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Chemistry 223
David Ronis
McGill University
Salt Bridge
e
e
Zn Cu
+2 +2
Zn Cu
1. General Considerations
Figure 1 shows a simple device used that functions as a battery, the so-called Galvanic or
Daniels cell. Basically, when the switch is closed, the zinc electrode will oxidize, loosing 2 elec-
trons per atom, and producing a zinc ion. These travel through the external circuit (doing work),
and reenter the cell at the cathode, where one copper ion is reduced to copper metal. Thus, we
can describe the redox chemistry in terms of the half-reactions:
Zn Zn+2 + 2e (at the anode)
where W nonPV is just the non-mechanical (here electrical) work being done by the system on
the surroundings, and where the inequality becomes an equality when the process is reversible.
Indeed, one can come close to having the cell operate reversibly by having very little current run
through the external circuit. Equation (1) is just what we saw when we used the law of definite
proportion in chemical reactions.
In electrical terms, suppose there is a voltage difference, , between the two electrodes1 .
Thus, by definition, each electron will change its energy by e as it moves trough the external
circuit (remember, by convention, electrons have negative charge). Equivalently, they do e
work on the surroundings. Hence, by using Eq. (1) we see that
G rxn
, (2)
nF
where n is the number of moles of electrons transferred in the reaction (2 for our example
above), F N A e is the charge associated with one mole of electrons, and is known as the
Faraday; It has the value
F = 96,487 coul/mol or 2. 891 1014 esu/mol.
Henceforth, we will restrict our discussion to reversible cells, in which case Eq.(2)
becomes an equality. Notice that the cell EMF is independent of the precise way you balance the
overall reaction. Actually, the main thing that is important in balancing the redox reactions given
above is that we produce the same number of electrons in the oxidation at the anode as are con-
sumed in the reduction at the cathode. Lets write the free energy change for each half-reaction as
G = + nF
half reaction , half reaction
where well use the - sign for reductions and the + sign for oxidations, i.e., we define the half-
reaction potentials for reductions; hence, for our example,
G rxn = 2F rxn = 2F Cu+2 |Cu Zn+2 |Zn .
For the reaction to proceed as written when the circuit is closed, we need G rxn 0, or equiva-
lently, 0. If we assume standard state conditions, we can simply look up the reduction
potentials in a table, which for our reaction has
1
For historical reasons, this is also known as the electromotive force or EMF.
Zn2 + 2e Zn -0.763
Cu2 + 2e Cu 0.337
Hence, the overall cell EMF is 0. 337 (0. 763) = 1. 100V and the cell operates as written. Note
that the standard state for electrochemical reactions is defined not with respect to elements in
their standard states, but rather, against a standard electrode, the so-called standard hydrogen
electrode (SHE).
What happens if the conditions arent standard? We can still get an expression for the
reversible cell EMF from Eqs. (1) and (2) if we know what the chemical potentials are. Recall
that we have
i = (0)
i + RT ln(a i ), (3)
where ai is the activity of compound i; it is the partial pressure in atm for ideal gases, or the
molar concentration in ideal solutions, but otherwise is more complicated. When the steps lead-
ing to Eq. (2) are repeated it follows that
RT 0. 05916
(0) ln(a11 ... ar r ) = (0) log10 (a11 ... ar r ), (4)
nF n
where (0) is the standard cell EMF, as calculated above, the term with the logarithm accounts
for any non-standard conditions and the last equality is what you get at 20C, converting to
base-10 logarithms. This is known as the Nernst equation.
a11 ... ar r = K = e nF
(0)
/RT
, (5)
where gives another connection between equilibrium constants and thermodynamic quantities.
Again, voltage is easy to measure very accurately, and this is a good way to measure con-
centration effects etc. on equilibrium.