

Cerium (IV): Ce4+ / H2SO4: E0 = 1.44V;

Ce4+ / HClO4: E0 = 1.70V
1) the rate of oxidation of chloride ion is slow
2) is stable in H2SO4
3) (NH4)2Ce(NO3)6 can be obtained as a primary
standard.

indicator: Ferroin

 Potassium dichromate: K2Cr2O7

a slightly weaker oxidizing agent than KMnO4
primary standard
Cr2O72- Cr3+
E0 = 1.33~1.00V in 1M HCl

Dr. S. M. Condren

Dr. S. M. Condren

Dr. S. M. Condren

Dr. S. M. Condren

Dr. S. M. Condren

Dr. S. M. Condren

Dr. S. M. Condren

REDOX TITRATION CURVE

16-1 The shape of a redox titration

curve
A redox titration is based on an oxidation-reduction
reaction between analyte and titrant.
Consider the titration of iron(II)
with standard cerium(IV),
monitored potentiometrically
with Pt and calomel electrodes.

The potentials show above is in 1 M HClO4

solution. Note that equilibria 16-2 and 16-3
are both established at the Pt electrode.

There are three distinct regions

in the titration of iron(II) with
standard cerium(IV), monitored
potentiometrically with Pt and
calomel electrodes.

1.

2.

3.

Before the equivalence point,

where the potential at Pt is
dominated by the analyte redox
pair.
At the equivalence point, where the
potential at the indicator electrode
is the average of their conditional
potential.
After the equivalence point, where
the potential was determined by the
titratant redox pair.

Before the equivalence point: using analytes concentration to calculate E +

At the equivalence point: needs both redox pairs to calculate (why?)

E of the cell

After the equivalence point:

There are two special points during the above titration process: (1)
when V = Ve, [Fe3+] = [Fe2+] and E+ = E(Fe3+ | Fe2+) ; (2) when V
= 2 Ve, [Ce4+] = [Ce3+] and E+ = E(Ce4+ | Ce3+) = 1.70 V.

Summary
The greater the difference in reduction potential between analyze and titrant,
the sharper will be the end point.

The voltage at any point in this titration depends only on the ratio of
reactants; it will be independent of dilution.

Prior to the equivalence point, the half-reaction involving analyze is used to

find the voltage because the concentrations of both the oxidized and the
reduced forms of analyte are known.

After the equivalence point, the half-reaction involving titrant is employed. At

the equivalence point, both half-reactions are used simultaneously to find
the voltage.

For the titration of Tl+ (Thallium) by IO3- in 1.00 M HCl solution

The curve is not symmetric

about the equivalence point.
This is because the
stoichiometry of reactants is
2:1, not 1:1.
Still, the curve is so steep near
the equivalence point that
negligible error is introduced if
the center of the steep part is
taken as the end point.

17C Constructing Redox Titration Curves

Example 17-8
Obtain an expression for the equivalence-point potential in
the titration of 0.0500 M U4+ with 0.1000 M Ce4+. Assume
that both solutions are 1.0 M in H2SO4.
U4+ + 2Ce4+ + 2H2O UO22+ + 2Ce3+ + 4H+

Sol: UO22+ + 4H+ + 2e- U4+ + 2H2O

E0 = 0.334 V

4
0
.
0592
[
U
] 0' = 1.44 V
Ce
+
e

E
2Ce
4
E eq E UO 2 /U
log
2
2
[ UO 2 ][H ]4

4+

0-

3+

E eq E 0 Ce 4 /Ce3

0.0592
[Ce 3 ]

log
1
[Ce 4 ]

2E eq 2E 0 UO 2 2 /U 4

[ U 4 ]
0.0592 log
2
[ UO 2 ][H ]4

3E eq 2E 0 UO 2 2 /U 4 E 0 Ce 4 /Ce3

[U 4 ][Ce 3 ]
0.0592 log
2
[ UO 2 ][Ce 4 ][H ]4

4
[
Ce
]
4
[U ]
2

3
[
Ce
]
2
[ UO 2 ]
2
2E 0 UO 2 2 /U 4 E 0 Ce 4 /Ce3 0.0592
2[Ce 4 ][Ce 3 ]
E eq

log
3
3
2[Ce 3 ][Ce 4 ][H ]4

2E 0 UO 2 2 /U 4 E 0 Ce 4 /Ce3 0.0592
1

log 4
3
3
[H ]

Table 17-1
Electrode Potential versus SHE in Titrations with 0.100 M Ce 4+
Potential, V vs. SHE
Reagent Volume,
mL

50.00 mL of
0.0500 M Fe2+

50.00 mL of
0.02500 M U4+

5.00

0.64

0.316

15.00

0.69

0.339

20.00

0.72

0.352

24.00

0.76

0.375

24.90

0.82

0.405

25.00

1.06

25.10

1.30

1.30

26.00

1.36

1.36

30.00

1.40

1.40

Equivalence
Point

0.703

Note: H2SO4 concentration is such that [H+] = 1.0 M throughout.

Titration curve : potentiometric titration of Fe2+ with

Ce4+.
Titration reaction: Ce4+ + Fe2+ Ce3+ + Fe3+

4+
3+
3+
2+
Cell:
Hgreference
Hg2Cl
| Pt
Reaction at the SCE
electrode:
2 Cl || Ce , Ce , Fe , Fe

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

Eo = 0.241V

Reaction at the Pt indicator electrode:

Fe3+ + e Fe2+

Eo = 0.767V (in 1M HClO4 )

Ce4+ + e Ce3+

Eo = 1.70V (in 1M HClO4 )

Cell reaction: 2Fe3+ + 2Hg(l) + 2 Cl 2 Fe2+ + Hg2Cl2(s)

2Ce4+ + 2Hg(l) + 2 Cl 2 Ce3+ + Hg2Cl2(s)
ECe = EFe = Esolution
Ecell = Ecathode Eanode = Esolution ESCE
Eocell = (0.767) (0.241) = 0.526 V
The equilibium constant for this titration reaction
K = 10 nEo/0.05916
log K = n E cell / 0.05916 = (1) (0.526) / (0.05916) =
o

K = 1.7 1017

Apparatus for potentiometric

titration of Fe2+ with Ce4+.

Initial Fe2+
Ve

Ve
[Ce4+]

[Ce4+] = [Ce3+]

Theoretical titration curve

for titration of 100ml of
0.050M Fe2+ with 0.100M
Ce4+ in 1M HClO4.

