Chapter 8.

 Redox titrations
OUTLINE
I. Introduction
Overview of the redox reactions. Electrochemical cells. Cell potential
and electrode potential. Calculation of the equilibrium constant.
II Redox titration curves
II.
Calculating the titration curves. Characteristics of the redox titration
curves. Factors affecting the titration curves.
III. Detection of the end point
Autoindicators. Specific indicators. Redox indicators.

IV. Previous treatments in redox titrations

Reducing
g auxiliary
y reagents.
g Oxidizing
g auxiliaryy reagents.
g

V. Applications

A li ti
Applications off reducing
d i standards.
t d d Applications
A li ti off oxidizing
idi i standards
t d d .
Analytical Techniques
Degree in Farmacy, 2nd Year Course 2019‐20
 Chapter 8. Redox titrations
• Based on a redox reaction between a titrant agent and an analyte.
• Wide range of applications: both inorganic and organic compounds.
• The main issue is the detection of the end point.
• Redox indicators
• Instrumental methods (potentiometric and amperometric).
• The low speed of some redox reactions causes the use of catalysts
and the indirect volumetric determination or “back-titration” [an
excess of the standard solution (R) is added, which is subsequently
determined via a second titration with another standard solution (R´)]
millimoles analyte = total millimoles R – millimoles of second titrant (R´)
• The pursued magnitude is the redox potential of a given system, which
is calculated by the Nernst equation

Analytical Techniques
Degree in Farmacy, 2nd Year Course 2019‐20
 Chapter 8. Redox titrations

CONCEPTS TO REVIEW
• Oxidation: Loss of electrons or increase in the oxidation state
Zn0 Zn2+ + 2e-

• Reduction:
R d ti G i off electrons
Gain l t or decrease
d i the
in th oxidation
id ti state
t t
Cu2+ + 2e- Cu0

• Redox reaction
Zn0 + Cu2+ Zn2+ + Cu0

• Oxidizing agent: Species that is reduced and causes an oxidation

(i.e. Cu2+)

• Reducing agent: Species that is oxidized and causes a reduction

((i.e. Zn0)

Analytical Techniques
Degree in Farmacy, 2nd Year Course 2019‐20
 Chapter 8. Redox titrations
An oxidation/reduction reaction (redox reaction) is that in
which electrons are transferred from the reducing agent (species
that gives e-) to the oxidizing agent (species that accepts e-):
n2 OX1 + n1 RED2  n2 RED1 + n1 OX2

OX1 + n1e-  RED1 (reduction)

RED2 – n2 e-  OX2 ((oxidation))

[OX1 + n1e-  RED1 ] x n2

[RED2 – n2 e-  OX2 ] x n1

Ce4+ + Fe2+  Ce3+ + Fe3+ Overall reaction

Ce4+ + e-  Ce3+ reduction half-reaction Ce4+ oxidizing agent
Fe2+  Fe3+ + e- oxidation half-reaction Fe2+ reducing
g agent
g

Analytical Techniques
Degree in Farmacy, 2nd Year Course 2019‐20
 Chapter 8. Redox titrations

The overall redox reaction can be split into two half-reactions.

The rules to balance each half-reaction are similar to those used in other
types of reactions:
• The number of atoms of each element at both sides of the equation
must be the same
• The
Th neatt charge
h att both
b th sides
id off the
th equation
ti mustt be
b ththe same

MnO4- + 8H+ + 5e-  Mn2+ + 4H2O reduction half-reaction

1) Adjust the element (i.e. Mn)
2) On the side where is deficiency of oxygen adjust with water molecules
3)) Adjust
j the other side of the equation
q with H+
4) Adjust the charges with e‐

Fe2+  Fe3+ + e- oxidation half

half-reaction
reaction
5 x (Fe2+  Fe3+ + e- )

MnO4- + 5Fe2+ + 8H+ 5Fe3+ +Mn2+ + 4H2O overall reaction

Analytical Techniques
Degree in Farmacy, 2nd Year Course 2019‐20
 Chapter 8. Redox titrations
Electrochemical cell
Device capable of either generating electrical energy from chemical reactions or
promoting chemical reactions through the application of electrical energy. Consists of: 
a)) TTwo conductors
d named d electrodes,
l d each
h iimmersed
d iin an electrolyte
l l solution
l i
b) External connection between the electrodes through a conducting wire
c) The electrolyte solutions are connected by a salt bridge (i.e. KCl) that avoids direct contact
between the oxidizing and reducing agents (i.e. Cu and Ag), while allows migration of ions
(K+ and Cl-) in opposite directions
Voltmeter

