Latimer Diagrams

Acidic solution:

E°Red
- +
ClO4 + 2 H + 2 e- →
←
-
ClO3 + H2O 1.19 V
ClO3- + 3 H+ + 2 e- →
← HClO2 + H2O 1.21 V
HClO2 + 2 H+ + 2 e- →
← HClO + H2O 1.65 V
HClO + H+ + e- → 1
← /2 Cl2 (g) + H2O 1.63 V

1.19 V 1.21 V 1.65 V 1.63 V 1.36 V

ClO4  ClO3  HClO2  HOCl  Cl2  Cl-
- -

| 1.47 V |

Reduction →
← Oxidation

Conclusions: all the species, except Cl-, are good oxidizing agents
HClO2 is the best oxidizing agent
Cl- is a poor reducing agent
E° = E°cathode - E°anode with the oxidation of Cl- at the anode

Basic solution:

0.36 V 0.35 V 0.65 V 0.40 V 1.36 V

ClO4  ClO3  ClO2  OCl  Cl2  Cl-
- - - -

| 0.88 V |

Conclusion: the oxyacids are poorer oxidizing agents in basic solution.

Missing reactions:

ClO3- + 2 H2O + 4 e- →
← OCl- + 4 OH-

E°Red ∆G° = -nFE°

-
ClO3 + H2O + 2 e- →
←
-
ClO2 + 2 OH -
0.35 V -67.5 kJ/mol
ClO2- + H2O + 2 e- →
← OCl- + 2 OH- 0.65 V -125.4 kJ/mol
ClO3- + 2 H2O + 4 e- →
← OCl- + 4 OH- -193.0 kJ/mol

Half-cell voltages are not additive!

∆G° = -193.0 kJ/mol and n = 4 E°Red = 0.50 V

0.36 V 0.35 V 0.65 V 0.40 V 1.36 V

ClO4  ClO3  ClO2  OCl  Cl2  Cl-
- - - -

| 0.50 V | 0.88 V |

Stability of hypochlorite, OCl-

ClO- + H2O + 2 e- →← Cl- + 2 OH- 0.88 V
- -→
ClO3 + 2 H2O + 4 e ← OCl- + 4 OH- 0.50 V

Cathode: reduction 2 ClO- + 2 H2O + 4 e- →

← 2 Cl
-
+ 4 OH-
→
Anode: oxidation OCl- + 4 OH- ← ClO3
-
+ 2 H2O + 4 e-
→
3 ClO- ← 2 Cl- + ClO3-

E° = E°cathode - E°anode = 0.88 V - 0.50 V = 0.33 V spontaneous

0.50 V 0.88 V
ClO3  OCl  Cl-
- -
E°R - E°L > 0 spontaneous
Stability of ClO3-
0.36 V 0.50 V
ClO4  ClO3  OCl-
- -

Perchlorate Chlorate Hypochlorite unstable

pH dependence hypobromite

1.49 V 1.59 V
acidic solution: BrO3  HOBr  Br2
-
HOBr unstable
0.54 V 0.45 V
basic solution: BrO3  OBr  Br2
- -
OBr- stable