[Fe2+] = [Fe3+]

Region

Major constituents

Before the titration begins

Fe2+

Before the equivalence point

Fe2+ , Fe3+, Ce3+

[Ce3+] = [Fe3+]

Comment
No calculation possible
Use the Nernst equation
for the analyte half reaction

At the equivalence point

Fe3+, Ce3+

Use e.p equation

After the equivalence point

Fe3+, Ce3+, Ce4+

Use the Nernst equation for

the titrant half reaction

1) Before the equivalence point

(amount Fe2+ remaining) = (amount Fe2+ initial) (amount Ce4+ added amount
Fe2+ used)
(amount Fe3+ produced) = (amount Fe2+ used)
[Fe2+] = amount Fe2+ (mmol) / vol(ml),

[Fe3+] = amount Fe3+ (mmol) / vol(ml)

Ecell = Ecathode Eanode = Esolution ESCE

= (0.767 0.05916 log{[Fe2+]/[Fe3+]}) (0.241)
= 0.526 0.05916 log{[Fe2+]/[Fe3+]}
When V = (1/2) Ve,

[Fe2+] = [Fe3+],

Ecell = 0.526 .

2) At the equivalence point

[Ce3+] = [Fe3+]
[Ce4+] = [Fe2+]
Eeq = EoCe4+ 0.05916 log[Ce3+]/ [Ce4+]
Eeq = EoFe3+ 0.05916 log[Fe2+]/ [Fe3+]
2Eeq = EoCe4+ + EoFe3+ 0.05916 log[Ce3+]/ [Ce4+] 0.05916 log[Fe2+]/ [Fe3+]
= EoCe4+ + EoFe3+ 0.05916 log[Ce3+] [Fe2+] / [Ce4+] [Fe3+]
= EoCe4+ + EoFe3+
= 1.70 + 0.767
= 2.467
Eeq = (EoCe4+ + EoFe3+ ) / 2 = 1.23 V
E(cell) = Eright Ecalomel = 1.23 0.241 = 0.99V

3) After the equivalence point

[Fe2+] = 0
E(cell) = E+ Ecalomel
= ( 1.70 0.05916 log [Ce3+]/[Ce4+]) 0.241
amount Ce4+ remaining = amount Ce4+ added amount Ce4+ used
= amount Ce4+ added (amount Fe2+ initial reacting ratio )

Titration curves for 0.1000M Ce4+ titration , Curve A: Titration of 50.00mL of

0.05000 M Fe2+. Curve B: Titration of 50.00 ml of 0.02500 M U4+.

General approach to redox titration

( titration with an oxidizing agent)
T

T +

titrant

Mass balance
[T ] + [T] = Ttotal

analyte

[T ] + (1/ ) [T ] = Ttotal
[T ] = ( Ttotal) / (1+ )

T + e

E = E T 0.05916 log [T ] / [T]

o

[T ] / [T] = 10

( EoT E) / 0.05916

[T ] = [T]
A+

+ e

[T ] = [A+ ]

1:1 mole ratio

( Ttotal) / (1+ ) = Atotal / (1+ )

Fraction of titration

E = EoA 0.05916 log [A ] / [A+

]

[A+ ] = Atotal / (1+ )

= Ttotal / Atotal

( = 1 at eq point)

= (1+) / { ( 1+ )}

Titration of a mixture
The titration of two species will exhibit two breaks if the
standard potentials of the redox couples are sufficiently
different.
Example :
Titration reactions
First : IO3 + 2Sn2+ + 2Cl + 6H+ ICl2 + 2Sn4+ + 3H2O
Second : IO3 + 2Tl+ + 2Cl + 6H+ ICl2 + 2Tl3+ + 3H2O
Half reactions
IO3 + 2Cl + 6H+ + 4e ICl2 + 3H2O
V

Eo = 1.24

= [ICl2 ] /[IO3 ] = 10 [4(1.24 E) / 0.05916] 2 pCl 6 pH

Sn4+ + 2e Sn2+

Eo = 0.139

Theoretical curve for titration of 100 ml of

0.01M Tl+ with 0.01M IO3 in 1M HCl

Theoretical curves for 0.01M Tl+

plus 0.01M Sn2+ titrated with
0.01M IO3. The initial volume of
analyte is 100ml and all solutions
contain 1M HCl.

 plot for the Fe2+/Ce4+ system.

Totration curve calculated

using the inverse master
equation approach.
= Fe3+ /Ce3+

Factors affecting the shape of titration curves :

1) concentration
concentrated

E(V)

diluted

V(ml)

2) completeness of reaction
E(V)

Higher Eo titrant
Lower Eo titrant

V(ml)

Effect of titrant electrode potential on reaction completeness.

Dr. S. M. Condren

Dr. S. M. Condren

RedoxTitrationCurve
Derivation of a titration curve
Fe+2 + Ce+4 <=> Ce+3 + Fe+3
EXAMPLE: Derive the titration curve for
50.00 mL of 0.0500 M Fe+2 with 0.1000 M
Ce+4 in a medium that is 1.0 M in H2SO4.

Dr. S. M. Condren

EXAMPLE: Derive the titration

curve for 50.00 mL of 0.0500 M Fe+2
with 0.1000 M Ce+4 in a medium
that is
1.0 M in H2SO4.
Fe+2 + Ce+4 <=> Ce+3 + Fe+3
E = Eo - (0.0592/n) log([red]/[ox])
At 0.00 mL of Ce+4 added, inital point
no Ce+4 present; minimal, unknown
[Fe+3]; thus, insufficient information to
calculate E
Dr. S. M. Condren

EXAMPLE:Derivethe
titrationcurvefor50.00
mLof0.0500MFe+2with
0.1000MCe+4inamedium
thatis1.0MinH2SO4.
Fe+2 + Ce+4 <=> Ce+3 + Fe+3
At 15.00 mL of Ce+4 added, VFeMFe >
VCeMCeV M (15.00 mL)(0.1000 M)
Ce
+3 Ce
[Fe ] = --------------- = ---------------------------VFe + VCe
(50.00 + 15.00)mL
= 2.308 x 10-2 M
Dr. S. M. Condren

EXAMPLE:Derivethe
titrationcurvefor50.00
mLof0.0500MFe+2with
0.1000MCe+4inamedium
thatis1.0MinH2SO4.
Fe+2 + Ce+4 <=> Ce+3 + Fe+3
At 15.00 mL of Ce+4 added, VFeMFe >
VCeMCe
[Fe+3] = 2.308 x 10-2 M
VFe MFe - VCe MCe
[Fe+2] = -----------------------VFe +Dr.V
Ce
S. M. Condren

