Latimer Diagram

Written with the most oxidized species on the left, and the most reduced species on the right.

Oxidation number decrease from left to right and the E0 values are written above the
line joining the species involved in the couple.
 Latimer diagram for chlorine in acidic solution

- +1.2 - +1.18 +1.65 +1.63 +1.36

ClO4 ClO3 HClO2 HClO Cl2 Cl-
+7 +5 +3 +1 0 -1

- +1.2
ClO4 ClO3-

Can you balance the equation?

+1.63
HClO Cl2
balance the equation

2 HClO(aq) + 2 H+(aq) + 2 e- Cl2(g) + 2 H2O(l) E0 = +1.63 V

 How to extract E0 for nonadjacent oxidation state?
E0 =?
- +1.2 - +1.18 +1.65 +1.63 +1.36
ClO4 ClO3 HClO2 HClO Cl2 Cl-
+7 +5 +3 +1 0 -1

1 2
Identify the two reodx couples
Find out the oxidation state of chlorine
Write the balanced equation for the first couple
G = G’ + G’’
HClO(aq) + H+(aq) + e ½ Cl2(g) + H2O(l) +1.63 V -nFE = -n’FE’ - n’’FE’’
E = n’E’+ n’’E’’
Write the balanced equation for the second couple
n’+n’’
½ Cl2(g) + e Cl- (l) +1.36 V

E0 = 1.5 V
 Latimer diagram for chlorine in basic solution

+0.37 +0.3 +0.68 +0.42 +1.36

ClO4- ClO3- ClO2 - ClO - Cl2 Cl-

E0 ??
+0.42
ClO- Cl2 +0.89
Balance the equation…

2ClO- (aq) + 2H2O(l) + 2e- Cl2(g) + 4OH-(aq) E0 = 0.42 V

Find out the E0 G = G’ + G’’
-nFE = -n’FE’ - n’’FE’’
+0.89 E = n’E’+ n’’E’’
n’+n’’
 Disproportionation
Element is simultaneously oxidized and reduced.
2 M+(aq) M(s) + M2+(aq)

‘the potential on the left of a species is less positive than that on the right- the species can
oxidize and reduce itself, a process known as disproportionation’.
Reaction is spontaneous???

Reaction is spontaneous
 What happens when Fe(s) react with H+?
Iron +2 and +3 G = -nFE
2+ -2 x F x -0.44 = 0.88 V
Fe + 2e Fe -0.440-0.440

Fe3+ + e Fe2+ 0.771 +0.77

-1 x F x +0.771 = -0.771 V

Fe3+ + 3e Fe + 0.109 F
= -3 x F x –0.036
+0.036 Fe3+
Fe

+0.44 Fe2+

-0.036

-0.44
Fe3+ +0.77 Fe2+ Fe
 -0.036

Fe3+ +0.77 Fe2+ -0.44 Fe

[Fe(CN)6]3- 0.36 [Fe(CN)6]4-

-1.16

oxidation of Fe(0) to Fe(II) is considerably more favorable in the cyanide/acid

mixture than in aqueous acid.
(1) Concentration
(2) Temperature
(3) Other reagents which are not inert
Latimer diagram for Oxygen

1.23 V
 Disproportionation
the potential on the left of a species is less positive than that on the right- the species can
oxidize and reduce itself, a process known as disproportionation.
NO2
What is the reaction of MnO4- with 5 equivalents of VO2+ ?

Thermodynamically favorable?
Arthur A. Frost
 Frost Diagram Arthur A. Frost

Graphically illustration of the stability of different oxidation states relative to its elemental
form (ie, relative to oxidation state= 0)

