Electrochemistry --

Electrochemistry
Voltaic Cells
Voltaic Cells

Chemicals Apparatus
Beaker
Cu strip
Multimeter
CuSO4 solutions
Salt bridge
Zn strip
Test tubes
ZnSO4 solutions
Pipette

OBJECTIVE
In this experiment the students will learn how to construct a voltaic cell to convert
chemical energy into electrical energy. The students will also learn how to measure the cell
voltage of the voltaic cell prepared using solutions with different concentrations.
Moreover, they will learn how to construct a concentration cell.

THEORY
Electrochemistry is the area of chemistry that deals with the relations between chemical
changes and electrical energy. Chemical reactions involving the transfer of electrons from
one reactant to another are called oxidation-reduction reactions or redox reactions. In a
redox reaction, two half-reactions occur; one reactant gives up electrons (undergoes
oxidation) and another reactant gains electrons (undergoes reduction).

A voltaic (galvanic) cell is a device that produces an electric current as the result of a
spontaneous electron transfer reaction. However, in an electrolytic cell, a non-spontaneous
reaction is forced to occur by application of an external voltage.

In order to generate electricity from the electron transfer during a redox reaction and to
covert chemical energy into electrical energy, the redox reactions has to be separated into
two different compartments. In such a redox reaction, oxidation reaction occurs at the
anode and the reduction reaction occurs at the cathode. Electrons flow spontaneously from
the negative anode to the positive cathode due to the potential differences between the
anode and cathode side. Here, the electrons flow from higher potential energy to lower
potential energy side spontaneously. The electrical circuit is completed by the movement

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of ions through a salt bridge or a membrane. A salt bridge contains an electrolyte solution
whose ions will not react with other ions in the cell or with the electrode material but
counter balance the solutions are the redox reactions take place.

Electrons that are generated at the anode of an electrochemical cell are driven toward the
cathode by a thermodynamic tendency called the electromotive force (emf), measured in
volts. The emf is also called the cell potential and depends on both the identities of the
substances involved in the redox reactions as well as their concentrations. Under standard
conditions (25 0C, 1 atm, and 1.0 M for both the anode and cathode solutions) the cell
potential is equal to

° ° °
𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐨𝐱𝐢𝐝𝐚𝐭𝐢𝐨𝐧 + 𝐄𝐫𝐞𝐝𝐮𝐜𝐭𝐢𝐨𝐧

Oxidation (anode) : Zn(s) → Zn2+ (aq) + 2e− Eoxº = 0.76 V

Reduction (cathode) : Cu2+ (aq) + 2e− → Cu(s) Eredº = 0.34 V
Overall reaction : Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Eºcell = 1.10 V

The maximum amount of work, wmax that can be obtained from a galvanic cell is equal to
the change in Gibbs free energy, G, for the process;

𝐰𝐦𝐚𝐱 = 𝚫𝐆 = −𝐧. 𝐅. 𝐄𝐜𝐞𝐥𝐥

where

 n is the number of electrons transferred

 F is Faraday’s constant, 1F = 96500 C

The change in Gibbs free energy can be used to derive a relation between the cell potential,
the concentration of the reactants and products, and the temperature.

𝚫𝐆 = 𝚫𝐆° + 𝐑𝐓 𝐥𝐧 𝐐

where

 Q is the reaction quotient (Q= anode/cathode)

 R is the gas constant, R= 8.314 Jmol-1K-1
 T is room temperature, T=298 K

Substituting 𝜟𝑮 = −𝒏. 𝑭. 𝑬𝒄𝒆𝒍𝒍 in the above equation, the Nernst equation is obtained. The
Nernst equation is useful in calculation of cell potential or concentration of the anode
and/or cathode solutions under non-standard conditions.

° 𝟎. 𝟎𝟓𝟗𝟐
𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐞𝐥𝐥 − 𝐥𝐨𝐠 𝐐
𝐧

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A voltmeter is inserted in the circuit to measure the cell voltage. The value of the voltage
or the electromotive force (emf), can be regarded as a quantitative measure of the tendency
for electrons to flow in the cell, in other words the tendency for the electrons to be
transferred from one reactant to the other.

