Chapter 20: Electrochemistry

The Nernst equation

If we consider a cell made up from a silver/silver ion
electrode and a copper/copper(II) ion electrode, the
291
​  reaction taking place is:

Cu(s)  +  2Ag+(aq) Cu2+(aq)  +  2Ag(s) E —O = +0.46 V

standard conditions and change the concentration of the

silver ions, we obtain the graph shown in Figure 20.23.
Note that we have plotted the value of Ecell (non-standard
conditions for the cell as a whole) against the logarithm of
the silver ion concentration.

0.5
​ 
0.46 V E—
O
cell 
0.4

0.3
Ecell / V

0.2

0.1

0
–8 –7 –6 –5 –4 –3 –2 –1 0
lg [Ag+]

Figure 20.23  Increasing the concentration of silver ions in the

cell reaction Cu(s)  +  2Ag+(aq) Cu2+(aq)  +  2Ag(s) makes
the value of Ecell more positive.
 Cambridge International A Level Chemistry

The effect of concentration and temperature on the value of

w rked exa ple
Ecell can be deduced using the Nernst equation. For a given
electrode, e.g. a Cu(s)/Cu2+(aq) electrode, the relationship is:
8 Calculate the value of the electrode potential at 298 K
[oxidised form]
RT ​ ln ______________ of a Cu(s)/Cu2+(aq) electrode that has a concentration of
E = E —O   +  ​ ___ ​     ​
  
zF [reduced form] Cu2+(aq) ions of 0.001 mol dm–3. E —
O
= +0.34 V
where Substituting the values in the relationship:
E is the electrode potential under non-standard conditions 0.059
E = E—
O
  +  ​ _____
z   ​  log10 [Cu2+(aq)]
E —O is the standard electrode potential
0.059
R is the gas constant, 8.314, in J K–1 mol–1 E = +0.34  +  ​ _____
2   
 ​ log10 (0.001)

T is the kelvin temperature E = +0.34 – 0.089 = +0.25 V

z is the number of electrons transferred in the reaction Note how log10 [oxidised form] changes the sign of the
F is the value of the Faraday constant in C mol–1 second term in the equation:
ln is the natural logarithm ■■ If the concentration is 1 mol dm–3,
log10 [oxidised form] is 0 and E = E —
O
.
[oxidised] refers to the concentration of the oxidised form
in the half-equation. ■■ If the concentration is less than 1 mol dm–3,
log10 [oxidised form] is negative and E is less
Fortunately for us, for a metal/metal ion electrode, we
positive than E —O
.
can simplify this equation in three ways:
■■ If the concentration is greater than 1 mol dm–3,
■■ The natural logarithm, ln, is related to log to the base 10 by log10 [oxidised form] is positive and E is more
the relationship positive than E —O
.
ln x  = 2.303 log10 x
At standard temperature the values of R, T and F are constant
■■
Feasibility predictions based on E —O don’t
■■ For a metal/metal ion electrode, e.g.
292 Cu2+(aq)  +  2e  +   Cu(s) the reduced form is the metal.
always work!
The concentration of the metal does not change. So The feasibility of a reaction based on E —O values is no
the ratio [oxidised form]/[reduced form] can be written guarantee that a reaction will proceed quickly. It only tells
[oxidised form], e.g. [Cu2+(aq)] us that a reaction is possible, and that the reverse reaction
does not occur. Some reactions are feasible, but they
So the relationship becomes:
proceed so slowly that they do not seem to be taking place.
0.059
E = E O   +  ​ _____
—
z   ​  log10 [oxidised form] Take, for example, the lack of reactivity of zinc with cold
water. Remember that water contains H+ ions. The relevant
Note that if the temperature is not 25 °C the full form of the
Nernst equation must be used. half-equations are:

H+  +  e– _​ 1  ​  H (g) E —O = 0.00 V

2 2
ues n Zn2+(aq)  +  2e– Zn(s) E —O = –0.76 V
27 a Calculate the value of the electrode potential +
Even when the low concentration of H ions is taken into
at 298 K of a Ni(s)/Ni2+(aq) electrode that has a
account, E —O values predict that a reaction should occur.
concentration of Ni2+(aq) ions of 1.5 mol dm–3.
E—O
= –0.25 V.
The rate of reaction between zinc and water, however, is
extremely slow. It is the rate of reaction rather than the
b Calculate the electrode potential of a silver/silver
ion electrode, Ag(s)/Ag+(aq), at 0 °C when the
value of E —O which is determining the lack of reactivity.
concentration of Ag+(aq) ions is 0.0002 mol dm–3.
E—O
= +0.80 V. ques ns

28 An industrial process relies on a reaction that is

impractically slow under normal conditions. How
might you try to solve this problem? Use your
knowledge of reaction rates to suggest several
different approaches.
29 Describe two limitations to using E —
O
values to predict
the feasibility of a reaction.