2302103 General Chemistry Laboratory, Experiment 5: Redox Reactions, Galvanic Cells, and the Nernst Equation 5-1

EXPERIMENT 5
Redox Reactions, Galvanic Cells, and
the Nernst Equation
PURPOSE
1. To understand the fundamental concepts of redox reactions
2. To determine the relative reactivity of a series of metallic elements
3. To measure the relative reduction potentials of several redox couples in a galvanic cell
4. To develop an understanding of the movement of electrons, anions, and cations in a galvanic cell
5. To determine the concentration of ions in solution using the Nernst equation

PRE-LAB PREPARATION
Reduction–oxidation, or redox, reaction is a chemical reaction that involves the transfer of
electrons from one substance to another. One broad area of chemistry that deals with the study of these
reactions is called electrochemistry. A redox reaction can be divided into two half-reactions: reduction
and oxidation, hence the name. Each half-reaction consists of a redox couple, which contains the
reduced state and the oxidized state of the species. A solid piece of copper (Cu) dissolving into a solution
of copper ions (Cu2+) is an example of an oxidation.

Cu (s) Cu2+ (aq) + 2 e– (5-1)

reduced form oxidized form

The oxidation number of solid Cu is zero whereas the oxidation number of the aqueous Cu2+ ions is two.
During the reaction, the oxidation number goes up, indicating that the substance (Cu) loses its electrons.
Reduction is a process whereby a substance gains electrons but decreases in oxidation number. An
example of reduction is the formation of solid silver (Ag) from silver ions (Ag+) in solution.

Ag+ (aq) + e– Ag (s) (5-2)

oxidized form reduced form

When these two half-reactions (oxidation and reduction) are combined carefully to maintain both
mass and charge balance, the net redox reaction that occurs at the interface is:

Cu (s) + 2 Ag+ (aq) Cu2+ (aq) + 2 Ag (s) (5-3)

reductant oxidant
In a redox reaction, electrons are not illustrated, as they are present equally on both sides of the
equation. Cu metal is referred to as the reducing agent or reductant since it reduces Ag+ ions.
Likewise, the aqueous Ag+ ion is called the oxidizing agent or oxidant due to the fact that it oxidizes
the Cu metal. Experimentally, when a solution of Ag+ ions is transferred to a beaker containing Cu wires

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2302103 General Chemistry Laboratory, Experiment 5: Redox Reactions, Galvanic Cells, and the Nernst Equation 5-2

(Figure 5-1), Ag+ ions migrate to the Cu atoms to receive electrons, yielding Ag atoms on the surface of
the Cu metal and Cu2+ ions that move into the solution.

Figure 5-1 Redox reaction between Cu wires and the solution of Ag+ ions

Galvanic Cell

Spontaneous redox reactions can be used to produce electrical energy in galvanic or voltaic
cells. In contrast, any desired reactions can be forced to occur by the consumption of electrical energy
in electrolytic cells. You will investigate some properties of galvanic cells in this experiment.

Figure 5-2 displays a schematic diagram of a galvanic cell. In this cell, two redox couples are
placed in separated compartments, named half-cells. Each half-cell consists of an electrode, usually
the metal (reduced state) of the redox couple, which is immersed into a solution containing the
corresponding cation (oxidized state) of the redox couple. Two electrodes of the half-cells are connected
by an electrical wire, providing the current (electron flow) for the external circuit. In addition, both half-
cells are connected by a salt-bridge that allows limited movement of ions from one half-cell to the other.
Hence, the electrical neutrality can be maintained in the half-cells. For example, when Cu2+ ions reduce
‒
to give Cu metal in its half-cell, either cations (Na+ ions from the salt-bridge) must enter, or anions (NO3
ions) must leave the Cu2+/Cu half-cell via the salt-bridge. Similarly, when Zn metal oxidizes to Zn2+ ions
in the Zn2+/Zn half-cell, either anions (Cl‒ ions from the salt-bridge) must enter or cations (Zn2+ ions)
must leave the half-cell to sustain neutrality in (and between) the half-cells.

