Module CCE 1102 Physical Theory

Data Sheet Experiment P4

Electrochemical Cells

Experimental Stage 1.
Complete the following table. Solution Temperature = 25oC/298K

Table 1.

Anode solution Cathode Cell voltage Cell voltage

solution (experimental) (theoretical)
[Zn2+]
[Cu2+]

+1.10
1M 1M +1.06

+1.07
1M 10–1 M +1.03

+1.04
1M 10–2 M +1.02

+1.01
1M 10–3 M +1.00

+0.98
1M 10–4 M +0.99
 Module CCE 1102 Physical Theory

Use the Nernst equation to calculate the theoretical cell voltage (Ecell) for each of the
assembled cells:

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 Module CCE 1102 Physical Theory

2. Plot a single graph of cell voltage, Ecell in volts, (y-axis) versus ln{[Zn2+]/[Cu2+]}
(x-axis), overlapping results for both i) the experimental and ii) theoretical values.
Determine the best straight-line and evaluate the slope, the intercept and regression
analysis (R2) values for each set of results.

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Intercept Slope R2

Experimental 137.69/130.48=1.055 -130.48 0.9633

Theoretical 84.428/76.753=1.1 -76.753 1

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 Module CCE 1102 Physical Theory

a) Write the balanced redox reaction between the copper and zinc species in the
electrochemical cell. What is the direction of spontaneous change for the redox
reaction, justifying your answer with reference to ΔG for the process (hint: relate
ΔG to Eºcell)?

Zn2+(aq) + 2e- —-> Zn(s) E0 = +0.76V

+
Cu(s) —-> Cu2+(aq) + 2e- E0 = +0.34V
—————————————————————
Zn(s) + Cu2+(aq) —-> Zn2+(aq) +Cu(s) Eºcell = +1.10V

ΔG = -nFEºcell = -(2 mol of e-)(96485J)(1.10V) = -212.267kJ/mol

The direction of spontaneous change is Left to Right as the Eºcell is positive and
ΔG is negative. The opposite direction would mean that Eºcell = -1.10V and ΔG
= +212.267kJ/mol therefore reaction will not be feasible as for a spontaneous
redox reaction to occur ΔG must be negative and Eºcell must be positive.
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b) Comment on the slope and the intercept values obtained from the graph for
experimental results for the Zn/Cu cell. Suggest two reasons for any deviation(s)
from theoretical values observed.

The slope of the experimental values is roughly 58% steeper compared to the slope
of the theoretical values. The intercept of the experimental values is 0.045 less than
the theoretical values. The reason for deviation from the theoretical values may be
due to internal resistance being caused due to differences in cell from age, size or
temperature. Also if is very difficult to ensure conditions are completely standard,
different pressures, temperatures and concentrations can result in lower
experimental values. The theoretical values are measured under ideal standard
 Module CCE 1102 Physical Theory

conditions (25oC, 1 bar and 1.00M concentration of aqueous ions) for a new unused
cell, if the electrodes are not clean with a fresh metal surface , there may be an
oxide layer that can interfere with the reaction.

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Experimental Stage 2.

Table 2.

Cell Anode reaction Cathode reaction Cell voltage (Ecell)

(Reduction) (Oxidation)

1 Cu2+(aq) +2e- —>Cu(s) Zn(s) —>Zn2+(aq)+2e

+0.99

2 Cu2+(aq) +2e- —>Cu(s) Sn(s) —> Sn2+(aq) +2e

+0.48

3 Cu2+(aq) +2e- —>Cu(s) Mg(s) —>Mg2+(aq)+2e

+1.73
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Table 3.

Mg / Cu lemon battery Observed cell voltage (Ecell)

Lemon Cell 1
+1.697
Lemon Cell 2
+1.789
Lemon Cell 3
+1.730
Lemon Cell 4
+1.730
 Module CCE 1102 Physical Theory

Predicted Battery Pack Voltage

+6.946
(Cell 1 + Cell 2 + Cell 3 +Cell 4)

Observed Battery Pack Voltage

+6.780

3 (a) Comment on trend of cell voltage values obtained in Table 2. Use ‘the
electrochemical series’ to support your answer.

The cell voltages decrease as the Standard Electrode Potentials of the

Cathode half-cell become more positive.
Mg2+(aq)+2e- —> Mg(s) Eo= -2.38V
Zn2+(aq)+2e- —> Zn(s) Eo= -0.76V
Sn2+(aq) +2e- —>Sn(s) Eo= -0.14V
As values for the reduction become more positive they become a weaker
reducing agent, therefore electrons are lost more readily from Mg2+(aq)
than Sn2+(aq). Oxidation reactions are reversed so the more -ve reduction
half equation will result in a more +ve oxidation half equation, creating a
greater cell voltage.

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(b) Write overall chemical equations, standard cell voltage (E°cell) and
corresponding Nernst equations for each of the cells (assume 1bar
atmospheric pressure):
 Module CCE 1102 Physical Theory

Cel Overall reaction E°cell Nernst Eqn.

l

Cu2+(aq) +Zn(s) —>Cu(s) + Zn2+(aq) +1.10V Ecell=1.10 - 0.0296*log10([Zn2+]/[Cu2+])

1

Cu2+(aq) +Mg(s) —>Cu(s) + Mg2+(aq) +2.72V Ecell=2.72 - 0.0296*log10([Mg2+]/[Cu2+])

2

Cu2+(aq) +Sn(s) —>Cu(s) + Sn2+(aq) +0.48V Ecell=0.48 - 0.0296*log10([Sn2+]/[Cu2+])

3

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(c) Considering that lemon juice pH = 2, use the Nernst equation to estimate the
molar concentrations for Zn2+ ions formed when the electrodes are placed into
the lemon (hint: first relate pH to [H+]):
 Module CCE 1102 Physical Theory

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(d) Compare the ‘observed’ to ‘predicted’ battery pack voltage values. Suggest
one reason for any deviation observed.
Deviation can result from a surface coating of oxide on metals. If metal is not
sufficiently sanded or contains some impurities it can cause a deviation
between the observed and predicted values. Resistance withinin the wires
can also cause deviation and the more lemons added to the circuit will mean
the current has to travel through a greater distance of resistance, resulting in
a more inaccurate result between observed and predicted voltage values.

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