OBJECTIVES

1. To construct electrochemical cells.

2. To determine the net cell potentials for three electrochemical cells.
3. To calculate the net cell potential based on the potentials of the half-reactions that
occur and to compare your experimental and calculated values.
4. To measure the Gibbs energy based on the potentials.

INTRODUCTION
The use of electrochemical cells to convert the Gibbs energy stored in the constituent half-
reactions into electrical work is of enormous industrial as well as fundamental significance.
We have all used batteries and these are simply galvanic cells that are similar to those you
will be constructing in this experiment. In the laboratory, a typical electrochemical cell has a
general construction as in Figure 2.1.

Figure 2.1: A Schematic diagram of galvanic cell

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 the reduction potential, the greater the tendency for
reduction to occur. For the half-reaction that represents the oxidation of a metal, you can
determine the standard oxidation potential (𝐸 𝑂 𝑜𝑥) for the half-reaction. This value has the
same numerical value as the standard reduction potential but the opposite sign. For
example, aluminium ion has a standard reduction value of -1.65V.

𝐴𝑙 3+ (aq) + 3e → Al(s) 𝐸 𝑂 𝑟𝑒𝑑 = −1.65𝑉

This means that the standard oxidation potential for aluminium metal is +1.65V.

Al(s) →𝐴𝑙 3+ (aq) + 3e 𝐸 𝑂 𝑜𝑥 = + 1.65V

The standard cell potential (𝐸 𝑂 cell) is the sum of the standard oxidation and reduction
potentials as shown below:

𝐸 𝑂 cell = 𝐸 𝑂 𝑜𝑥 + 𝐸 𝑂 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 off 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 the place a strip of copper
into a copper (II) salt solution. The next step is 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 𝑂 𝑟𝑒𝑑 value for nickel ion is -0.26V and +0.34V for copper ion. This means that 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 now 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 parts of 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)
iron is being reduced. The metal strips are called electrodes. The electrode in the half-cell
where oxidation occurs is called the anode and the electrode in the half-cell where reduction
occurs is called the cathode.
The cell potential can be measured by connecting a voltmeter between the half-cells. If
you wanted to approximate what your 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.

𝐶𝑢 2+ (𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠) 𝐸 𝑂 𝑟𝑒𝑑 = +0.34𝑉

𝑁𝑖(𝑠) → 𝑁𝑖 2+ (𝑎𝑞) + 2𝑒 − 𝐸 𝑂 𝑜𝑥 = +0.26𝑉
For measurement taken under non-standard conditions, the Nernst equation is used to
calculate 𝐸𝑐𝑒𝑙𝑙 . The Nernst equation is:
𝑅𝑇 𝑅𝑇
𝐸 = 𝐸𝑂 − ln 𝑄 𝑂𝑅 𝐸 = 𝐸 𝑂 − 2.303 𝑙𝑜𝑔𝑄 (2)
𝑛𝐹 𝑛𝐹
Where F is Faraday constant. R the universal gas constant, n the number of electrons
transferred and Q is the reaction quotient. When R = 8.314 J𝐾 −1 𝑚𝑜𝑙 −1, T = 298 K and F =
96500 𝐶𝑚𝑜𝑙 −1, the equation becomes:
0.0591
𝐸 = 𝐸𝑂 − log Q (3)
𝑛
THERMODYNAMICS
The Gibbs Free Energy (G) is the function derived from enthalpy (H) and entropy (S). The
change in free energy (ΔG) is a composite function that gives a measure of the spontaneity
of reaction. If ΔG < 0, a reaction will occur spontaneously. If ΔG < 0, the reaction is not
spontaneous. If ΔG = 0, the system is at equilibrium. When the state changes at constant
temperature:
ΔG = ΔH – TΔS (4)

Where T is the absolute temperature in Kelvin

For a general reaction or process of A and B giving C and D:
aA + bB → cC + dD
the reaction quotient, Q, is:

[𝐶]𝑐 [𝐷]𝑑
Q= (5)
[𝐴]𝑎 [𝐵]𝑏

The ΔG of a process at any concentration of A, B, C and D, is given by:

