Experiment 1: Galvanic and Electrolytic Cells

Objectives:

a) To distinguish between galvanic and electrolytic cells.

b) To measure the relative reduction potentials for a number of redox couples in a galvanic cell.
c) To develop an understanding of the movement of electrons, anions and cations in a galvanic
cell.
d) To identify the reactions occurring at the anode and cathode during the electrolysis of various
aqueous salt solutions.

Introduction:

Chemical reactions occurred involving the transfer of electrons from one reactant to another
reactant called oxidation – reduction reactions or redox reactions. In this reaction, two half-reactions
will occur where one reactant loss electrons which undergo oxidation and another reactant gain
electrons which undergo reduction. In a spontaneous reaction, electrons flow from oxidized reactant
(reducing agent) to the reactant that is reduced (oxidizing agent). These half reactions will be separated
by a wire, this flows of electrons instead occurring at the surface of metal, it will occurs through the
external wire and electric current is generated. This is called as galvanic cell and it showed exactly how
batteries work.

In this experiment, we will measure the voltage of a few voltaic cells such as zinc, magnesium,
iron and copper. A typical voltaic cell consists of two half cells linked by a wire and a salt bridge. Each
half-cell consists of a metal electrode in contact with solution containing a salt of that metal. One is
anode where oxidation takes place and another one is cathode where reduction takes place. Electrons
flow from anode to cathode via wire and the salt bridge allows the migration of ions to prevent the
imbalance charge from building up as electrons leave from anode to the cathode. Using a voltmeter, it
will permit a measurement of voltage or potential difference between half-cell.
Methods:

A. Galvanic Cell – Reduction Potentials of Several Redox Couples.

1. Copper, zinc, magnesium and iron is polished with emery paper or steel wool before used as
electrodes and put in their respective beakers.
2. Then briefly rinsed using 1 M HNO3 and rinsed again with deionized water.
3. To set up the copper/zinc cell:
a. Cu strip (electrode) is placed in the Cu(NO3)2 solution and Zn strip (electrode) in the
Zn(NO3)2 solution.
b. A salt bridge is prepared by rolling a piece of filter paper.
c. Then the filter paper is wetted with 0.1 M KNO3 solution.
d. After that, folded the filter paper and the end of it is inserted into the salt solutions.
e. New salt bridge is prepared for each galvanic cell.
f. One electrode is connected to negative terminal of the potentiometer and one
another to the positive terminal.
4. If the voltmeter read a negative potential, the connections is reversed.
5. The positive cell potential is recorded.
6. The metal strips that serve as cathode (positive) and anode (negative) is identified.
7. These steps are repeated for another four redox couples.
B. Electrolytic Cell – Electrolysis of Aqueous Salt Solutions.

Solution Electrodes
2 g NaCl / 100 mL Carbon (graphite)
2 g NaBr / 100 mL Carbon (graphite)
0.1 M CuSO4 Carbon (graphite)
0.1 M CuSO4 Polished Copper Metal Strips

1. Two wire leads is connected with different colors attached to alligator clips to a direct current
power supply.
2. Then, a glass U-tube is mounted on a ring stand or clamp at a retort stand.
3. The alligator clips are connected to the responding electrodes.
4. The U-tube is filled ¾ with the solutions in Table 1 and is electrolyzed for 5 minutes using the
suggested electrode.
5. During electrolysis, any evidences of reaction in anode and cathode are recorded.
a. pH changed is tested using litmus and the color changed is compared with original
solution.
b. Gas evolved at either or both electrodes?
c. Is a metal depositing or slowly disappearing on the electrode?
Data & Results:

A. Galvanic Cell – Reduction Potentials of Several Redox Couples.

Galvanic Measured Equation for Equation for

Anode Cathode
cell E˚cell (V) anode reaction cathode reaction
Cu – Fe 0.778 Fe Fe → Fe2+ + 2e- Cu Cu2+ + 2e- → Cu
Zn – Fe 289.0 mV Zn Zn → Zn2+ + 2e- Fe Fe2+ + 2e- → Fe
Cu – Mg 1.628 Mg Mg → Mg2+ + 2e- Cu Cu2+ + 2e- → Cu
Fe – Mg 1.153 Mg Mg → Mg2+ + 2e- Fe Fe2+ + 2e- → Fe
Zn – Mg 0.877 Mg Mg → Mg2+ + 2e- Zn Zn2+ + 2e- → Zn
Table 1

Write the overall equations for the six cell reactions.