0,412 V

High resistance
Cl- K+
Salt Bridge 
Cu Ag
AgNO3
2Ag+ + Cu (s)  2Ag(s)  Cu2+ 
Cu(s)  CuSO4
(s) + Cu
Solution Solution
Direct contact reducing-oxidixing agent:
“Silver tree”, formed by immersion of
[Cu2+]=0,02M [Ag+]=0,02M
a Cu wire in a AgNO
g 3 solution.
2Ag+ + Cu (s)  2Ag(s) + Cu2+ 
2

Analytical Techniques
Degree in Farmacy, 2nd Year Course 2019‐20
 Chapter 8. Redox titrations
When a high resistance voltmeter is connected, the cell is said to be at “open circuit”,
no overall reaction takes place, although the cell has potential to perform work.
The voltmeter measures the voltage between the two electrodes, a measure of the
tendency towards the equilibrium of the cell reaction
Voltmeter

0,412 V

High resistance
High resistance
Cl- K+
Cu Ag
Salt Bridge

CuSO4 AgNO
g 3

[Cu
C 2+
2 ]=0,02M [Ag+]=0,02M
[A ] 0 02M
Analytical Techniques Galvanic cell at open circuit
Degree in Farmacy, 2nd Year Course 2019‐20
 Chapter 8. Redox titrations

Anode – Electrode where the oxidation takes place

Anodic reactions: 

Cathode – Electrode where the reduction takes place

Catodic reactions: 
reactions:

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 Chapter 8. Redox titrations
Cell connected to an external low resistance circuit that allows flow of e-. As the
reaction takes place, the potential decreases from 0.412 V (open circuit) to 0
((equilibrium).
q ) At the equilibrium,
q , the direct and inverse reactions take p
place at the
same speed, and no work is carried out.
The concentration of Cu2+ and Ag+ is given by the equilibrium constant :
Low resistance circuit
2

_ +

Cu Ag
Salt Bridge

Solution Ecell decreases from Solution

CuSO4 0.412 to 0 AgNO3

ANODE CATHODE
C (s)  Cu
Cu C 2+ + 2e
2 - Ag+ + e-  Ag
A A (s)
Galvanic cell carrying out work
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 TYPES OF ELECTROCHEMICAL CELLS

• Galvanic or voltaic cell: The energy released by an spontaneous redox

reaction (ΔG < 0) is converted into electrical energy

The electrons flow from the

The ions flow through the
anode to the cathode 2 Ag+ + Cu(s)  2 Ag(s) + Cu2+
salt bridge: Cl- to the anode
through the external circuit
e‐ and K+ to the cathode
e‐
e-
CuSO4 Cu Ag AgNO3
e‐
ions

Reduction at the
at the

Cu0  Cu2+ + 2e-

oxidation at the cathode/solution interfase
2Ag+ + 2e-  Ag0Ag towards electrode.
towards electrode. (aCu2+ = 0,02) (aAg+ = 0,02) NO move away from the
anode/solution interfase +
‐
SO42‐ 3
Cu2+ 
2+ move away from the electrode
electrode ANODE CATHODE
 • Electrolytic cell: Electrical energy (battery) is used to induce a
nonspontaneous
p redox reaction ((ΔG > 0))
Connect the + terminal of  2 Ag(s) + Cu2+  2 Ag+ + Cu (s)
the battery to the anode
Occurs when
G > 0,41 V e- e- a voltage
higher than
e‐ that of the
‐ 0 41 V
0,41 + galvanic cell
is applied
Cu Ag
e‐ The flow of electrons
e- is opposite to that of 
the ggalvanic cell !

Cu2+ + 2e-  Cu0 Ag0  Ag+ + e-

CÁTODO (-)
ÁNODO (+)
The reactions at the electrodes, the global reaction and the sign
of the electrodes are opposite to those of the galvanic cell. 
 Schematic Representation of Cells:
I
Daniel Cell e Positive lead of the multimeter

- M +
connected to the right-hand electrode

Zn Cu

ZnSO 4 CuSO 4

CATHODE
ANODE
Zn 0  Zn 2+ + 2e - Cu 2+ + 2e -  Cu 0
( a Zn 2+ = 1,00) ( a Cu 2+ = 1,00)

Zn ZnSO4 (aZn2+ = 1,00) CuSO4 (aCu2+ = 1,00) Cu

 Chapter 8. Redox titrations

Schematic Representation of Cells:

by agreement start with the anode on the left

1) A vertical line (I) phase limit or interphase where a potential can be developed.