XN + Ne- X0

NE0 = -G0/F
 Look at the Latimer diagram of nitrogen in acidic solution

a b c d e

G = G’ + G’’
f g h
-nFE = -n’FE’ - n’’FE’’
E = n’E’+ n’’E’’
n’+n’’
a NO3- + 6H+ + 5e- ½ N2 + 3H2O E0 = 1.25V

b ½ N2O4 + 4H+ + 4e- ½ N2 + 2H2O E0 = 1.36V

c HNO2 + 3H+ + 3e- ½ N2 + 2H2O E0 = 1.45V

G = G’ + G’’
d NO + 2H+ + 2e- ½ N2 + H2O E0 = 1.68V
-nFE = -n’FE’ - n’’FE’’
e ½ N2O + H+ + e- E = n’E’+ n’’E’’
½ N2 + ½ H2O E0 = 1.77V
n’+n’’
f ½ N2 + 2H+ + H2O + e- NH3OH+ E0 = -1.87V

g ½ N2 + 5/2 H+ + 2e- ½ N2H5+ E0 = -0.23V

h ½ N2 + 4H+ + 3e- NH4+ E0 = 0.27V

Oxidation state: species NE0
N(V): NO3- (5 x 1.25, 5)

N(IV): N2O4 (4 x 1.36, 4)

N(III): HNO2 (3 x 1.35, 3)

N(II): NO (2 x 1.68, 2)

N(I): N2O (1 x 1.77, 1)

N(-I): NH3OH+ [-1 x (-1.87), -1]

N(-II): N2H5+ [-2 x (-0.23), -2]

N(-III): NH4+ (-3 x 0.27, -3)

 Frost Diagram – N2

Acidic
What do we really get from the Frost diagram?

the lowest lying species corresponds to

the most stable oxidation state of the
element
 E0 of a redox couple
HNO2/NO

3, 4.4

2, 3.4

N’E0’-N”E0”
Slope = E0=
N’-N”
1V
 Oxidizing agent? Reducing agent?

The oxidizing agent - couple with more positive slope - more positive E

The reducing agent - couple with less positive slope

If the line has –ive slope- higher lying species – reducing agent

If the line has +ive slope – higher lying species – oxidizing agent
Identifying strong or weak agent?
 Disproportionation
Element is simultaneously oxidized and reduced.
2 M+(aq) M(s) + M2+(aq)
E0 E0’
M(s) 2M+(aq) M2+(aq)

‘the potential on the left of a species is less positive than that on the right- the species can
oxidize and reduce itself, a process known as disproportionation’.
Disproportionation
What Frost diagram tells about this reaction?
A species in a Frost diagram is unstable with respect to disproportionation
if its point lies above the line connecting two adjacent species.
Disproportionation…. another example
Comproportionation reaction
Comproportionation is spontaneous if the intermediate species
lies below the straight line joining the two reactant species.
Comproportionation another example…

In acidic solution…
Mn and MnO2

Mn2+
Rate of the reaction hindered
insolubility?

In basic solution…
MnO2 and Mn(OH)2

Mn2O3
 From the Frost diagram for Mn….
* Thermodynamic stability is found at the bottom of the diagram.
Mn (II) is the most stable species.

* A species located on a convex curve can undergo disproportionation

example: MnO43- MnO2 and MnO42- (in basic solution)

•Any species located on the upper right side of the diagram will be a strong oxidizing
agent. MnO4- - strong oxidizing agent.

•Any species located on the upper left side of the diagram will be a reducing agent. Mn -
moderate reducing agent.
 * Although it is thermodynamically favorable for permanganate ion to be reduced to
Mn(II) ion, the reaction is slow except in the presence of a catalyst. Thus, solutions of
permanganate can be stored and used in the laboratory.

* Changes in pH may change the relative stabilities of the species. The potential of any
process involving the hydrogen ion will change with pH because the concentration of this
species is changing.

* Under basic conditions aqueous Mn2+ does not exist. Instead Insoluble Mn(OH)2 forms.
Can you identify the odd one out among the Transition metals?

*All metals are good reducing agents

*Exception: Cu
*Reducing strength: goes down smoothly from
Ca to Ni
*Ni- mild reducing agent

*Early transition elements: +3 state

Latter +2 state

*Fe and Mn – many oxidation states

*High oxidation state: Strong oxidizing agents
 Hydrazine is a versatile reducing agent in acidic

Use the Latimer and Frost diagrams for nitrogen in acidic solution to find the potential
+
for HNO2→N2H5