ΔG = Δ𝐺 𝑜 + RT ln Q (6)

Where Δ𝐺 𝑜 is the change in free energy of the reaction under the defined standard
conditions of 1 atm and 1M concentration of reactants. ΔG is the observed change in free
energy at conditions other than standard. At equilibrium Q= 𝐾𝑒𝑞 . ΔG = 0. Under these
conditions Equation (6) becomes:
Δ𝐺 0 = - RT ln Q or Δ𝐺 0 = - RT ln K (7)
The cell potential of a redox process is related to the free-energy change as follows:

Δ𝐺 0 = −𝑛𝐹𝐸 𝑂 (8)

In this experiment, you will construct three electrochemical cells, a zinc-copper cell, an
iron-copper cell and an iron-zinc 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-reactions and the net reactions as well. The Gibbs
energy which is one of the thermodynamics functions also will be determined from the cell
potentials obtained.
APPARATUS
1. Test tubes
2. Pipettes
3. Standard flasks
4. High resistance voltmeter
5. Alligator clips
CHEMICALS

1. 0.5M potassium nitrate solution

2. 0.10M zinc (II) sulphate solution
3. 0.20M copper (II) sulphate solution
4. 0.5M iron (II) ammonium sulphate solution
5. Zinc metal strip
6. Copper metal strip
7. Iron strip
PROCEDURE
Prepare a Salt-bridge for each electrochemical cell by completely dipping a filter paper in
0.5M KN𝑂3 solution.
Part I: Constructing the zinc-copper electrochemical cell

1. Two clean test tube was filled to about 3⁄4 full with 0.10 M zinc (II) sulphate and 0.20 M
copper (II) sulphate solution.
2. Strips of zinc and copper was cleaned with steel wool.
3. The copper strip was clipped to one voltmeter terminal used an alligator clip and use
another alligator clip to connect the zinc strip to the other voltmeter terminal. The
copper strip was dipped in the test tube containing the copper solution and the zinc strip
in the test tube containing the zinc solution at the same time. Be sure that the wires do
no come in contact with the solution. Insert the salt-bridge, made earlier, into both test
tubs. The voltage was noted and the salt-bridge was removed immediately. If you have
negative reading on your voltmeter, reverse the connections to the metal strips and dip
salt bridge again.
4. Three readings of voltage were recorded and the anode and cathode of the cell was
identified.
5. The temperature at which the measurement is taken was recorded.
Part II: Constructing the iron-copper electrochemical cell

1. A clean test tube was filled with 3⁄4 full of 0.50 M iron (II) ammonium sulphate solution
into a clean test tube.
2. The iron strips were cleaned with steel wool. The iron strips were connected to one
terminal of the voltmeter as before. The copper strip from Part I attached to the other
terminal was kept.
3. The metal strips were dipped into the proper solution and connect them with the salt-
bridge as before. Three positive readings were recorded and the anode and cathode wad
identified.
4. The temperature at which the measurement is taken was recorded.
Part III: Constructing the iron-zinc electrochemical cell
1. Keeping the iron strip attached to the voltmeter, the copper strip in Part II was replaced
with the zinc strip Part I.
2. The metal strips were dipped into the proper solution and connect them with a new salt-
bridge. Three positive readings were recorded and the anode and cathode were
identified.
3. The temperature at which the measurement is taken was recorded.
CALCULATION
Calculation the standard cell at standard condition:
(I) zinc-copper Electrochemical Cell
𝑍𝑛 2+ (aq) + 2𝑒 − → Zn (s) 𝐸 𝑜 = - 0.76 V