2) 2 vertical
ti l lines
li (II) t
two li id li id junctions
liquid-liquid j ti att both
b th sides
id off the
th salt
lt bridge.
b id

3) The e- carry the charge between the electrodes through the external conductor.
By agreement,
agreement the electrical current I flows in opposite direction to the e
e- flow.
flow

Course 2019‐20
 Chapter 8. Redox titrations
Cellll Potentiall
The potential difference between the electrodes of the cell (Ecell) is a
measure of the tendencyy of the reaction

Example Cu(s) + 2Ag+  Cu2+ + 2Ag(s)

to proceed from a non-equilibrium to an equilibrium state.
Ecell is related to the free energy change of the reaction by: ΔG = -nFEcell

n is the total number of moles of electrons exchanged in the overall balanced

reaction and F is the Faraday’s constant (96487 C mol-1)
When both reactants and products are in their standard states, the resulting cell
potential
t ti l is
i called
ll d standard
t d d cellll potential
t ti l (Eocell),
) which
hi h is
i related
l t d to
t the
th standard
t d d
free energy change and the equibrium constant:
ΔGo = -nFE
nFEocell = -RT
RT ln Keq

The standard state of a substance is a reference state that allows to obtain

relative values of thermodynamic
y quantities like free energy,
q gy enthalpy,
py entropy,
py
etc. (p = 1 atm; a = 1)

Course 2019‐20
 Chapter 8. Redox titrations
According to the IUPAC and taking into account that the cell is composed
of two half-cells :

Ecell = Eright – Eleft Ecell = Ecathode – Eanode (galvanic cell)

This implies
p that we always
y measure the cell p potential by
y connectingg the
positive lead of the voltmeter to the right-hand electrode (plus right rule)
Ecell is a measure of the tendency of the cell reaction
Ej. Cu(s) + 2Ag+  Cu2+ + 2Ag(s) to occur spontaneously from left to right.
Cu Cu2+ Ag
g+ Ag
g ΔG = -nFEcell
Cu metal is oxidized to Cu2+ in the left-hand compartment and Ag+ is reduced
to Ag metal in the right-hand compartment
If Ecell is positive, ΔG is negative spontaneous reaction.

If Ecell is negative,
g , ΔG is p
positive non-spontaneous
p reaction
The reverse reaction tends to occur
Course 2019‐20
 Chapter 8. Redox titrations
Electrode potential or Half-Cell Potential
E (half-cell potential) cannot be measured alone (absolute electrode
potential) since all devices measure differences of potential
need to compare with another electrode relative electrode potential
The potential of the half-reaction is determined vs. a reference electrode
(i standard
(i.e. t d d hydrogen
h d electrode
l t d (SHE))
• The electrode potential is the potential of a cell in which the electrode
in q
question ((i.e. Ag/Ag
g g+) is the right-hand
g electrode and a reference
electrode (i.e. SHE) is the left-hand electrode. It is a reduction
potential.
• Ecell = Eright – Eleft = EAg – ESHE = EAg – 0,000
0 000 = EAg
Depends on:
• Electrode
El t d Chemical
Ch i l nature
t ▪ Reactant
R t t concentrations
t ti
• Speed of the reactants towards the electrode surface
• Electrode physical properties (shape and size)
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 Chapter 8. Redox titrations
Universal
U i l reference
f electrode,
l t d easy to
t construct,
t t reversible
ibl and
d highly
hi hl reproducible.
d ibl
It is a gas electrode
Electrode
Standard hydrogen potential
electrode
The representation for SHE:
H2 gas at Pt(s), H2 (g, 1 atm) I H+ (aq, a = 1.00)
1 atm
a

By convention, the
potential for SHE
h been
has b asigned
i d
a value of 0.000 V
V at any temperature
The metal conductor is a piece of Pt
coated with platinum black to increase
its specific surface area.
Solution of HCl The electrode is immersed in 1M HCl
1M solution. The solution is kept saturated
with H2 by bubbling the gas at a
pressure off 1 atm
t over the
th electrode
l t d
surface
Course 2019‐20
 Chapter 8. Redox titrations
Standard electrode potential (E0):
Electrode potential when the activities of the reactants and products are all unity.

