Oxidation/Reduction Limits for H2O

Consider the Oxidation of H2O to yield O2(g), the half reaction can be written as;

2 H2O === O2(g) + 4 H+ + 4 e- Eo = -1.23 V (from tables)

Re-writing this as a reduction (by convention) and dividing by 4 (for convenience) yields;

¼ O2(g) + H+ + e- ==== ½ H2O Eo = 1.23 V

(note the sign change in Eo, but the magnitude remains unchanged)

Writing an equilibrium expression for the half reaction yields;

1
K eq = 1/4 + = PO2 {H + }-1 {e - }-1
-1/4
-
PO2 {H } {e }

Isolating {e-}-1 yields; {e-}-1 = Keq PO21/4 {H+}

and taking log of both sides yields; log {e-}-1 = log Keq + log PO21/4 + log {H+}

Defining pe = -log {e-} and pH = -log {H+} yields;

pe = log Keq + log PO2-1/4 – pH

At the boundary of chemical oxidation of H2O, the PO2 = 1 atm and so;

pe = log Keq – pH
ΔG o
− − ΔG o
Since, K eq = 10 2.3 RT
, log K eq = and ΔGo = - nFEo, then
2.3RT
nFE o
log K eq = and
2.3RT
nFE o
pe = − pH
2.3RT

In the present case, where n = 1 and Eo = 1.23 V, the dependence of pe on pH is given by;

pe = 20.8 – pH for the boundary for the oxidation of H2O to O2

where F = 96,485 C/mol, R = 8.314 J/mol K, T = 298 K and 1 CV = J/mol.

When H+ is at standard state (i.e., 1 M, pH = 0) at 25oC, then

nFE o
pe = pe o = = 20.8 (for the oxidation of H2O to O2)
2.3RT
− ΔG o Eo E
In general; pe o = log K eq = = , and pe = for any one electron
2.3RT 0.0591 0.0591
process at 25oC.

water redox boundaries.doc

Consider the Reduction of H2O to yield H2(g), the half reaction can be written as;

2 H2O + 2 e- === H2(g) + 2 OH- Eo = - 0.827 V (from tables)

Re-writing this reduction dividing by 2 (for convenience) yields;

1/2 H2O + e- === ½ H2(g) + OH- Eo = - 0.827 V

(note the magnitude of Eoremains unchanged)

Writing an equilibrium expression for the half reaction yields;

Keq = PH21/2 {OH-} {e-}-1

Isolating {e-}-1 and taking log of both sides yields;

log {e-}-1 = log Keq + log PH2-1/2 + log {OH-}-1

Defining pe = -log {e-} and pOH = -log {OH-} yields;

pe = log Keq + log PO2-1/2 + pOH

At the boundary of chemical reduction of H2O, the PH2 = 1 atm and so;

pe = log Keq + pOH

Since pKw = pOH + pH, we can substitute pOH = pKw – pH thus;

pe = log Keq + pKw - pH

As before,
nFE o
log K eq = and
2.3RT
nFE o
pe = + pK w − pH
2.3RT

In the present case, where n = 1, Eo = - 0.827 V and pKw = 14, the dependence of pe on
pH is given by;
(1)(96485)(−0.827)
pe = + 14 − pH = − pH (note that the units in nFEo/2.3RT cancel)
2.3(8.314)(298)

When H+ is at standard state (i.e., 1 M, pH = 0) at 25o, then pe = peo = 0 for the reduction
of H2O to H2.

At other {H+}, the boundary between H2O and H2 is given by; pe = - pH

water redox boundaries.doc