The electrochemical cell used on this experiment is comprised of a standard zinc electrode,

which provides a reference throughout, and a redox electrode involving platinum metal
immersed in the redox system to be investigated. The overall cell reaction is given by:
Zn + 2 [ Fe(CN)6 ] 3Zn 2+ + 2 [Fe(CN)6]4Reaction for the Cathode:
Zn2+ + 2e-

Zn

The electrode potential of this half-cell, Ec, is expressed by the Nernst Equation:
E c = Ec 0 +
.

R T ln

[ Zn2+ ]

nF

[Zn]

F is the Faraday constant and n is the number of electrons involved in the cell reaction. Since the
activity of the cathode remains at 1.0 during the experiment, the electrode potential of this halfcell Ec is always equal to E0c.
Reaction for the Anode:
[Fe(CN)6]3- + e-

[Fe(CN)6]4-

ferricyanide

Ea = Ea0 + R T ln
.
nF

ferrocyanide

[Fe3+]
[Fe2+]

Complete Cell
The overall cell equation depends on the redox processes occurring in both half-cells. Hence, the
EMF of the cell is the difference between the electrode potentials of the anode and cathode halfcells:
Ecell = E0cell + R T ln [ Fe3+ ]
.
.

[ Fe2+ ]

nF

The standard Gibbs free energy change for a cell with reversible electrodes is
G = - n F E0cell
Since G is also given by:
G = H - TS ( )
then:
-n F E0cell = H - TS
()
and so
S = n F d E0cell
()
dT
P

Is the following a galvanic or an electrolytic cell?

Write the balanced cell reaction and calculate Ecell.

Zn(s) | Zn2+(aq)

E = 0.34 v
E = - 0.76 v

||

Cu2+ + 2 e-

Cu2+(aq) | Cu(s)
Cu

Cathode:

Zn2+ + 2 e-

Anode:

Zn + Cu2+

Zn2+ + Cu

Cell Rx:

Eoxid

= (+ 0.76 v) + 0.34 v

Zn

Ered

Galvanic

+ 1.10 v

Ecell

An E > 0 means the cell will be spontaneous (produce a voltage). An E < 0 means the cell
must be supplied that voltage from an external power supply in order for the cell reaction to run
in the direction it is written. If anything, that cell would want to run in the reverse direction.
Often these nonspontaneous cells are called electrolytic cells. We will see a mathematical
equation that relates cell potential and spontaneity as well as look at an example of an
electrolytic process later in this handout.
What happens when the cell is not under standard conditions? The Nernst equation will
have to be applied under nonstandard conditions:
Ecell Ecell

RT
ln Q
nF

Ecell = nonstandard cell potential in volts where

Ecell = standard cell potential in volts
R = constant, 8.314 J/molK
T = temperature in Kelvin
n = moles of electrons transferred
F = Faradays constant = 96485 C/mol e
note: C represents the coulombs (unit of charge)
Q = the reaction quotient expression
Alternative representations of the Nernst Equation may be used if the temperature is
standard temperature (298K) and one has a choice of natural logarithm (ln) or common
logarithm, base 10 (log):

Ecell Ecell

0.0257 V
ln Q
n

or

Ecell Ecell

0.0592 V
log Q
n

Lets modify our previous cell as follows:

Zn(s) | Zn2+(aq), 3.00M; SO42-(3.00M) || Cu2+(aq), 0.0015M; SO42-(0.0015M) | Cu(s)
We already have Ecell = +1.10V. Let the temperature be standard (298K). The Nernst equation
expression becomes:
Ecell Ecell

0.0257 V [Zn2 ]
0.0257 V
3.00 M
ln
1.10 V
ln
2
n
[Cu ]
2 mol e
0.0015 M

Evaluating the above expression gives:

Ecell = +1.10 V 0.098 V = 1.00 V
Cell potentials have many other uses. As mentioned earlier, the cell potential indicates whether
the cell reaction is spontaneous or nonspontaneous. If you recall, spontaneity for a process is
often associated with its Gibbs free energy change, G. There is a mathematical relationship
between cell potential and this Gibbs free energy change:
G = nFE under standard conditions
G = nFE under nonstandard conditions
where

G = change in Gibbs free energy in Joules

n = moles of electrons transferred
F = Faradays constant = 98485 C/mol e-

E = cell potential
Using the units of Faradays constant, coulombs/mol e- and volts for cell potential, the Gibbs free
energy units would work out to coulomb-volts. Interestingly enough, the units, coulomb-volts,
are equivalent to Joules!
Lets calculate the Gibbs free energy change for the nonstandard cell we described in the
previous problem:
G = nFE = (2 mol e-)(96485 C/mol e-)(1.00 V) = 1.94 x 105 J
Lets quickly review some thermodynamics to see how other information may be obtained from
the Gibbs free energy change.

If you recall from thermodynamics:

G = G + RTlnQ
At equilibrium, G = 0, thus Q becomes Keq and the expression simplifies to:
G = RTlnKeq
Now that the Gibbs free energy is known, it can be related to the equilibrium constant, as well as
the cell potential:
G = nFE = RTlnKeq
So if we wanted to know the equilibrium constant value for our standard cell, it can be easily
calculated:
G = RTlnKeq
1.94 x 105 J = (8.314 J/molK)(298 K) lnKeq
Solving for lnKeq:
lnKeq

1.94 x 105 J/mol

78.3
(8.314 J/mol K)(298 K)

Take the antilog to find Keq:

Keq e78.3 1.01 x 1034

The large value for Keq indicates the reaction will proceed significantly towards products.