i.e. For the cell: Pt, H2(p=1.00 atm) H+ (aH+ =1,00) Ag+(aAg+ =1,00) Ag
SHE    Ag+(aAgg+ =1,00)      The standard electrode potential for the silver half reaction or Ag+/Ag 
couple is:              Ag+ + 1e‐  Ag(s) EoAg+/Ag = +0,799 V
E0 is independent of the number of moles of reactant and product shown in the
balanced half-reaction.
half reaction Thus,
Thus Fe2+  Fe3+ + e- E0 = 0
0.771
771 V
5Fe2+  5Fe3+ + 5e- E0 = 0.771 V
When a half-reaction is multiplied by a number, E0 value should not be
multiplied by such number.
Example: Calculate Eo for the reaction: Cd(s) + 2 Ag+  Cd2+ + 2Ag(s)
DATA: EoAg+/Ag = +0,799
+0 799 V; EoCd2+/Cd = -0,403
0 403 V;
2 x (Ag+ + e-  Ag(s)) reduction
Cd(s)  Cd2+ + 2 e- oxidation
Eo = 0,799
0 799 –(-0,403)
( 0 403) = 1,202
1 202 V

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 Chapter 8. Redox titrations

Salt bridge

In contrast to the silver electrode, E0  for the half‐reaction Cd2+ + 2 e‐  Cd((s) ) is 

negative with respect to the SHE. Therefore, E0 of the Cd/Cd2+ couple is by 
convention given a negative sign EoCd2+/Cd = ‐0,403 V
The spontaneous reaction occurs in the
in the opposite way:
Cd(s) + 2H+  Cd2+ +H2 (g)
Course 2019‐20
 Chapter 8. Redox titrations
Formal potential (Eº´)
It applies under a specific set of conditions (pH, ionic strength, concentration,
etc ) Electrode potential when the ratio of the concentrations of the reactants
etc.).
and products of the
half-reaction is exactly 1 and
the molar concentrations of
the other species are specified.
Salt Bridge
Example:  Ag+ + 1e-  Ag(s)
( )

Eº´ is 0.792 V en 1M HClO4
Eº is 0.799 V.

Fe3+ + 1e-  Fe2+

Eº = 0.771 V
E 0 771 V
Eº´ = 0.44 V en 1M H3PO4
Eº´ = 0.735 V en 1M HClO4
Eº´ = 0.68 V en 0.5M H
E 0 68 V en 0 5M H2SO4
The cathode is a Ag electrode immersed in a AgNO3
1.00 M and HClO4 1.00 M solution
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 Chapter 8. Redox titrations
S d d Electrode
Standard El d Potentials
P i l
Half-Reaction E0 at 25ºC, V

Cl2 + 2e- 2 Cl- + 1,359

CTER

REEDUCING CHARACTTER
Br2 + 2e- 2Br-
G CHARAC

+ 11,087
087
Ag+ + 1e‐ Ag0 + 0,799
Fe3+ + 1e
+ 1e‐ Fe2+
OXIDIZING

+ 00,771
771
Cu2+ + 2e‐ Cu0 + 0,337
2H+ + 2e
+ 2e‐
O

R f
Reference H2 0 000
0,000
Cd2+ + 2e‐ Cd0 - 0,403
Z 2+ + 2e
Zn 2 ‐ Z 0
Zn - 0,763
0 763

A positive electrode potential indicates that the half-reaction is spontaneous

vs. the half-reaction of the SHE and that the oxidant in the half-reaction is
stronger than the H+. A negative electrode potential means the opposite.
 Chapter 8. Redox titrations
Eff t off the
Effect th concentration
t ti on the
th electrode
l t d potentials:
t ti l Nernst
N t Equation
E ti
Equation that relates the reduction potential of an electrochemical reaction (half-
cell or full cell reaction) to the standard electrode potential, temperature, and
activities (often approximated by concentrations) of the chemical species
undergoing reduction and oxidation.
Consider the global reversible
re ersible balanced reaction:
reaction
n2Ox1 + n1Red2  n2Red1 + n1Ox2
The electrode p
potential is g
given by:
y E0= standard electrode potential
R = ideal gas constant (8.316 J mol-1 K-1)
o RT [Red1]n2 [Ox2]n1 T = absolute temperature (K)
E=E ‐ ln n = n1 x n2 = total number of moles of e-
nF [Ox1]n2 [Red2]n1 exchanged in the redox reaction
F = Faraday’s constant (96487 C mol-1)
Q Ln= 2.303 log
The equation should use activities, but generally are
Q is the reaction quotient substituted by molar concentrations.
At the equilibrium, Q = Keq If a species is gas, its concentration is substituted by
it partial
its ti l pressure pA in
i atm.
t
If it is a pure liquid or solid, its activity is 1
Course 2019‐20
 Chapter 8. Redox titrations
o 0.0592 [Red1]n2 [Ox2]n1
Substituting the values of R, F and E=E ‐ log
T at 25 ºC (298,15K) and since Ln = 2.3 log: n [Ox1]n2 [Red2]n1

