Latimer Diagrams

O, S, N Descriptive Chemistry
 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/ Cl
2 2 (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

0.36 V 0.35 V 0.65 V 0.40 V 1.36 V

ClO4-  ClO3-  ClO2-  OCl-  Cl2  Cl-
| 0.88 V |
Acid: 1.19 V 1.21 V 1.65 V 1.63 V 1.36 V
ClO4-  ClO3-  HClO2  HOCl  Cl2  Cl-
| 1.47 V |
Basic:
0.36 V 0.35 V 0.65 V 0.40 V 1.36 V
ClO4-  ClO3-  ClO2-  OCl-  Cl2  Cl-
| 0.88 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 |
 Disproportionation of H2O2

0.69 V 1.77 V
acidic solution: O2  H2O2  H2O

2 H2O2 O2 + 2 H2O E = 1.77 – 0.69 = 1.08 V

• H2O2 unstable
 Sulfur
0.16 V 0.41 V 0.49 V 0.17 V
SO42-  SO2(g)  S2O32-  S  H2S
| 0.54 V 0.02 V |
| S O 2- |
4 6
Basic solution:
-0.94 V -0.57 V -0.75 V -0.00 V -0.09 V
SO42-  SO32-  S2O32-  S  S42-  HS-
| -0.66 V | -0.06 V |

Thiosulfate, S2O32-, is unstable with respect to disproportionation

Thiosulfate is made by boiling S and SO32- in slightly basic solution
SO2 and SO32- are good reducing agents
S42- polysulfide ions, catenation: formation of chains of identical atoms (esp. C)
 Nitrogen
Acidic solution:
0.96 V .
| 0.79 V 1.12 V 1.00 V | 1.59 V 1.77 V 0.27 V
NO3-  NO2(g)  HNO2  NO  N2O  N2  NH4+
| 1.25 V |

+5 +4 +3 +2 +1 0 -3

NO2, NO unstable with respect to disproportionation

2 NO2(g) + H2O HNO2 + H+ + NO3- Dilute solution — acid rain

3 NO2(g) + H2O NO (g) + 2 HNO3 Synthesis of nitric acid