Galvanic cell Overall Equation

Cu – Fe Cu2+ + Fe → Cu + Fe2+
Zn – Fe Zn + Fe2+ → Zn2+ + Fe
Cu – Mg Cu2+ + Mg → Cu + Mg2
Fe – Mg Fe2+ + Mg → Mg2+ + Fe
Zn – Mg Zn2+ + Mg → Zn + Mg2+
Table 2

Reduction Potential.

Reduction Reduction % Error

Redox Couple Potential potential 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 − 𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑
𝑥 100%
(Measured) (Calculated) 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑
Cu – Fe 0.778 0.78 0.26
Zn – Fe 289.0 mV 0.35 17.43
Cu – Mg 1.628 2.71 39.93
Fe – Mg 1.153 1.93 40.26
Zn – Mg 0.877 1.58 44.49
Table 3
 B. Electrolytic Cell – Electrolysis of Aqueous Salt Solutions.

Gas
Solutions Electrodes Litmus test Equation for reactions
evolved
Anode: 2Cl- → Cl2 + 2e-
NaCl C (gr) No changes Yes Cathode: 2H+ + 2e- → H2
Overall: 2Cl- + 2H+ → Cl2 + H2
Anode: 2Na → 2Na+ + 2e-
NaBr C (gr) Blue → Red Yes Cathode: Br2 + 2e- → 2Br-
Overall: 2Na + Br2 → 2Na+ + 2Br-
Anode: SO2 + H2O → SO42- + 4H+ + 2e-
CuSO4 C (gr) Blue → Red Yes Cathode: Cu2+ + 2e- → Cu
Overall: SO2 + H2O + Cu2+ → SO42- + 4H+ + Cu
Anode: Cu → Cu2+ + 2e-
CuSO4 Cu (s) Blue → Red No Cathode: Cu2+ + 2e- → Cu
Overall: Cu + Cu2+ → Cu2+ + Cu
Table 4

Calculations:

Reduction Potential Reduction potential

(Measured) (Calculated)
Redox Couple Ecell = E˚cell – Ecell = E˚cell –
𝑅𝑇 𝑅𝑇
𝑛𝐹
(ln Q) (V) 𝑛𝐹
(ln Q) (V)
Cu – Fe Ecell = 0.778 – 0 = 0.778 Ecell = 0.78 – 0 = 0.78
Zn – Fe Ecell = 289.0 mV – 0 = 289.0 Ecell = 0.35 – 0 = 0.35
Cu – Mg Ecell = 1.628 – 0 = 1.628 Ecell = 2.71 – 0 = 2.71
Fe – Mg Ecell = 1.153 – 0 = 1.153 Ecell = 1.93 – 0 = 1.93
Zn – Mg Ecell = 0.877 – 0 = 0.877 Ecell = 1.58 – 0 = 1.58
Table 5

Galvanic cell Calculated : E˚cell = Ecathode – Eanode (V)

Cu – Fe 0.34 – (-0.44) = 0.78
Zn – Fe -0.44 – (-0.79) = 0.35
Cu – Mg 0.34 – (-2.37) = 2.71
Fe – Mg -0.44 – (-2.37) = 1.93
Zn – Mg -0.79 – (-2.37) = 1.58
Table 6
Discussion:

Electrochemical cells work based on oxidation – reduction reactions. When oxidation and
reduction occurs, the electrons will move where the movement of electrons is based on electricity. This
movement can be measured with a voltmeter as it produces voltage. Oxidation involved losing an
electron while reduction involved in gaining electron. The anode is reducing agent and the cathode is
oxidizing agent. Electrons will flow from anode to cathode accordingly to show that the reaction is
spontaneous. This spontaneity will indicate that the cell potential is positive.