For a reversible half-reaction aAox + ne‐  bAred o 0.0592 [Ared]b

Nernst equation can be expressed as: E=E ‐ log
n [Aox] a
Examples of Nernst Equation

Zn2+ + 2e-  Zn(s)

Fe3+ + e-  Fe2+

2H+ + 2e-  H2(g)

MnO4- + 5e- + 8H+  Mn2+ + 4H2O

AgCl(s) + e-  Ag(s) + Cl- E = E0 – 0,0592

0 0592 llog [Cl-]

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Chapter 8. Redox titrations

Course 2019‐20
 Chapter 8. Redox titrations

Applications of the electrode potentials

• Calculation of cell potentials

• Calculation of the equilibrium constant of a redox

reaction

• Plot of redox titration curves

Course 2019‐20
 Chapter 8. Redox titrations

Calculation of cell potentials

CuICu2+ (0,0200
(0 0200 M) II Ag+ (0,0200
(0 0200 M) I Ag

Ag+ + e-  Ag((s)) Eº= + 0,799 V

Cu2+ + 2e-  Cu(s) Eº= + 0,337 V
The same
e sa e result
esu t iss obta
obtained
ed by
applying the Nernst equation
to the balanced half‐reaction: 
2Ag+ + 2e-  2Ag(s)

= 0,799 – 0,1006 = 0,6984 V

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 Chapter 8. Redox titrations

Calculation of cell potentials

CuICu2+ (0,0200
(0 0200 M) II Ag+ (0,0200
(0 0200 M) I Ag

Ag+ + e-  Ag((s)) Eº= + 0,799 V

Cu2+ + 2e-  Cu(s) Eº= + 0,337 V

= 0,337
0 337 – 0,0503
0 0503 = 0
0,2867
2867 V

Ecell = Eright – Eleft = 0,6984

0 6984 – 0,2867
0 2867 = 0,4117
0 4117 V
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 Chapter 8. Redox titrations

Calculation of cell potentials

PtIU4+ (0,200
(0 200 M)
M), UO22+ (0,0150
(0 0150 M)
M), H+ (0,0300
(0 0300 M)IIF
M)IIFe2+ (0,0100
(0 0100 M)
M), F
Fe3+ (0,0250
(0 0250 M)IPt

Salt bridge

Platinum Platinum
electrode electrode

Course 2019‐20
 Chapter 8. Redox titrations

Calculation of the cell potentials

PtIU4+ (0,200
(0 200 M)
M), UO22+ (0,0150
(0 0150 M)
M), H+ (0,0300
(0 0300 M)IIF
M)IIFe2+ (0,0100
(0 0100 M)
M), F
Fe3+ (0,0250
(0 0250 M)IPt

Fe3+ + e-  Fe2+ Eº= + 0,771 V

UO22+ + 4H+ + 2e-  U4+ + 2H2O Eº= + 0,334 V

= 0,771
0 771 – (-0,0236)
(-0 0236) =0
=0,7946
7946 V

Course 2019‐20
 Chapter 8. Redox titrations

Calculation of the cell potentials

PtIU4+ (0,200
(0 200 M)
M), UO22+ (0,0150
(0 0150 M)
M), H+ (0,0300
(0 0300 M)IIF
M)IIFe2+ (0,0100
(0 0100 M)
M), F
Fe3+ (0,0250
(0 0250 M)I
M)Iptt

Fe3+ + e-  Fe2+ Eº= + 0,771 V

UO22+ + 4H+ + 2e-  U4+ + 2H2O Eº= + 0,334 V

Ecell = Eright – Eleft = 0,7946 – 0,1204 = 0,6742 V

Course 2019‐20
 Chapter 8. Redox titrations

Calculation of cell potentials

Ag
g I AgCl
g ((saturated),
) HCl ((0,0200 M)) I H2 ((0,800 atm),
) Pt

Ag electrode
AgCl solid

Cell without liquid junction

(lack of salt
of salt bridge)