EXAMPLE:Derivethe
titrationcurvefor50.00
mLof0.0500MFe+2with
0.1000MCe+4inamedium
thatis1.0MinH
SO
.
2
4
+2
+4
+3
+3

Fe + Ce <=> Ce + Fe
At 15.00 mL of Ce+4 added, VFeMFe > VCeMCe
[Fe+3] = 2.308 x 10-2 M

(50.00 mL)(0.0500 M) - (15.00 mL)(0.1000 M)

[Fe ] = -------------------------------------------------------(50.00 + 15.00)mL
= 1.54 x 10-2 M
+2

Dr. S. M. Condren

EXAMPLE:Derivethe
titrationcurvefor50.00
mLof0.0500MFe+2with
0.1000MCe+4inamedium
thatis1.0MinH
SO
.
2
4
+2
+4
+3
+3

Fe + Ce <=> Ce + Fe
At 15.00 mL of Ce+4 added, VFeMFe > VCeMCe

[Fe+3] = 2.308 x 10-2 M[Fe+2] = 1.54 x 10-2 M

for Fe+2 -> Fe+3 Eo = 0.69 v
+2
0.0592
[Fe
]
o
Ecell = Ecell - ----------- log ----------n
[Fe+3]
Dr. S. M. Condren

EXAMPLE:Derivethe
titrationcurvefor50.00
mLof0.0500MFe+2with
0.1000MCe+4inamedium
thatis1.0MinH
SO
.
2
4
+2
+4
+3
+3

Fe + Ce <=> Ce + Fe
At 15.00 mL of Ce+4 added, VFeMFe > VCeMCe

[Fe+3] = 2.308 x 10-2 M[Fe+2] = 1.54 x 10-2 M

for Fe+2 -> Fe+3 Eo = 0.69 v
0.0592
1.54 x 10-2
Ecell = 0.68 v - ---------- log ----------------- v = 0.69
v
1 2.31
Dr. S. M.x
Condren
10-2

EXAMPLE:Derivethe
titrationcurvefor50.00
mLof0.0500MFe+2with
0.1000MCe+4inamedium
thatis1.0MinH2SO4.
Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 25.00 mL of Ce+4 added,

VFeMFe = VCeMCe, equivalence point
nFe EFeo + nCe ECeo
1(1.44) + 1(0.68)
Ecell = ----------------------- = ------------------------ v
nFe + nCe
1 + 1
= 1.06 v

Dr. S. M. Condren

EXAMPLE:Derivethe
titrationcurvefor50.00
mLof0.0500MFe+2with
0.1000MCe+4inamedium
thatis1.0MinH2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 26.00 mL of Ce+4 added, VCeMCe > VFeMFe
VFe MFe
(50.00 mL)(0.0500 M)
+3
[Ce
]
=
---------------=
------------------------------VFe + VCe
(50.00 + 26.00)mL
= 3.29 x 10-2 M
Dr. S. M. Condren

EXAMPLE:Derivethe
titrationcurvefor50.00mL
of0.0500MFe+2with0.1000
MCe+4inamediumthatis
1.0MinH
SO
.
2
4
+2
+4
+3
+3
Fe + Ce <=> Ce + Fe
At 26.00 mL of Ce+4 added, VCeMCe >
VFeMFe
[Ce+3] = 3.29 x 10-2 M
VCe MCe - VFe MFe
[Ce+4] = --------------------------VFe +
V Condren
Dr. S. M. Ce

EXAMPLE:Derivethe
titrationcurvefor50.00mL
of0.0500MFe+2with0.1000
MCe+4inamediumthatis
1.0MinH
SO
.
2
+2
+4 4
Fe + Ce <=> Ce+3 + Fe+3
At 26.00 mL of Ce+4 added, VCeMCe > VFeMFe
[Ce+3] = 3.29 x 10-2 M
(26.00 mL)(0.1000 M) - (50.00 mL)(0.0500 M)

[Ce ] = ------------------------------------------------------+4

(50.00 + 26.00)mL
= 1.32 x 10-3 M
Dr. S. M. Condren

EXAMPLE:Derivethe
titrationcurvefor50.00mL
of0.0500MFe+2with0.1000
MCe+4inamediumthatis
1.0MinH2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 26.00 mL of Ce+4 added, VCeMCe > VFeMFe

[Ce+3] = 3.29 x 10-2 M

[Ce+4] = 1.32 x 10-3 M
for Ce+4 -> Ce+3 Eo = 1.44 v
+3
0.0592
[Ce
]
o
Ecell = Ecell - ----------- log ---------n
[Ce+4]
Dr. S. M. Condren

EXAMPLE:Derivethe
titrationcurvefor50.00mL
of0.0500MFe+2with0.1000
MCe+4inamediumthatis
1.0MinH2SO4.

Fe+2 + Ce+4 <=> Ce+3 + Fe+3

At 26.00 mL of Ce+4 added, VCeMCe > VFeMFe

[Ce+3] = 3.29 x 10-2 M

[Ce+4] = 1.32 x 10-3 M
for Ce+4 -> Ce+3 Eo = 1.44 v
0.0592 3.29 x 10-2
Ecell = 1.44 v - ------------ log --------------- v = 1.39
v
-3
1
1.32
x
10
Dr. S. M. Condren

3. TITRATION END POINT

Detection of the end point

1- Self indication: If the titrant is highly colored, this color
may be used to detect the end point. For example;
potassium permanganate is deep purple, the production
of its reduction Mn2+ is nearly colorless, being a very faint
pink.
2- Starch indicator: this indicator is used for titrations
involving iodine. Starch forms a complex color with I2,
That is a very dark blue color. The color is sensitive to
very small amounts of iodine. In titration of reducing
agents with iodine, the solution remains colorless up to
the equivalent point. A fraction of a drop of excess titrant
turns the solution a definitive blue.

3- Redox indicators: most types of redox titrations are

detected using redox indicators. These are highly
colored dyes that are weak reducing or oxidizing agents
that can be oxidized or reduced, the colors of the
oxidized and reduced forms are deferent. The oxidation
state of the indicator and its color will depend on the
potential of the solution. A half-reaction and Nernst
equation can be written for the indicator
Ox indicator + ne- Redindicator
So the ratio [Redin]/[Oxin], and therefore the color will
change as the potential of the solution changes. The
redox indicator reaction must be rapid and eversible, if
the reaction is slow or is irreversible, the color change
will be gradual and a sharp end point will be not
detected.