The electrode at which oxidation occurs is called the anode; the electrode at which reduction
takes place is called the cathode. In a galvanic cell, the anode is considered as the negative electrode
since oxidation releases electrons to provide a current in the external circuit. On the other hand,
reduction at the cathode pulls electrons from the circuit to the ions in solution. Thus, the cathode is
designated as the positive electrode.

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2302103 General Chemistry Laboratory, Experiment 5: Redox Reactions, Galvanic Cells, and the Nernst Equation 5-3

Figure 5-2 Schematic diagram of a galvanic cell

https://2012books.lardbucket.org/books/principles-of-general-chemistry-v1.0/s23-electrochemistry.html

A DC voltmeter or a potentiometer is located at the external circuit between the two electrodes
to measure the cell potential (Ecell). The Ecell of a galvanic cell is the difference between two electrode
potentials or conventionally the difference between the reduction potentials (Ered) of the two redox
couples (i.e. the difference between the tendencies of the metal ions in their respective half-cells to
undergo reduction). Thus, Ecell is generally given by:

Ecell = Ered (cathode ) − Ered (anode ) (5-4)

For the galvanic cell of Cu–Zn (Figure 5-2) where the spontaneous transfer of electrons occurs,
the cell potential is therefore:

2+
Ecell = Ered (Cu /Cu) ‒ Ered (Zn2+ /Zn) (5-5)

Since Cu2+ ion has a greater (more positive) reduction potential than Zn2+ ion (i.e. Cu2+ ion has
a greater tendency to undergo reduction process than Zn2+ ion does), Ered (Cu2+/Cu) is positioned before
Ered (Zn2+/Zn) to obtain a positive value of Ecell in equation (5-5). The positive voltage for the cell potential
indicates that the reaction is spontaneous, and that the reaction would produce an electric current when
set up as a galvanic cell.

When the concentrations of all ions are 1.0 M and the temperature of all solutions is 25 °C, the
0
cell potential is called the standard cell potential ( E cell ).

0
Ecell = Ered
0
(cathode) − Ered
0
(anode) (5-6)

The standard electrode potentials for any half-reactions are tabulated for reduction reactions, and they
0
are denoted by a symbol Ered .

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2302103 General Chemistry Laboratory, Experiment 5: Redox Reactions, Galvanic Cells, and the Nernst Equation 5-4

The Nernst Equation

When redox systems are not at the standard conditions, usually when the concentrations of the
ions in the solution deviate from 1.0 M, the Nernst equation can be applied. At 25 °C, the measured
0
cell potential (Ecell) is related to the standard cell potential ( E cell ) and concentrations of ions by

0.0592
E cell = E cell
0
− log Q (5-7)
n

where n represents the moles of electrons involved in the redox reaction, and Q, the reaction quotient,
is the mass action expression for the cell reaction. For example,

Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s) (5-8)

Then,
[ Zn2+ ]
Q= and n = 2 (5-9)
[Cu2+ ]

Thus, the Nernst equation for this redox reaction becomes:

0.0592 [Zn2+ ]
Ecell = E cell
0
− log (5-10)
2 [Cu2+ ]

which can be rearranged to yield an equation of a straight line, y = mx + b, where y is Ecell and x is
log [Cu2+].

0.0592 0.0592
E cell = E 0cell - log[Zn 2+ ] + log[Cu 2+ ] (5-11)
2 2

y = b + m x

A plot of Ecell vs. log [Cu2+] for solutions of known copper ion concentration (Figure 5-3) can be used to
determine the concentration of an unknown copper solution.