Electrolytic cells are very similar to voltaic (galvanic) cells in the sense that both require a salt
bridge, both have a cathode and anode side, and both have a consistent flow of electrons from the
anode to the cathode. Electrolytic cell converts electrical energy into chemical energy. The redox
reaction is not spontaneous as the electrical energy has to be supplied into the reaction. Here, the
anode is positive (oxidation) and the cathode is negative (reduction).

In this experiment, we are using zinc, magnesium, copper and iron as an electrode. These
electrodes are paired up as a redox couple such as copper – magnesium, zinc – iron and much more. The
reduction potential measured in the experiment is shown as in Table 1 and Table 3 for galvanic cell.
Table 4 indicates the result for experiment 1 B for electrolytic cell. The electrode is undergoing similar
reaction but in two differ concentrations. Due to this differ, there is differ in voltage. At the anode,
copper atoms dissolve into solution and give up electrons while at cathode, copper ions deposit at
electrode and acquire electrons. With the gradual discharge of ions at the electrodes, the undischarged
ion that remains in solution is responsible for changing the pH. As you can see in NaCl solution, the
hydrogen and chloride ions discharge at negative and positive electrodes respectively, leaving behind
sodium and hydroxide ions. These then combine to form sodium hydroxide a strong base which
increased pH of solution and changed the litmus paper color.

The most common error in this experiment is the measurement of voltage which was measured
incorrectly due to improper voltmeter use. Another error is made sure to wet the salt bridge in the KNO3
solution before recording the voltmeter reading.

Conclusion:

We are able to distinguish between galvanic and electrolytic cells and also able to measure the
relative reduction potentials for a number of redox couples in galvanic cell.
Questions:

1. Compare the sum of Zn-Mg and Cu-Mg cell potentials with Zn-Cu cell potential.
a. Cell potential of Zn-Mg = 0.877 V
Cell potential of Cu-Mg = 1.628 V
b. Sum of Zn-Mg & Cu-Mg = 2.505 V
c. Cell potential Zn-Cu = 0.455 V
d. The sum value is higher than Zn-Cu potential by 2.05 V.

2. Compare the sum of Zn-Fe and Zn-Mg cell potentials with the Fe-Mg cell potential.
a. Cell potential of Zn-Fe = 289.0 mV
Cell potential of Zn-Mg = 0.877
b. Sum of Zn-Fe & Zn-Mg = 1.166 V
c. Cell potential of Fe-Mg = 1.153
d. The sum value is slightly higher than Fe-Mg potential by 0.013 V.

3. If copper electrodes had been used instead of the carbon (graphite) electrodes for all of the
electrolytic cells, the observed may have been different. Why?
Carbon electrode is an inert electrode, thus it will not compete with the ions present in
the solutions. By replacing carbon with copper which is not an inert electrode, it will undergo
erosion or electrodeposition instead of producing gas at the electrode.

4. In the electrolysis of an aqueous salt solution, the nitrate ion NO-3, migrates to the anode.
Considering that the nitrogen in the nitrate ion (aq) is at its maximum oxidation state (of +5),
what electrolysis product(s) might you expected to observe at the anode?
Based on the electrochemical series, NO-3 won’t be discharge because it is located at the
upper top while OH- located at the bottom. Hence, expected product would be oxygen gas.
O2+ 4H+ + 4e- → 2H2O
References:

1. Electrochemistry. Retrieved September 29, 2017 from

https://www.lahc.edu/classes/chemistry/arias/Lab7Electrosp11.pdf
2. Electrolytic cells. Retrieved September 29, 2017 from
https://chem.libretexts.org/Core/Analytical_Chemistry/Electrochemistry/Electrolytic_Cells
3. Experiments in Electrochemistry. Retrieved September 29, 2017 from
http://www.funsci.com/fun3_en/electro/electro.htm
4. Galvanic cell. Retrieved September 29, 2017 from
https://www.uccs.edu/Documents/chemistry/nsf/106%20Expt9V-GalvanicCell.pdf
5. How does pH change during electrolysis? Retrieved September 29, 2017 from
https://socratic.org/questions/how-does-ph-change-during-electrolysis