16-2 Finding the end point

A redox indicator is a
compound that changes
color when it goes from its
oxidized to its reduced
state.

or
For ferroin, with E = 1.147 V
we expect the color change to
occur in the approximate range
1.088 V to 1.206 V with respect SHE

A redox titration is feasible if the difference between analyte and titrant

is > 0.2 V.
If the difference in the formal potential is > 0.4 V, then a redox
indicator usually gives a satisfactory end point.

Starch-Iodine Complex

Starch is the indicator of choice for those

procedures involving iodine because it forms an
intense blue complex with iodine. Starch is not a
redox indicator; it responds specifically to the
presence of I2, not to a change in redox potential.
The active fraction of starch is amylose, a
polymer of the sugar -d-glucose.
In the presence of starch, iodine forms I6 chains
inside the amylose helix and the color turns dark
blue

17D Oxidation/Reduction Indicators

Self-indication:
If the titrant is highly colored, this color may be
used to detect the end point.

Ex :

MnO4- Mn2+
purple

faint pink

 Starch indicator:
This indicator is used for titrations
involving iodine
Starch + I2 dark-blue color complex

 Redox Indicators:
These are highly colored dyes that are weak
reducing or oxidizing agents that can be
oxidized or reduced

Oxind + ne- Redind

E ind E

0
ind

[Inred] 1

[Inox ] 10

Redind
0.059

log
n
Ox ind
[Inred]
10
[Inox ]

A potential equal to 2(0.059/n)V is required for

a sharp color change
n = 1 0.12V
n = 2 0.060V

The redox indicator reaction must be rapid and

reversible.
Table 17.2
Ex:
(1) Ferroin:
[tris(1,10-phenanthroline)ion(II) sulfate]

for titrations with cerium(IV)

(2) Starch/Iodine soln.

Redox indicator

In(oxidized) + ne In(reduced)
E = Eo (0.05916 / n) log [In(reduced)] / [In(oxidized)]
[In(reduced)] = [In(oxidized)]

E = Eo (0.05916 / n)

[In(reduced)] / [In(oxidized)] (10/1)

[In(reduced)]

[In(reduced)] / [In(oxidized)] (1/10)

[In(oxidized)]

Indicator transition range

vs SCE

= transition range E(calomel)

vs SHE

Color changes for general redox indicators depend only on the potential of the system.
The range of potentials over which a color change occurs (the transition potential) is
often pH dependent.

Iron complexes of 1,10-phenanthrolines (orthophenanthrolines)

Starch-Iodine complex
Starch solution(05~ 1%) is not redox indicator.
The active fraction of starch is amylose, a polymer of the sugar -D-glucose
( 1,4 bond).
The polymer exists as a coiled helix into which small molecules can fit.
In the presence of starch and I, iodine molecules form long chains of I5 ions
that occupy the center of the amylose helix.
[I I I I I] [I I I I I]
Visible absorption by the I5 chain bound within the helix gives rise to the
characteristic starch-iodine color.

Structure of the repeating unit of the sugar

amylose.

Schematic structure of the starch-iodine

complex. The amylose chain forms a
helix around I6 unit.
View down the starch helix, showing
iodine, inside the helix.

Potentiometric end points for redox titrations:

reference electrode || analyte solution | Pt

Reference electrode : SCE

The end point can be determined from a plot of the measured potential as a
function of titrant volume.
E(vs SCE)

Titrant volume

4. ADJUSTMENT OF
OXIDATION STATE

16-3 Adjustment of analyte

oxidation state
Sometimes one needs to adjust the oxidation state of analyte before
it can be titrated.
Pre-adjustment must be quantitative and one must eliminate excess
pre-adjustment reagent so that it wont interference the subsequent
titration.
Pre-oxidation: powerful oxidants that can be easily removed after
preoxidation include peroxydisulfate, silver(II) oxide, sodium
bismuthate.
Definition:

Disproportionation: a reactant oxidizes and reduces itself, such as H2O2 in

boiling water.
Pre-reduction: Process of reducing an analyte to a lower oxidation state
prior to performing a titration with an oxidizing agent.
Amalgam: a solution of anything in mercury.

ADJUSTMENT OF ANALYTE OXIDATION STATES

Before titration we adjust the oxidation state of the analyte, eg
Mn2+ can be pre-oxidised to MnO4- and then titrated with Fe2+
Pre-adjustment must be quantitative and all excess reagent must
be destroyed.
Pre-oxidation :
Persulphate S2O82- is a powerful oxidant that requires Ag+ as a
catalyst: S2 O82- + Ag+
SO42- + SO4- + Ag2+
Two powerful oxidants

Excess reagent is destroyed after by boiling the solution

after oxidation is complete

2S2O82- + 2 H2O

boiling 4SO42- + O2 + 4H+

H2O2 is a good oxidant in basic solution and reductant in

acidic solution. The excess spontaneously disproportionate
in boiling water.
H2O2

H2O + O2

PRE-REDUCTION
Stannous & chromous chloride, SO2 , H2S are used to prereduce analytes to a lower oxidation state.
An important pre-reduction technique uses a packed column
to pre-reduce analyte to a lower oxidation state (analyte is
drawn by suction).

Jones reductor, which contains Zn coated

with Zn amalgam. Zn is a powerful reducing
agent (Eo = -0.764V) making the Jones
reductor unselective, other species eg, Cr3+
are reduced and may interfere with the
titration analysis.

Preadjustment of analyte oxidation state

It is necessary to adjust the oxidation state of the analyte to one that can be titrated
with an auxiliary oxidizing or reducing agent.
Ex.

