Objective

1. To construct electrochemical cells.

2. To determine the net cell potentials for 3 electrochemical cells.
3. To calculate the net cell potential based on the potential of the half reactions that occur
and to compare your experimental and calculated values.
4. To measure the Gibbs energy based on the cell potentials.
Introduction
The use of electrochemical cells to convert the Gibbs energy stored in the constituent half
reactions in two electrical work is of enormous industrial as well as fundamental significance.
We all have used batteries and these are simply galvanic cells that are similar to those you will
be construct in this experiment. In the laboratory, a typical electrochemical cell has a general
construction has in figure 2.1.
The standard reduction potential is a quantitative measure of a substance’s tendency to accept
electrons under standard conditions (1 atm of gases and 1M concentration) and is measured in
volts. The more positive reduction, the greater the tendency for the reduction to occur. For the
half reaction that represents the oxidation of a matter, you can determine the standard oxidation
potential (E°ox) for the half reaction. This value has the same numerical value has the standard
reduction potential but the opposite sign. For example, aluminium ion has a standard reduction
potential value of -1.65V.

Al3+ (aq) + 3e Al(s) E°red = -1.65V

This means that the standard oxidation potential for aluminum metal is +1.65V.
Al (s) Al3+ (aq) + 3e E°ox = +1.65V
The standard cell potential ( E°cell) is the sum of the standard oxidation and reduction potentials
has shown below:
E°cell = E°ox + E°red (1)
An example will be provided as well on how to calculate a standard net potential and compare it
to your experimental or net cell potential value. For nickel-copper electrochemical cell, you
would start of by placing a strip of nickel into a nickel(II) salt solution. It should be pointed out
to you that all of the solutions are aqueous. You would then place a strip of copper into a
copper(II) solution. The next step to connect one end of a wire to the nickel strip and the other
end to the copper strip. Electrons will pass through this wire between the nickel and the copper
strip. If you wanted to predict which direction the electrons would flow through the wire, you
can look up the standard reduction potentials for nickel and copper. The E°red value for the nickel
ion is -0.26V and +0.34V for copper ion. This means that the Cu2+ ion has a greater tendency to
accept electrons than the nickel(II) or Ni2+ ion. Therefore, the electrons will pass through the
wire from the nickel strip to the copper strip. However, this can only happen if a second
connection is provided to complete the electrical circuit.

This second connection is called a salt bridge and is placed in both solutions of the two
containers. You know have an electrochemical cell. The electrochemical cell is a system that
utilizes a spontaneous oxidation – reduction reaction to pump electrons through an electrical
circuit. This system is composed of two part or half cells. In this example there is the nickel half
cell where nickel metal is being oxidized and the copper half cell where the copper(II) ion is
being reduced. The metal strips are called electrodes. The electrode in the half cell where
oxidation occur is called the anode and the electrode in the half cell where reduction occur is
called cathode.
The cell potential can be measured by connecting a voltmeter between the half cells. If you
wanted to approximate what you observed voltage should be for this oxidation-reduction
reaction, you can simply add the two half reactions together and calculate the standard net
potential. Since copper half cell is undergoing reduction, the half reaction will be represented as
a reduction and the nickel half cell will have the half reaction represented as an oxidation.
Cu2+(aq) + 2e- Cu(s) E°red = +0.34V
Ni(s) Ni2+(aq) + 2e- E°ox = +0.26V
Cell reaction Ni(s) + Cu2+(aq) Ni2+(aq) + Cu(s) E°cell = +0.60V
For measurements taken under non-standard conditions, the Nernst equation is used to calculate
Ecell. The Nernst equation is:
E = E° - RT ln Q or E = E° - 2.303 RT log Q (2)
nF nF
where F is Faraday constant. R the universal gas constant, n the number of electron transferred
and Q is the reaction quotient. When R = 8.314JK-1mol-1, T = 298K and F = 96500Cmol-1 , the
equation becomes :
E = E° - 0.0591 log Q
n

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THERMODYNAMICS
The Gibbs Free Energy(G) is the function derived from enthalpy (H) and entropy (S). The
change in free energy (∆G) is the composite function that gives a measure of the spontaneity of a
reaction. If ∆G < 0, a reaction will occur spontaneously. If ∆G > 0, the reaction is not
spontaneous. If ∆G = 0, the system is at equilibrium. When the state of the system changes at
constant temperature:
∆G = ∆H - T∆S (4)
Where T is the absolute temperature in Kelvin.
For a general reaction or process of A and B giving product C and D:
aA + bB cC + dD
the reaction quotient, Q, is:

[𝐶]𝑐 [𝐷]𝐷
𝑄=
[𝐴]𝑎 [𝐵]𝑏

The ∆G of a process at nay concentration of A, B, C, and D, is given by:

∆G = ∆G° + RT ln Q (6)

Where ∆G° is the change in free energy of the reaction under the defined standard of 1 atm and
1M concentration of reactant. ∆G is the observed change in free energy at condition other than
standard. At equilibrium, Q = K eq and ∆G = 0. Under this condition equation (6) becomes:
∆G° = - RT ln Q or ∆G° = - RT ln K (7)
The cell potential of a redox process is related to the free-energy change as follow:
∆G° = - nFE° (8)
In this experiment, you will construct three electrochemical cells, a zinc-copper cell, an iron-
copper cell and a zinc-iron cell. You will obtain your experimental or net cell potential and then
compare this value to the standard net potential that you will calculate for each cell writing
equations for all of the half-reaction and the net reaction as well. The Gibbs energy which is one
of the thermodynamic function also will be determined from the cell potentials obtained.