Appendix A tells how to convert ln into log.

Converting the natural logarithm in Equation 14-13 into the base 10 logarithm and
inserting T
298.15 K (25.00C) gives the most useful form of the Nernst equation:
Nernst equation at 25C:

E
E 

A bB
0.059 16 V
log a
n
AA

(14-15)

The potential changes by 59.16/n mV for each factor-of-10 change in Q.

Example Writing the Nernst Equation for a Half-Reaction

Lets write the Nernst equation for the reduction of white phosphorus to phosphine gas:
white)  3H  3e T PH3 (g)

1
4 P4 (s,

E
0.046 V

Solution

We omit solids from the reaction quotient, and the concentration of a gas is
expressed as the pressure of the gas. Therefore, the Nernst equation is
PPH3
0.059 16
E
0.046 
log  3
3
[H ]
Example Multiplying a Half-Reaction Does Not Change E 

If we multiply a half-reaction by any factor, E does not change. However, the factor n
before the log term and the form of the reaction quotient, Q, do change. Lets write the
Nernst equation for the reaction in the preceding example, multiplied by 2:
1
2 P4 (s,

white)  6H  6e T 2PH3 (g)

E
0.046 V

Solution

E
0.046 

P2PH3
0.059 16
log  6
6
[H ]

Even though this Nernst equation does not look like the one in the preceding example,
Box 14-2 shows that the numerical value of E is unchanged. The squared term in the
reaction quotient cancels the doubled value of n in front of the log term.

Nernst Equation for a Complete Reaction

In Figure 14-6, the negative terminal of the potentiometer is connected to the Cd electrode
and the positive terminal is connected to the Ag electrode. The voltage, E, is the difference
between the potentials of the two electrodes:
Nernst equation for a complete cell:

E
E  E

(14-16)

where E is the potential of the electrode attached to the positive terminal of the potentiometer and E is the potential of the electrode attached to the negative terminal. The potential

Box 14-2 E and the Cell Voltage Do Not Depend on How You Write the Cell Reaction
Multiplying a half-reaction by any number does not change the
standard reduction potential, E. The potential difference between
two points is the work done per coulomb of charge carried
through that potential difference (E
work/q). Work per coulomb
is the same whether 0.1, 2.3, or 104 coulombs have been transferred. The total work is different in each case, but work per
coulomb is constant. Therefore, we do not double E if we multiply a half-reaction by 2.
Multiplying a half-reaction by any number does not change
the half-cell potential, E. Consider a half-cell reaction written
with either one or two electrons:
1
E
E  0.059 16 log a
Ag  e T Ag(s)
b
[Ag]

280

2Ag  2e T 2Ag(s)

E
E 

0.059 16
1
log a
b
2
[Ag]2

The two expressions are equal because logab
b log a:

0.059 16
1
2  0.059 16
1
log a
b
b

log a

2
2
[Ag ]
2
[Ag]

0.059 16 log a

1
b
[Ag]

The exponent in the log term is canceled by the factor 1/n that
precedes the log term. The cell potential cannot depend on how
you write the reaction.

CHAPTER 14 Fundamentals of Electrochemistry