Preadjustment by auxiliary reagent

Fe(II), Fe(III)

Fe(II)
4

Titration
Ce

4+

2 )
Preoxidation : Peroxydisulfate ( (NH
4)2S2O8
)
Sodium bismuthate ( NaBiO
3)

Hydrogen peroxide (H
2O2)
Prereduction : Stannous chloride ( SnCl
2)
Chromous chloride
Jones reductor (zinc coated with zinc amalgam)
Walden reductor ( solid Ag and 1M HCl)

Jones reductor :
2Zn (s) + Hg2+ Zn2+ + Zn(Hg) (s)

Redox Titrations
Common Redox Reagents
2.) Adjustment of Analyte Oxidation State

Before many compounds can be determined by Redox Titrations, must be

converted into a known oxidation state
-

Reagents for prereduction or preoxidation must:

-

This step in the procedure is known as prereduction or preoxidation

Totally convert analyte into desired form

Be easy to remove from the reaction mixture
Avoid interfering in the titration

Examples:
-

Preoxidation:
a)
Peroxydisulfate or persulfate (S2O82-) with Ag+ catalyst

Powerful oxidants
Oxidizes Mn2+, Ce3+, Cr3+, VO2+
excess S2O82- and Ag+ removed by boiling the solution

Redox Titrations
Common Redox Reagents
2.) Adjustment of Analyte Oxidation State

Examples:
Preoxidation:
b) Silver(II) oxide (AgO) in concentrated mineral acids also yields Ag2+
excess removed by boiling
c)

Hydrogen peroxide (H2O2) is a good oxidant to use in basic solutions

Oxidizes Co2+, Fe2+, Mn2+
Reduces Cr2O72-, MnO4excess removed by boiling

Prereduction:
a) Stannous chloride (SnCl2) in hot HCl
Reduce Fe3+ to Fe2+
excess removed by adding HgCl2
b) Jones reductor (Zn + Zn amalgam anything in mercury)

5. PERMANGANAT

16-4 Oxidation with potassium

permanganate
KMnO4 is a strong oxidant with an intense
violet color. In strongly acidic solutions (pH
< 1), it is reduced to Mn2+.
In neutral or alkaline solution, it is reduced
to brown solid MnO2.
In strongly alkaline solution ( 2 M NaOH),
green manganate ion (MnO42-) is
produced.

Dr. S. M. Condren

Redox Titrations
Common Redox Reagents
3.) Common Titrants for Oxidation Reactions

Potassium Permanganate (KMnO4)

-

Strong oxidant
Own indicator

pH 1

Titration of VO2+ with KMnO4

Eo = 1.507 V
Violet

colorless

pH neutral or alkaline
Violet

brown

Eo = 1.692 V

pH strolngly alkaline

Before
Near
After
Equivalence point

Eo = 0.56 V
Violet

green

Using KMnO4 as Oxidising

Agents

One of the most common oxidising agent used

in redox titrations is KMnO4.
KMnO4. reacts differently in both acid and bases.
In Acidic Solution
In acid solutions, the reduction of KMnO4 can be
represented by the following equation:
MnO4- + 8H+ + 5eMn2+ + 4H2O
Sulfuric acid is the most suitable acid, as it does not
react with permanganate in dilute solutions
With hydrochloric acid, there is a likelihood of the
reaction
2MnO4- +10Cl- + 16H+ +2eMn2+ + 4H2O + 5Cl2

Using KMnO4. as Oxidising

Agents
In Basic Solution
In basic solutions, the reduction of KMnO4
will be reduced to form manganese dioxide
and can be represented by the following
equation:
MnO4- + 8H20 + 2eMnO2 + 4OH-

Permanganate Titration
In using Potassium permanganate, the
following conditions must be used
Stored at low temperatures and away
from light
Experiments performed at 60oC
Sulfuric acid used in the titration

Permanganate Titration
The reason for refrigeration
Refrigeration is used to prevent the degradation of potassium
permanganate by light.
The reason why the experiment was performed at 60 C
The reaction does not proceed if the temperature is low. A
temperature greater than 60 C is necessary for this experiment.
The oxidative reaction by potassium permanganate in sulfuric
acid is sometimes performed even at 100 C.
The reaction why sulfuric acid is used in this experiment
If hydrochloric acid is used, Cl- is oxidized by potassium
permanganate. Since nitric acid itself is oxidizing agent, its use
is also inappropriate.

Common oxidising agents

Problems using potassium permanganate
The solid is rarely pure
The solutions are relatively unstable due to partial
decomposition of the permanganate ion

MnO 4( aq ) 4H (aq ) 3e MnO 2(s ) 2H 2O ( l )

The production of MnO2 has a catalytic effect,
increasing the rate of decomposition
Dust and organic matter in the air also cause
oxidation to MnO2
Solutions of permanganate are stored in dark bottles
away from sunlight to prevent decomposition

Standardisation of
potassium permanganate
Potassium permanganate cannot be used as a
primary standard because it is unstable
Ammonium iron sulfate, sodium oxalate and
oxalic acid are used as primary standards to
standardise potassium permanganate
The permanganate goes in the buret and the
primary standard in the conical flask

Titration Setup
for volumetric
analysis using
permanganate

Permanganate goes in the

buret

Indicator is
unnecessary
Primary standard
solution goes in the
conical flask

End Point
Acidified potassium permanganate solution,
which is a deep purple in colour, is a
commonly used secondary standard. It has
the advantage of being self indicating as its
products are almost colourless

Common titrations using potassium

permanganate solution as the oxidising agent

Problem : Redox Titration- I

Volume (L) of KMnO4 Solution
a)

M (mol/L)
Moles of KMnO4

b)

Molar ratio
in redox reaction.
Moles of CaC2O4

c)

Chemical Formulas

Moles of Ca+2

Problem: Calcium Oxalate was

precipitated from 1.00 mL blood by the
addition of Sodium Oxalate so the Ca2+ conc. in
the blood could
be determined. This precipitate was
dissolved in a sulfuric acid solution,
which then required 2.05 mL of
4.88 x 10-4 M KMnO4 to reach the
endpoint via the rxn.
a) Calculate the moles of Ca2+.
b) Calculate the Ca2+ conc. in blood.
Plan: a) Calculate the moles of
Ca2+ in the H2SO4 solution (and blood sample).
b) Convert the Ca2+ conc.into units of mg Ca2+/
100 mL blood.

Problem :Redox Titration - Calculation - II

Equation:
2 KMnO4 (aq) + 5 CaC2O4 (aq) + 8 H2SO4 (aq)
2 MnSO4 (aq) + K2SO4 (aq) + 5 CaSO4 (aq) + 10 CO2 (g) + 8 H2O(l)
a) Moles of KMnO4

b) Moles of CaC2O4

c) Moles of Ca+2

Problem : Redox Titration - III

Moles of Ca2+/ 1 mL of blood
multiply by 100

a) Calc of mol Ca2+ per 100 mL

Moles of Ca2+/ 100 mL blood

M (g/mol)

b) Calc of mass of Ca2+ per 100 mL

Mass (g) of Ca2+/ 100 mL blood

1g = 1000mg
Mass (mg) of Ca2+ / 100 mL blood

c) convert g to mg!