Example 12.1

Calculate the cell potential for the following cell,

Zn l Zn2+ (0.75M) ll Cu2+ (0.20M) l Cu

Given the following:
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Eºcell = 1.10 V

Solution

° 0.0592
Ecell = Ecell − log Q
n
0.0592 0.75
= 1.10V − log
2 0.20

= 1.10 - 0.017

= 1.083 V

In this experiment, a Cu / Zn voltaic cell with the following net cell reaction will be used to
generate electrical energy. The overall reaction can be divided into two half-cell reactions,
an oxidation and a reduction halves, each one having a different electrode (by convention,
the electrode potentials are always given for reduction reactions). The species with half-
cell reactions that have more positive value of the reduction potentials have greater
tendency to be reduced.

Figure 12.1 Schematic representation of the voltaic cell to be constructed

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The cell consists of the following parts:

1. A Zn strip (gray) immersed in ZnSO4 solution (colorless)

2. A Cu strip immersed in CuSO4 solution (blue)
3. A salt bridge constructed from a U-tube filled with concentrated and solidified
K2SO4.
4. A pair of wire with crocodile ends and banana plugs at each end in order to attach
metal strips to voltmeter terminals.

Concentration Cells

Since cell potential depends not only on the half-reactions occurring in the cell, but also on
the concentrations of the reactants and products in those half reactions, it is possible to
construct a voltaic cell in which both half reactions are the same, but there is a difference
in their concentration, which drives the current flow due to the chemical potential
differences.

In a concentration cell, electrons spontaneously flow from the half-cell with the lower
concentration (anode) to the half-cell with the higher concentration (cathode) until the
concentrations becomes the same in the both half cell.

Consider the electrochemical cell in which zinc metal is oxidized at the anode and zinc
ions are reduced at the cathode. Since the half-reactions are identical, the standard cell
potential, Eºcell, is zero.

Oxidation (Anode) : Zn(s) → Zn2+ (aq) + 2e− Eº = 0.76 V

Reduction (Cathode) : Zn2+ (aq) + 2e− → Zn(s) Eº = - 0.76 V

Overall reaction : Zn(s) + Zn2+ (aq)(cathode) → Zn2+ (aq)(anode) + Zn(s)

° ° °
Ecell = Eoxidation + Ereduction = 0.00 V

Because of the different concentrations in the two half-cells, the cell potential, Ecell, is
calculated using the Nernst equation:

° 𝟎. 𝟎𝟓𝟗𝟐 [𝐙𝐧𝟐+ ]𝐚𝐧𝐨𝐝𝐞

𝐄𝐜𝐞𝐥𝐥 = 𝐄𝐜𝐞𝐥𝐥 − 𝐥𝐨𝐠
𝐧 [𝐙𝐧𝟐+ ]𝐜𝐚𝐭𝐡𝐨𝐝𝐞

The formation of Zn2+ ions in the dilute half-cell creates electrons. These electrons flow to
the more concentrated cell side through the external wire, where they react with Zn2+ ions
and reduce them to Zn(s). This process continues until the concentration of Zn2+ ions
becomes the same in both cells by which the cell potential becomes zero (0). Thus the
highest cell potential is observed when the concentration difference is the highest, which is
at the beginning. Then it decreases to zero as the concentrations in both half-cells becomes
equal.

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PROCEDURE
The instrument employed for measuring emf and the cell potential, is called a multimeter,
which is a digital instrument capable of performing multi-purpose measurements such as
resistance, voltage difference, and current. When the wires are connected to the electrodes,
the voltage generated by the cell can be read directly.

For the construction of Cu / Zn voltaic cell, connect the Cu electrode (cathode) to the V/Ω
terminal of the multimeter and connect the Zn electrode (anode) to the COM terminal of
the multimeter. Adjust the voltage scale to the millivolt scale because of the low voltage
difference that you will read. If the wires are connected in reverse, a negative value on the
multimeter will be displayed. This information can also be used to determine which
electrode is cathode and which electrode is the anode, and consequently in which direction
electrons flow through the external cell circuit.

Salt bridge
Zn strip Cu strip

Multimeter

ZnSO4 solution CuSO4 solution

Figure 12.2 Experimental set-up of the voltaic cell to be constructed

A. Cell Voltage

1. Take 6 clean test tubes.

2. Transfer about 25 mL of 0.50 M CuSO4 into a beaker.

3. Take 15 mL of 0.50 M CuSO4 from this beaker, using a pipette and transfer into a clean
test tube. Label it as “A”.

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4. Take 7.5 mL of 0.50 M CuSO4 from the beaker, using a pipette, and transfer into
another clean beaker and dilute it to 15 mL with distilled water. Transfer this into a
clean test tube and label it as “B”.