Ecell

0.0592
m=
2

log [Cu2+]

Figure 5-3 A graph of Ecell versus log [Cu2+]

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2302103 General Chemistry Laboratory, Experiment 5: Redox Reactions, Galvanic Cells, and the Nernst Equation 5-5

In addition, the Nernst equation can be written for the reduction potential (Ered). According to
equation (5-6), equation (5-10) can be expressed as

0.0592 [Zn 2+ ]
E cell = E red
0
(Cu2+ /Cu) − E red
0
(Zn2+ /Zn) − log
2 [Cu2+ ]

0.0592 0.0592 1
= E red
0
(Cu2+ /Cu) − E red
0
(Zn 2+ /Zn) − log[Zn 2+ ] − log
2 2 [Cu 2+ ]

 0 0.0592 1   0 0.0592 
=  E red (Cu 2+ /Cu) − log  −  E red (Zn 2+ /Zn) +
2+ 
log[Zn 2+ ] 
 2 [Cu ]   2 

 0 0.0592 1   0 0.0592 1 
=  E red (Cu 2+ /Cu) − log  −  E red (Zn 2+ /Zn) −
2+ 
log  (5-12)
 2 [Cu ]   2 [Zn 2+ ] 

Since
E cell = E red (Cu2+ /Cu) − E red (Zn 2+ /Zn) (5-13)

thus, the Nernst equations for Ered of Cu2+/Cu and Zn2+/Zn redox couples become:

0.0592 1
E red (Cu2+ /Cu) = E red
0
(Cu2+ /Cu) − log (5-14)
2 [Cu 2+ ]
and
0.0592 1
E red (Zn 2+ /Zn) = E red
0
(Zn 2+ /Zn) − log (5-15)
2 [Zn 2+ ]

Today Work
To gain general concepts of redox reactions, the reactions between metals and a hydronium
ion (H3O+) from HCl are observed and studied. At the right condition, a hydronium ion can be reduced
by a metal to give hydrogen gas. In addition, three sets of galvanic cells (Cu–Zn, Cu–Pb, and Pb–Zn)
are constructed to determine their relative reduction potentials and the concentration of an unknown
Cu2+ solution using the Nernst equation.

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2302103 General Chemistry Laboratory, Experiment 5: Redox Reactions, Galvanic Cells, and the Nernst Equation 5-6

EXPERMENTAL PROCEDURE
Equipment: DC voltmeter, alligator clips and electrical wires, tweezers, abrasive (sand) paper, filter
paper, test tubes, 25-mL beakers
Chemicals: Al strip, Cu strip, Fe strip, Pb strip, Zn strip, HCl, HNO 3, KNO3, Cu(NO3)2, Pb(NO3)2,
Zn(NO3)2

Part 1 Redox Reactions between Metals and a Hydronium Ion

1. Add about 3 mL of 5 M HCl into each of three test tubes.
2. Polish pieces of Cu, Fe, and Zn with abrasive (sand) paper to remove any oxide coating.

Cu Fe Zn

Figure 5-4 Cu, Fe, and Zn metal pieces

3. Immediately place each of the polished metal in a test tube of 5 M HCl. Start a timer.
4. Observe the metal piece in each test tube. Record the time when you see gas bubble in the
solution or on the surface of the metal piece.
5. Allow 10-15 minutes for any reactions to occur. Record what you observe and list the metal in
order of decreasing activity with a hydronium ion.

Part 2 Galvanic Cells: Redox Potentials of Several Redox Couples

1. In three separate 25-mL beakers, add approximately 3/4 full of the following 0.100 M solution:
Cu(NO3)2, Pb(NO3)2, and Zn(NO3)2.
2. Polish 6-cm strips of Cu, Pb, and Zn with abrasive (sand) paper and rinse them thoroughly with
deionized water. These metal strips are used as electrodes.

Cu Pb Zn

Figure 5-5 Cu, Pb, and Zn metal strips

3. Place a Cu strip (electrode) in the Cu(NO3)2 solution and a Zn strip (electrode) in the Zn(NO3)2
solution in a way that none of the strips (just the part that is dipped in the solution) touches inside
surface of the beakers. In addition, the metals should be bent to extend over the top edge of their
beakers.