Course 2019‐20
 Chapter 8. Redox titrations

Calculation of cell potentials

Ag I AgCl (saturated), HCl (0,0200 M) I H2 (0,800 atm), Pt

2H+ + 2e-  H2 Eº= + 0,000

Eº 0 000 V
AgCl(s) + e-  Ag(s) + Cl- Eº= + 0,222 V

Course 2019‐20
 Chapter 8. Redox titrations

Calculation of cell potentials

Ag I AgCl (saturated), HCl (0,0200 M) I H2 (0,800 atm), Pt

2H+ + 2e-  H2 Eº= + 0,000

Eº 0 000 V
AgCl(s) + e-  Ag(s) + Cl- Eº= + 0,222 V

Electrodeleft = 0,222 – 0,0592 log [Cl-] =

= 0,222
0 222 – 0,0592
0 0592 log 0
0,0200
0200 = 0,3226
0 3226 V

Ecell = Eright – Eleft = -0,0977

, – 0,3226
, = -0,420
, V

2H+ + 2Ag(s) + 2Cl- H2(g) + 2AgCl(s) non-spontaneous

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 Chapter 8. Redox titrations
Calculation of redox equilibrium constants
Reaction: Cu(s) + 2Ag+  Cu2+ + 2Ag(s)

The reaction can take place

in a galvanic cell: Cu I Cu2+ (xM) II Ag+ (yM) I Ag

Ecell = Eright – Eleft = EAg+/Ag – ECu2+ /Cu

equilibrium Ecell is equal to 0.

At the equilibrium,

Ecell = 0 = Eright – Eleft = EAg – ECu

Eright = Eleft = EAg = ECu

At the equilibrium,
q , the electrode p
potentials of all the half-reactions take the
same value

Course 2019‐20
 Chapter 8. Redox titrations
Calculation of the redox equilibrium constants
g+  Cu2+ + 2Ag
Reaction: Cu(s) + 2Ag g(s)
¡The Nernst
equation is EAg = ECu
applied to
each balanced
half-reaction!

Eo Cu2+/Cu = 0.337 V
Eo Ag+/Ag = 0.799 V
l 15,61 = 4,1 x 1015
Keq = antilog
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 Chapter 8. Redox titrations
General Equation to calculate the equilibrium constant of redox reactions

General half‐reactions
f at  Aox + n1e-  Ared
the electrodes
Box + n2e-  Bred

n2Aox + n2n1 e-  n2Ared (1)

Multiply by n2 and  n1,
n1Box + n1n2e-  n1Bred ((2))
Substract the first equation from the second to obtain: 

Balanced redox equation n2Ared+ n1Box  n2Aox + n1Bred

At the equilibrium
At the EA = E
= EB

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 Chapter 8. Redox titrations
n2Ared+ n1Box  n2Aox + n1Bred
Apply the Nernst Equation to each half‐reaction (1) and (2) 

Course 2019‐20
 Chapter 8. Redox titrations
Calculation of the redox equilibrium constants
The same equation can be obtained from the change in free energy of the
reaction:
ΔGo = -nFEocell = -RT ln Keq

n F Eocell

At 298,15 K
n Eocell n (E0right – E0left )

The higher the difference between the standard potentials and the
l
larger th number
the b off electrons
l t exchanged
h d in
i the
th redox
d reaction,
ti th
the
higher the equilibrium constant.

Course 2019‐20
 Chapter 8. Redox titrations
Calculation of the redox equilibrium constants
Reaction: 2MnO4- + 3Mn2+ + 2H2O  5MnO2(s) + 4H+
MnO4-+ 4H+ + 3e-  MnO2(s) + 2H2O
MnO2(s) + 4H+ + 2e-  Mn22+ + 2H2O

2(MnO4- + 4H+ + 3e-  MnO2(s) + 2H2O) EºMnO4- /MnO2 = 1,695 V

3(MnO 2e-  Mn
3(M O2(s) + 4H+ + 2 M 2+ + 2H2O) EºMnO2 /Mn2+ = 1,23 V

2MnO4- + 8H+ + 6e-  2MnO2(s)

( ) + 4H2O
3MnO2(s) + 12H+ + 6e-  3Mn2+ + 6H2O
In the equilibrium
q : EMnO4- /MnO2 = EMnO2 /Mn22+
Apply the Nernst equation to each balanced half-reaction:

Course 2019‐20
 Chapter 8. Redox titrations
Calculation of the redox equilibrium constants
Reaction: 2MnO4- + 3Mn2+ + 2H2O  5MnO2(s) + 4H+

47,1 = log
g Keq

Keq = antilog 47,1 ≈ 1047

Course 2019‐20