Standardisation of
permanganate
Using oxalic acid
H2C2O4

The half reactions are:

H 2 C 2O 4 ( aq ) 2CO 2( g ) 2H (aq ) 2e

}x5

MnO -4(aq) 8H (aq ) 5e Mn (2aq ) 4H 2 O ( l )

Overall:

}x2

5H 2 C 2 O 4( aq ) 2MnO 4( aq ) 6H (aq ) 2Mn (2aq ) 8H 2O ( l ) 10CO 2 ( g )

Example: Standardisation of
permanganate with oxalic acid

Example:
A 20 mL solution of 0.0512 M oxalic acid
was used to standardise an unknown
solution of potassium permanganate. An
average of 21.24 mL of permanganate
was required.
Calculate the concentration of the
potassium permanganate solution

Example: A 20 mL solution of 0.0512 M

oxalic acid was used to standardise an
unknown solution of potassium
permanganate. An average of 21.24 mL
of permanganate was required.
Calculate the concentration of potassium
permanganate solution

Given: 20 mL of 0.0512 M H2C2O4, 21.24

mL K2MnO4
Find: Conc. K2MnO4 (moles/L)
SM: L H2C2O4mol. H2C2O4mol.
K2MnO4conc. K2MnO4

5H 2 C 2 O 4 2MnO 4 ( aq ) 6H (aq )

2Mn (2aq
) 8H 2 O ( l ) 10CO 2 ( g )

Apply solution map

1L
0.0512 mol H 2 C 2O 4 2 mol MnO 4
20.0 mL H 2 C 2O 4

4.096 10 4 mol MnO 4

1000 mL
1L
5 mol H 2C 2 O 4

1L
liters MnO 21.24 mL
0.02124 L
1000 mL
4

moles solute 4.096 10-4 moles MnO 4

molarity

0.0193 M
liters solution
0.02124 L

Question
25 mL of 0.0627 M acidified oxalic acid
solution required 31.2 mL of potassium
permanganate solution for complete
oxidation.
Calculate the concentration of
permanganate solution

DICHROMATE

Volumetric analysis using

potassium dichromate
Potassium dichromate can be used as an
oxidising agent
It has the advantages that it forms stable
solutions and can be used as a primary
standard
The half reaction is:
Cr2 O 72( aq ) 14H (aq ) 6e 2Cr(3aq ) 7 H 2 O ( l )

Oxidation with potassium dichromate

Cr2O72 + 14H+ + 6e = 2Cr3+ + 7H2O
K2Cr2O7 is a primary standard.
Indicator : diphenylamine sulphonic acid

Eo = 1.36 V

( hydroquinone vs dichromate
standard solution )
Ex. Redox titration

3
HO

Cr2O72 + 14H+ + 6e
Eo= 1.33

2 Cr3+ + 7 H2O

HO

OH

OH + Cr2O72 + 8H+
O

Eo= Eocathode Eoanode = 1.33 0.700

V
K = 10 nEo/0.05916

+ 2H+ + 2e

Eo= 0.700

O + 2 Cr3+ + 7
H2O

= 0.63

= 10 6(0.63) / 0.05916 = 10 64

redox indicator : diphenylamine

Very large : quantitative : complete reaction

colorless to violet

CERIUM (CE4+)

16-5 Oxidation with Ce

4+

Reduction of Ce4+ to Ce3+ proceeds cleanly in acidic

solutions.
The aquo ion, Ce(H20)n4+, probably does not exist in any
of these solutions, because Ce(IV) binds anions (ClO4-,
SO42- NO3-, Cl-) very strongly.

Oxidation with Ce4+

Ce4+ + e = Ce3+
yellow

1.7 V in 1 N HClO4

colorless

1.61 V in 1N HNO3
1.47 V in 1N HCl
1.44 V in 1M HSO4

Indicator : ferroin, diphenylamine

Preparation and standardization:
Ammonium hexanitratocerate, (NH4)2Ce(NO3)6, (primary standard
grade)
Ce(HSO4)4,
Standardized with Sodium oxalate.

(NH4)4Ce(SO4)42H2O

Applications of cerimetry
(1) Menadione (2-methylnaphthoquinon: vitamin K3)
HCl, Zn

O
CH3

OH
CH3

Reduction

2 Ce(SO4)2

OH

(2) Iron
2FeSO4 + 2 (NH4)4Ce(SO4)4 = Fe2(SO4)3 + Ce2(SO4)3 + 4
(NH4)2SO4

IODINE

Titration Involving Iodine: Iodimetry And Iodometry

Redox titrations are among the most important types of
analysis performed in many areas of application.
Example in clinical laboratories are rare, since most
analyses are for traces, but these titrations are still
extremely useful for standardizing reagents.
A- Iodimetry
iodine is a moderately strong oxidizing agent and can be
used to titrate reducing agents.
Titration with I2 are called Iodimetric methods. These
titrations are usually performed in neutral or mildly
alkaline (pH 8) to weakly acid solutions. If the pH is too
alkaline, I2 will disproportionate o hypoiodate and iodide:
I2 +2OH = IO- + I- +H2O

There are three reasons for keeping he solution from

becoming strongly acidic:
1-the starch used for the end point detection tends to
hydrolyze or decompose in strong acid which will affect
the EP.
2-the reducing power of several reducing agents is
increased in neutral solution.
3-the I- produced in the reaction tends to be oxidized by
dissolved oxygen in acid solution:
4I- +O2 + 4H+ 2I2 +2H2O
Iodine has a low solubility in water but the complex,I3-, is
very soluble. So iodine solutions are prepared by
dissolving I2 in a concentrated solution of potassium
iodide:
I2 + I - I 3 I3- IS Therefore the actual species used in the reaction.