5. Take 1.5 mL of 0.50 M CuSO4 from the beaker using a pipette, transfer into another
beaker and dilute it to 15 mL with distilled water. Transfer it into a test tube and
label it as “C”.

6. Repeat the procedure from 2 to 5 for 0.50M ZnSO4. Label the solutions as “D”, “E”
and “F”.

7. At the end, you will have three CuSO4 solutions and three ZnSO4 solutions with
different concentrations.

8. Take test tube “A” containing CuSO4. Bend a sandpapered Cu strip and hang over the
side of the test tube so that it is partly immersed in the solution.

9. Bend the Zn strip and hang it over the side of the test tube “D” containing ZnSO4.

10. Use the crocodile clips to connect the terminals of the multimeter to the metal
electrodes.

11. Construct the salt bridge as described above (Figure 12.2) and immediately read the
initial cell voltage.

WARNING
Immerse the salt bridge as a final step to complete the circuit, then read the
voltage difference.

Dispose your waste into the aqueous waste container.

B. Concentration Effects on Cell Voltage

In order to observe the effect of concentration on the cell voltage, the concentration of the
salt solution in one of the compartments will be changed either by adding successive
amounts of salt or by dilution. In this experiment, dilution of the solution is chosen.

1. Measure the cell potential, Ecell, using the solutions given in Table 12.1 and determine
the effect of concentration change on the cell potential. Write the results in Table 2 in
your report sheet.

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 Table 12.1. Cells constructed for measuring Ecell.

Exp Cu2+(M) Zn2+(M)

1 A D
2 B D
3 C D
4 A E
5 A F
6 C E

C. Concentration Cell

1. Take 3 clean test tubes.

2. Transfer about 25 mL of 2.0 M ZnSO4 into a beaker.

3. Take 15 mL of 2.0 M ZnSO4 from this beaker, using a pipette and transfer into a clean
test tube. Label it as “G”.

4. Take 7.5 mL of 2.0 M ZnSO4 from the beaker, using a pipette, and transfer into
another clean beaker and dilute it to 15 mL with distilled water. Transfer this into a
clean test tube and label it as “H”.

5. Take 1.5 mL of 2.0 M ZnSO4 from the beaker using a pipette, transfer into another
beaker and dilute it to 15 mL with distilled water. Transfer it into a test tube and label
it as “I”.

6. Construct a cell using two zinc strips and two ZnSO4 solutions.

7. Vary the solutions as given in Table 12.2 to construct concentration cells and measure
the cell potential, Ecell.

Table 12.2. Concentration cells constructed

Exp Zn2+ (anode) Zn2+(cathode)

1 H G
2 I G
3 I H

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 CALCULATIONS

A. Cell Voltage
1. Calculate the concentrations of the solutions in test tubes A-F.
2. Write the cathode and anode half reactions and the overall reaction.

B. Concentration Effects on Cell Voltage

1. For the cells given in Table 12.1, calculate Ecell (calculated) using the Nernst
equation and the standard cell potential Eºcell, and then calculate wmax.
Complete Table 1 in your report sheet.

2. Calculate wmax and standard cell potential Eºcell using the experimental Ecell
values by using Nernst equation and compare it with the theoretical value.
Complete Table 2 in your report sheet.

3. Calculate the % error in Ecell and wmax in your measurement for one set of
data.

𝐞𝐱𝐩𝐞𝐫𝐢𝐦𝐞𝐧𝐭𝐚𝐥 𝐯𝐚𝐥𝐮𝐞 − 𝐭𝐡𝐞𝐨𝐫𝐞𝐭𝐢𝐜𝐚𝐥 𝐯𝐚𝐥𝐮𝐞

% 𝐞𝐫𝐫𝐨𝐫 = 𝐱 𝟏𝟎𝟎
𝐭𝐡𝐞𝐨𝐫𝐢𝐭𝐢𝐜𝐚𝐥 𝐯𝐚𝐥𝐮𝐞

C. Concentration Cell

1. Calculate the theoretical cell potentials for each experiment and complete Table 3
in your report sheet.

2. Calculate the % error in Ecell.

Show all of your calculations on back page of the report sheet for one set of data
for each table, separately

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