𝐶𝑢 2+ (aq) + 2𝑒 − → Cu (s) 𝐸 𝑜 = + 0.34 V

𝐸 𝑜 cell = 0.34 V - (-0.76 V) = 1.10 V
(II) iron-copper Electrochemical Cell

𝐹𝑒 2+ (aq) + 2𝑒 − → Fe (s) 𝐸 𝑜 = - 0.44 V

𝐶𝑢 2+ (aq) + 2𝑒 − → Cu (s) 𝐸 𝑜 = + 0.34 V

𝐸 𝑜 cell = 0.34 V - (-0.44 V) = 0.78 V

(III) iron-zinc Electrochemical Cell
𝐹𝑒 2+ (aq) + 2𝑒 − → Fe (s) 𝐸 𝑜 = - 0.44 V

𝑍𝑛2+ (aq) + 2𝑒 − → Zn (s) 𝐸 𝑜 = - 0.76 V

𝐸 𝑜 cell = -0.44 V - (-0.76 V) = 0.32 V

Write the cell symbol/cell notation

(I) zinc–copper Electrochemical Cell
Zn(s) I 𝑍𝑛 2+ (aq,0.10 M) I 𝐾𝑁𝑂3 I 𝐶𝑢 2+ (aq,0.20M) I Cu(s)

(II) iron-copper Electrochemical Cell

Fe(s) I 𝐹𝑒 2+ (aq,0.50M) I 𝐾𝑁𝑂3 I 𝐶𝑢 2+ (aq,0.20M) I Cu(s)

(III) iron-zinc Electrochemical Cell

Zn(s) I 𝑍𝑛 2+aq,0.10M) I 𝐾𝑁𝑂3 I 𝐹𝑒 2+ (aq,0.50M) I Fe(s)
Calculation of the 𝑬𝒐 cell from the experimental data
(I) zinc–copper Electrochemical Cell
0.0591
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 - log Q
𝑛

0.0591 [𝑍𝑛 2+]

1.081 = 𝐸 𝑜 - log
2 [𝐶𝑢 2+ ]

0.0591 [0.1]
1.081 = 𝐸 𝑜 - log [0.2]
2

0.0591 [0.1]
𝐸 𝑜 = 1.081 + log [0.2]
2

𝐸 𝑜 = 1.07 V

(II) iron-copper Electrochemical Cell

0.0591
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 - log Q
𝑛

0.0591 [𝐹𝑒 2+ ]
0.67 = 𝐸 𝑜 - log
2 [𝐶𝑢 2+ ]

0.0591 [0.5]
0.67 = 𝐸 𝑜 - log [0.2]
2

0.0591 [0.5]
𝐸 𝑜 = 0.67 + log [0.2]
2

𝐸 𝑜 = 0.68 V

(III) iron-zinc Electrochemical Cell

0.0591
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 - log Q
𝑛

0.0591 [𝑍𝑛 2+]

0.41 = 𝐸 𝑜 - log
2 [𝐹𝑒 2+ ]

0.0591 [0.1]
0.41 = 𝐸 𝑜 - log [0.5]
2

0.0591 [0.1]
𝐸 𝑜 = 0.41 + log
2 [0.5]

𝐸 𝑜 = 0.39 V

Half reaction and electrode potential value

(I) zinc–copper Electrochemical Cell

Oxidation (anode) = 𝑍𝑛2+ (aq) + 2𝑒 − → Zn (s) 𝐸 𝑜 = - 0.76 V

Reduction (cathode) = 𝐶𝑢2+ (aq) + 2𝑒 − → Cu (s) 𝐸 𝑜 = + 0.34 V

Overall reaction = Zn (s) + 𝐶𝑢2+ (aq) → 𝑍𝑛2+ (aq) + Cu (s)

(II) iron-copper Electrochemical Cell

Oxidation (anode) = 𝐹𝑒 2+ (aq) + 2𝑒 − → Fe (s) 𝐸 𝑜 = - 0.44 V

Reduction (cathode) = 𝐶𝑢2+ (aq) + 2𝑒 − → Cu (s) 𝐸 𝑜 = + 0.34 V

Overall reaction = Fe (s) + 𝐶𝑢2+ (aq) → 𝐹𝑒 2+ (aq) + Cu (s)

(III) iron-zinc Electrochemical Cell

Oxidation (anode) = 𝐹𝑒 2+ (aq) + 2𝑒 − → Fe (s) 𝐸 𝑜 = - 0.44 V

Reduction (cathode) = 𝑍𝑛2+ (aq) + 2𝑒 − → Zn (s) 𝐸 𝑜 = - 0.76 V

Overall reaction = Zn (s) + 𝐹𝑒 2+ (aq) → 𝑍𝑛2+ (aq) + Fe (s)