Iodometry
Iodide ion is a weak reducing agents and will reduce strong
oxidizing agents. It is not used, however, as a titrant mainly
because of lack of convenient visual indicator system, as well
as other factors such as speed of the reaction.
When an excess of iodide is added to a solution of an oxidizing
agent I2 is produced in an amount equivalent to the oxidizing
agent present.
This I2 can therefore be titrated with a reducing agent and the
result will be the same as if the oxidizing agent were titrated
directly. The titrating agent used is SODUIM THIOSULFATE.
Analysis of an oxidizing agent in this way is called an Iodometric
method. Consider, for example, the determination of
dichromate:
Cr2O72- + 6I- (excess) + 14H+ 2Cr 3+ +3I2 + 7H2O
I2 + 2S2O3 2- 2I- + S4O62-

Why not titrate the oxidizing agents directly with the

thiosulfate? Because strong oxidizing agents oxidize
thiosulfate to oxidation states higher than that of
terathionate, but the reaction is generally not
stochiometric.
The end point for iodometric titrations is detected with
starch. The disappearance of the blue starch-I2 color
indicates the end of the titration. The starch is not added
at the beginning of the titration when iodine
concentration is high. instead, it is added just before the
EP when the dilute iodine color becomes pale yellow.
There are tow reasons for such timing:
1- the iodine-starch complex is only slowly dissociated, and
a diffuse end point would result if a large amount of the
iodine were adsorbed on the starch.
2- most iodometric titrations are performed in strongly acid
medium and the starch has a tendency to hydrolyze in
acid solution.

The titration should be performed rapidly to minimize air

oxidation of the iodide. Stirring should be efficient in
order to prevent local excesses of thiosulfate, because it
is decomposed in acid solution.
In iodometric methods, a large excess of iodide is added to
promote the reaction. The unreacted iodide dose not
interfere, but it may be air-oxidized if the titration is not
performed immediately.
Sodium thiosulfate solution is standardized iodometrically
against a pure oxidizing agent such as K2Cr2O7, KIO3,
KBrO3, or metallic copper (dissolved to give Cu2+). With
potassium dichromate, the deep green color of the
resulting chromic ion makes it a little more difficult to
determine the iodine-starch end point.

Common Titrant for Oxidation Reactions

Iodine (Solution of I2 + I-)
I3- is actual species used in titrations with iodine

K = 7 x 102
Either starch of Sodium Thiosulfate (Na2S2O3) are used as
indicator
I3-

I3- + S2O32-

Before
endpoint

I3- + Starch

Before
endpoint

At
endpoint

16-7 Methods Involving Iodine

Iodimetry: a reducing analyte is titrated directly with
iodine (to produce I).
iodometry, an oxidizing analyte is added to excess I to
produce iodine, which is then titrated with standard
thiosulfate solution.
Iodine only dissolves slightly in water. Its solubility is
enhanced by interacting with I-

A typical 0.05 M solution of I2 for titrations is prepared by

dissolving 0.12 mol of KI plus 0.05 mol of I2 in 1 L of
water. When we speak of using iodine as a titrant, we
almost always mean that we are using a solution of I 2
plus excess I.

Preparation and Standardization of Solutions

Acidic solutions of I3- are unstable because the excess I
is slowly oxidized by air:
In neutral solutions, oxidation is insignificant in the
absence of heat, light, and metal ions. At pH 11,
triiodide disproportionates to hypoiodous acid (HOI),
iodate, and iodide.
An excellent way to prepare standard I3- is to add a
weighed quantity of potassium iodate to a small excess
of KI. Then add excess strong acid (giving pH 1) to
produce I2 by quantitative reverse disproportionation:

Volumetric analysis using iodine

Iodine (I2) is used as a weak oxidising
agent
The half equation is:

I 2 ( aq ) 2e 2I ( aq )

Starch is used as an indicator. Excess

iodine causes the formation of a blue
starch-iodine complex
Starch

Analysis of wine
The sulfur dioxide content of wine
can be determined by oxidation with
iodine
The iodine only reacts with the sulfur
dioxide in wine and not with the
alcohols (as would permanganate or
dichromate)
The oxidation reaction for SO2 is:
SO 2 ( g ) 2H 2 O ( l ) SO 24( aq ) 4H (aq ) 2e

16-7 Methods Involving Iodine

Iodimetry: a reducing analyte is titrated directly with
iodine (to produce I).
iodometry, an oxidizing analyte is added to excess I to
produce iodine, which is then titrated with standard
thiosulfate solution.
Iodine only dissolves slightly in water. Its solubility is
enhanced by interacting with I-

A typical 0.05 M solution of I2 for titrations is prepared by

dissolving 0.12 mol of KI plus 0.05 mol of I2 in 1 L of
water. When we speak of using iodine as a titrant, we
almost always mean that we are using a solution of I 2
plus excess I.

Preparation and Standardization of Solutions

Acidic solutions of I3- are unstable because the excess I
is slowly oxidized by air:
In neutral solutions, oxidation is insignificant in the
absence of heat, light, and metal ions. At pH 11,
triiodide disproportionates to hypoiodous acid (HOI),
iodate, and iodide.
An excellent way to prepare standard I3- is to add a
weighed quantity of potassium iodate to a small excess
of KI. Then add excess strong acid (giving pH 1) to
produce I2 by quantitative reverse disproportionation:

Bromatimetry
KBrO3

BrO3 + 5Br + 6H+

3Br2 + H2O

2I + Br2 I2 + 2Br
I2 + 2 S2O32 2I + 2S4O62
Substitution reactions

BrO3 + 5Br + 6H+

3Br2 + H2O

2I + Br2 I2 + 2Br
I2 + 2 S2O32 2I + S4O62

pH 4-9
Al3+ + 3HOC9H6N Al(OC9H6N)3 (s) + 3H+
hot 4M HCl
Al(OC9H6N)3 (s)

3HOC9H6N + Al3+

3HOC9H6N + 6 Br2 3HOC9H4NBr2 + 6HBr

1 mol Al3+ 3 mol HOC9H6N 6 mol Br2 2 mol KBrO3

Addition reactions

Determining water with the Karl Fisher Reagent

The Karl Fisher reaction :
I2 + SO2 + 2H2O 2HI + H2SO4
For the determination of small amount of water, Karl Fischer(1935)
proposed a reagent prepared as an anhydrous methanolic solution
containing iodine, sulfur dioxide and anhydrous pyridine in the mole
ratio 1:3:10. The reaction with water involves the following reactions :
C5H5NI2 + C5H5NSO2 + C5H5N + H2O 2 C5H5NHI + C5H5NSO3
C5H5N+SO3 + CH3OH C5H5N(H)SO4CH3
Pyridinium sulfite can also consume water.
C5H5N+SO3 + H2O C5H5NH+SO4H
It is always advisable to use fresh reagent because of the presence
of various side reactions involving iodine. The reagent is stored in a
desiccant-protected container.
The end point can be detected either by visual( at the end point, the
color changes from dark brown to yellow) or electrometric, or
photometric (absorbance at 700nm) titration methods. The detection