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2302103 General Chemistry Laboratory, Experiment 5: Redox Reactions, Galvanic Cells, and the Nernst Equation 5-7

4. Prepare a salt-bridge by rolling a piece of a filter paper and wetting it with saturated KNO3. Then,
fold and insert each end of the filter paper into the Cu(NO3)2 and Zn(NO3)2 solutions. Place the
salt-bridge so that it is immersed into each solution.
5. Attach two electrical wires (red/positive and black/negative) with alligator clips to a DC voltmeter.
Connect the wires to the Cu and Zn electrodes. If the voltage readout is positive, the electrodes
are connected correctly. If not, reverse the connection. Figure 5-6 displays an image of the
constructed Cu–Zn galvanic cell.

Cu / Cu(NO3)2 Zn / Zn(NO3)2

Figure 5-6 Cu–Zn galvanic cell

6. Read and record the cell potential (Ecell) with proper units. Only leave the electrodes attached to
the DC voltmeter long enough to get a stable reading for Ecell. Identify the metal strips that serve
as the cathode (positive terminal) and the anode. Write an equation for the half-reaction occurring
at each electrode. Merge the two half-reactions to obtain the equation for the cell reaction.
7. Determine Ecell for galvanic cells of Cu–Pb and Pb–Zn by repeating the procedure (step 3 to step
6) for constructing the Cu–Zn galvanic cell. Use a freshly prepared filter paper strip for the salt-
bridge of each cell.
8. If the reduction potential of the Zn2+(0.100 M)/Zn redox couple is –0.79 V, find out the reduction
potentials of the Cu2+(0.100 M)/Cu and Pb2+(0.100 M)/Pb redox couples.

Part 3 The Nernst Equation: Determination of the Concentration of an Unknown Cu 2+ Solution

by the Cu–Zn Galvanic Cells

1. Initially, remove the Cu and Zn strips from the solutions used previously, re-polish the strips with
abrasive (sand) paper, and rinse them thoroughly with deionized water.
2. Set up the Cu–Zn galvanic cell by using the Zn2+(0.100 M)/Zn as a reference half-cell and the
Cu2+/Cu with 0.0001 M Cu(NO3)2 solution as another half-cell. Connect the two half-cells with a
freshly prepared salt-bridge. Then, connect the electrodes to the DC voltmeter to obtain Ecell, exp.
0
Calculate the theoretical Ecell (Ecell, calc) by using a table of standard reduction potentials ( Ered ) and

the Nernst equation.

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2302103 General Chemistry Laboratory, Experiment 5: Redox Reactions, Galvanic Cells, and the Nernst Equation 5-8

3. Repeat the measurement of Ecell for the remaining four standard Cu2+ solutions: 0.001 M, 0.010
M, 0.100 M, and 1.000 M Cu(NO3)2, starting with the most dilute solution, and for an unknown
Cu2+ solution. Note that a freshly prepared salt-bridge is required for each cell. Re-polish the strips
everytime you set up a new system (change the concentration).
4. Construct graphs of Ecell, exp and Ecell, calc (Y-axis) vs. log [Cu2+] (X-axis) on the same piece of graph
paper for the five standard Cu(NO3)2 solutions. From these graphs, determine the concentration
of the unknown Cu2+ solution.

Waste Disposal
Take all metal strips out from the solutions and put them into provided beakers.
Salt-bridge paper go to “Combustible Solid (XIIIa)” container.
5 M HCl solutions from Part 1 go to “Acid Waste (VII)” container.
0.100 M solutions of Pb(NO3)2, and Zn(NO3)2 go to “Heavy Metal Waste (VI)” container.
0.0001 M, 0.001 M, and 0.010 M solutions of Cu(NO3)2 go to “Miscellaneous Aqueous Waste
(XIV)” container
0.100 M and 1.000 M solution of Cu(NO3)2 go to “Heavy Metal Waste (VI)” container
Other solutions go to “Miscellaneous Aqueous Waste (XIV)” container.

REFERENCES
1. Beran, J. A. Laboratory Manual for Principles of General Chemistry, 6th ed., John Wiley & Sons:
New York, 2000.
2. Roberts, J. L., Jr.; Hollenberg, J. L.; Postma, J. M. Chemistry in the Laboratory, 4th ed., W. H.
Freeman and Company: New York, 1997.

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