Calculation of the Δ𝑮𝑶 from the experimental data

(I) zinc–copper Electrochemical Cell

Δ𝐺 𝑂 = − 𝑛𝐹𝐸 𝑜

= - (2)(96500)(1.07)

= - 206510 J

= -206.51 kJ

(II) iron-copper Electrochemical Cell

Δ𝐺 𝑂 = − 𝑛𝐹𝐸 𝑜

= - (2)(96500)(0.68)

= - 131240 J

= - 131.24 kJ

(III) iron-zinc Electrochemical Cell

Δ𝐺 𝑂 = − 𝑛𝐹𝐸 𝑜

= - (2)(96500)(0.39)

= - 75270 J

= -75.27 kJ

Calculate the equilibrium constant K.

(I) zinc–copper Electrochemical Cell
[𝑍𝑛2+ ]
K = [𝐶𝑢2+]

0.1
=
0.2

= 0.5
(II) iron-copper Electrochemical Cell
[𝐹𝑒 2+ ]
K = [𝐶𝑢2+]

0.5
=
0.2

= 2.5

(III) iron-zinc Electrochemical Cell

[𝑍𝑛2+ ]
K = [𝐹𝑒 2+]

0.1
=
0.5

= 0.2

DISCUSSION

CONCLUSION

The electrochemical cells has been constructed and the net cell potentials for three electrochemical
cell has been determined. The net cell potential that obtained from the experiment for Zinc-copper
cell is E° cell =+ 1.07 V, for iron-copper cell is E° cell =+0.68 V and iron-zinc cell is E° cell= +0.39 V. The
Gibbs energy for zinc-copper cell ∆G is -206.51 kJ, for iron-copper cell is - 131.24 kJ and iron-zinc cell
is -75.27 kJ
REFERENCES

1. AnonymousLibreTexts, Anonymous, LibreTexts, & Author Anonymous. (2020,

August 11). Unit 7: Thermodynamics & Electrochemistry. Chemistry LibreTexts.
https://chem.libretexts.org/Courses/Howard_University/General_Chemistry%3A_An_At
oms_First_Approach/Unit_7%3A_Thermodynamics_and_Electrochemistry
2. Thermodynamics of a galvanic cell - lublin. (n.d.).
http://www.katedrachf.umcs.lublin.pl/cwiczenia/Ang/PhysChem/Cw-3.pdf

QUESTION

1. What is the reason for using a salt bridge?

= Salt bridge used for connecting the half-cell of oxidation and reduction. Salt bridge help
maintaining the electrical neutrally in the circuit.
2. Calculate the standard cell potential of a cell constructed from 𝑀𝑔2+ /Mg and 𝑁𝑖 2+ /Ni. Which is
the anode and which is cathode?

Anode: 𝑀𝑔2+ /Mg 𝐸 𝑜 = -2.37V

Cathode: 𝑁𝑖 2+ /Ni 𝐸 𝑜 = -0.26V

𝐸 𝑜 𝑐𝑒𝑙𝑙 = 𝐸 𝑜 (cathode) - 𝐸 𝑜 (anode)

= - 0.26 –(-2.37)

= + 2.11V

3. Using the Nerst Equation, what would be the potential of a cell with [𝑁𝑖 2+ ] = [𝑀𝑔2+ ] = 0.10M ?
0.0591 0.1
𝐸𝑐𝑒𝑙𝑙 = 2.11 - log 0.1
2

= 2.11V

4. What is the information deduced from the sign and magnitude of ∆𝐸 and ∆𝐺 from this
experiment?
= If 𝐸 𝑜 𝑐𝑒𝑙𝑙 > 0, then ∆𝐺 is negative and the reaction is spontaneous. This is the principle of
galvanic cell where chemical energy is converted to electrical energy. Electrons supplied by
electrodes move in external circuit.