Pyridine free Karl Fisher reagent

In recent years, pyridine, and its objectionable odor, have been replaced
in the Karl Fisher reagent by other amines, particularly imidazole.
(1) Solvolysis

2ROH + SO2 RSO3 + ROH2+

(2) Buffering

B + RSO3 + ROH2+ BH+SO3R + ROH

(3) Redox
2 BH+I

BI2

+ BH+SO3R + B + H2O

BH+SO4R +

Applications

Combustion
Bleaching
Batteries and fuel cells
Metallurgy
Corrosion
Respiration

Copyright 2008
Pearson Prentice Hall,

Chapter 1/176

Determination of Amount of Vitamin C in a

Sample by Redox Titration

Experiment 3

Experiment 3
Goal:
To detemine the amount of vitamin C (Lascorbic acid) in a sample

Method:
Use AA/DCP redox titration reaction
Perform titrations with known concentrations
Perform titrations with sample of unknown vit
C concentration

Vitamin C Oxidation HalfReaction

Oxidation: Loss
of eOH

OH

H
OH

H2C

O
C

HO

HO

H
OH

H2C

O
C

Reduced
Ascorbic Acid

L-Ascorbic
reduced,
vitaminAcid
form

+ 2e- + 2H+

C
O

Oxidized
Ascorbic
Acid
oxidized,
L-Dehydroascorbic
excreted
Acidform

DCP Reduction Half-Reaction

OH

Cl

Reduction: Gain
of e-

+ 2e- + 2H+

OH

Cl

NH

HO
Cl

Oxidized DCP
(Dark
Blue in
Oxidized
DCP
Base
PinkDark
in acid) blue in

base

Cl

Reduced
DCP
Reduced
DCP
(Colorless in acid)
Colorless
DCP = Dichloroindophenol

Redox Reaction
Oxidatio
n:
Reductio
n:

Overall
:

AA red AA ox
DCPox

AA red DCPox

2H 2e

2 H 2e

DCPred

AA ox DCPred

Redox Reaction
AA red DCPox
colorless
colorless

AA ox DCPred

pink
colorless

DCP: titrant and indicator

Solution:
gone

colorless until all AAred is

Then: excess DCPox appears pink

Amount Profiles
AAox

mole
s

AAred

DCPr
ed

AAred =
0

mL DCP added

Titration
At as close to
endpoint as
possible:
DCP
titrant

Vit C
analyte

Pink should fade after 30

seconds

Part 1
Standardization: Find mg AA/mL DCP
Use 10.00 mL AA solution
VAA=10.00 mL
of known conc. in ~30 mL buffer
CAA
Titrate AA with DCP to endpoint

VDCP

Repeat 4 times (1* trial, 3 good)

Find mg AA consumed per mL DCP
DCP

mgAA/mL

Part 1
Standardization mg AA/mL DCP example
0.0500 g AA weighed
Dissolved in 100.0 mL
10.00 mL aliquot used
20.12 mL DCP required
weighed
out

mL AA used

0.0500gAA 10.00 mLAA 1000mgAA 0.246 mg AA

100.0 mL 20.12 mL DCP

1 g AA
mL DCP

total
volume

mL DCP
reqd

Part 2
Determine AA content in sample
Use Kool-Aid provided
Estimate mg AA in sample
mgAAest
Want to use ~10-20 mL DCP
Calculate required dilution
dilution factor
and aliquot volume
Valiqout
Titrate 4 times (1* trial; 3 consistent)
Aliquot dilution OK

VDCP

Part 2
Estimated AA content desired example
Want to use ~ 10 - 20 mL DCP
How many mg AA desired in sample aliquot?

from Part 1

0.246 mg AA
20 mL DCP
4.92 mg AA
mL DCP

Part 2
AA content in Countrytime lemonade example
Serving: 18 g
6 mg AA
so
Vit C: 10% RDA
18 g CTL
RDA: 60 mg

AA in CTL
AA desired

Amount CTL to
use

18 g CTL
4.92 mg AA
14.8 g CTL
6 mg AA

Part 2
Vit C content in fruit example
1. 5.00 g fruit 20.00 mL acid & prepped
2. 5.00 mL liquid diluted to 30.0 mL
3.13.13 mL DCP reqd
Find mg AA/gram fruit:
mL DCP
from Part 1 soln to fruit
conversion
reqd
13.13 mL DCL
0.246 mg AA 20.00 mL AA sol' n 2.58 mg AA

5.00 mL AA sol' n
mL DCP
5.00 g fruit
g fruit
sample
volume

PROBLEMS

Problems
Would indigo tetrasulfonate be a suitable redox indicator
for the titration of Fe(CN)64- with Tl3+ in 1 M HCl?
Solution:
Standard potentials: indigo tetrasulfonate is 0.36 V;
Fe(CN)63-/ Fe(CN)64- is 0.356 V;
Tl3+/Tl+, 0.77 V.
The end-point potential will be between 0.356 and
0.77 V. Indigo tetrasulfonate changes color near 0.36 V.
Therefore it will not be a useful indicator for this titration.

 Given the following data select the best indicator for the titration
of iron(II) with thallium(III), using a S.C.E. reference electrode.

(a) methylene blue

(b) diphenylamine sulfonic acid
(c) diphenylamine

Which of the following titrations would give a titration curve

symmetric around the equivalence point?
(a) Na2S2O3 titrated with I2.
(b) ascorbic acid titrated with I2.
(c)As4O6 titrated with I2.

Problems
Would indigo tetrasulfonate be a suitable redox indicator
for the titration of Fe(CN)64- with Tl3+ in 1 M HCl?
Solution:
Standard potentials: indigo tetrasulfonate is 0.36 V;
Fe(CN)63-/ Fe(CN)64- is 0.356 V;
Tl3+/Tl+, 0.77 V.
The end-point potential will be between 0.356 and
0.77 V. Indigo tetrasulfonate changes color near 0.36 V.
Therefore it will not be a useful indicator for this titration.

H18 C4
4.22, 4.23, 4.29, 4.85, 4.87, 4.91*, 4.107*,
4.113*

Gustav Robert Kirchhoff(1824-1877)

was a German physicist who made
many important contributions to
physics and chemistry. In addition to
his work in spectroscopy, he is known
for Kirchhoffs laws of current and
voltage in electrical circuits. These
laws can be summarized by the
following equations:
I = 0 and E = 0.
These equations state that the sum of
the currents into any circuit point
(node) is zero and the sum of the
potential differences around any circuit
loop is zero.