Latimer Diagrams

Latimer diagrams summarize a large amount of redox information. In acidic solution:

ERed
- +
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
Can be summarized as:

1.19 V 1.21 V 1.65 V 1.63 V 1.36 V

ClO4 ClO3 HClO2 HOCl Cl2 Cl-
- -

| 1.47 V |

The diagrams are always written in the same direction:

Reduction
Oxidation
Conclusions: all the species, except Cl-, are good oxidizing agents since they all have positive
voltages. Under standard conditions, HClO2 is the best oxidizing agent. Also, Cl- is a poor
reducing agent, since E = Ecathode - Eanode and the oxidation of Cl- would be at the anode. In
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 |

All the half-cell reactions that have H+ as a reactant in acidic solution have decreased standard
cell potentials, making the oxyacids poorer oxidizing agents in basic solution.
What if important reactions are missing from the list of half-cell reactions or the Latimer
diagram? For example, ClO3- + 2 H2O + 4 e- - -
OCl + 4 OH is not listed. We can add two
other half-cells to give the desired reaction:
ERed 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

However, half-cell voltages are not additive! Instead we must calculate G for each reaction,
add the G's and then convert back to a voltage all using G = -nFE. For this overall reaction
G = -193.0 kJ/mol and n = 4, so the final voltage is 0.50 V. We can now add this new half-cell
to the basic solution Latimer diagram:
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 |

Latimer diagrams also give us other very useful information. Perchlorate salts and solutions
are stable unless a reducing agent is available (then watch out). But, what about hypochlorite,
OCl- ? At first you might think that hypochlorite, OCl-, solutions would be stable if no reducing
agent was available. However, hypochlorite can act as its own reducing agent:
ClO- + H2O + 2 e- Cl- + 2 OH- 0.88 V
-
-
ClO3 + 2 H2O + 4 e OCl- + 4 OH- 0.50 V
Multiplying the top half-cell by two, reversing the ClO3- half-cell to act at the anode, and adding
gives the balanced cell reaction:
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-
with a cell voltage of E = Ecathode - Eanode = 0.88 V - 0.50 V = 0.33 V, which is spontaneous. A
redox reaction where a substance reacts with itself to be both oxidized and reduced is called a
disproportionation. Hypochlorite is unstable with respect to disproportionation.
Latimer diagrams provide a very easy way to determine if disproportionation is spontaneous.
For example, consider just the two reactions important for OCl- disproportionation:
0.50 V 0.88 V
ClO3- OCl- Cl-
If the voltage to the right of the species in question is greater than the voltage to the left of the
species, the species is unstable with respect to disproportionation. For another example, we can
determine if ClO3- is stable or unstable:
0.36 V 0.50 V
ClO4- ClO3- OCl-
Perchlorate Chlorate Hypochlorite
Chlorate ion is unstable with respect to disproportionation to perchlorate and hypochlorite ions.
Often the stability of substances is very pH dependent. For example, hypobromite is unstable
in acid and stable in basic solution:
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
Oxygen: Disproportionation of H2O2
ERed
H2O2 + 2 H +
+ 2 e-
2 H2O 1.77 V
O2 + 2 H+ + 2 e-
2O2
H 0.69 V

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

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

Sulfur1
Acidic solution:

0.16 V 0.41 V 0.49 V 0.17 V

SO4 2-
SO2(g) S2O3 S H2S
2-

| 0.54 V 0.02 V |
|
S4O6 |
2-

Basic solution:
-0.94 V -0.57 V -0.75 V 0.00 V -0.09 V
SO4 SO3 S2O3 S S42- HS-
2- 2- 2-

| -0.66 V | -0.06 V |

Thiosulfate, S2O32-, is unstable with respect to disproportionation to S and SO2 in acidic solution.
However, thiosulfate is manufactured by boiling S and SO32- in slightly basic solution, which is
seen to be favorable from the basic solution Latimer diagram. Notice the small positive potential
for the reduction of SO42- to SO2 and the negative potential for reduction of SO42- to sulfite, SO32-
in basic solution. In other words, SO2 and especially SO32- are good reducing agents. Sulfites and
SO2 have long been used in the food industry for food preservation as antioxidants, however
some individuals have allergies to sulfites. Sulfites have been banned for use on food to be eaten
raw, such as in salad bars.

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 |

1. B. M. Mahan, R. J. Myers, University Chemistry, Benjamin Cummings, Menlo Park, CA,

1987.