Helia Bazargan

IB Chemistry
Mr. Plunkett
May 26th, 2021

Voltaic Cells
Abstract:

Introduction:
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 loses electrons (undergoes oxidation) and another reactant gains electrons
(undergoes reduction). For example, a piece of magnesium going into a solution as magnesium
ions, with each Mg atom giving up 2 electrons, is an example of an oxidation half-reaction.
Mg(s)  Mg2+(aq) + 2e-

The oxidation number of Mg(s) is 0 and the oxidation number of Mg2+ is +2. Therefore, in
this half reaction, the oxidation number increases, which is another way of defining
oxidation. In contrast, the reverse reaction, in which Mg2+ ions gain 2 electrons to become
Mg atoms, is an example of reduction.
Mg2+(aq) + 2e-  Mg(s)

In a reduction, there is a decrease (or reduction) in oxidation number. Chemical equations

representing half-reactions must be balanced both in terms of mass and charge. In the half-
reactions above, there is one magnesium on both sides of the equation. The charge is balanced
because the 2+ charge on the magnesium ion is balanced by two electrons, 2e-, giving zero net
charge on both sides. Another example of reduction is the formation of solid copper from
copper ions in solution.
Cu2+(aq) + 2e- Cu(s)
In this half-reaction the oxidation number of aqueous copper is +2, which decreases to O for
solid copper, and again charge and mass are balanced. However, no half-reaction can occur by
itself. A redox reaction results when an oxidation and a reduction half-reaction are combined to
complete a transfer of electrons as in the following example:

Mg(s) + Cu 2+(aq)  Mg2+(aq) + Cu(s)

The electrons are not shown because they are neither reactants nor products but have simply
been transferred from one species to another (from Mg to Cu2+ in this case). In this redox
reaction, the Mg(s) is referred to as the reducing agent because it causes the Cu2+ to be reduced
to Cu. The Cu2+ is called the oxidizing agent because it causes the Mg(s) to be oxidized to
Mg2+

Any half-reaction can be expressed as either a reduction or an oxidation simply by reversing the
reaction. A measure of the tendency for a reduction to occur is its reduction potential, E,
measured in units of volts. At standard conditions (25°C and concentrations of 1.0 M for the
aqueous ions), the measured voltage of the reduction half-reaction is defined as the standard
reduction potential, E°s. Standard reduction potentials have been measured for many half-
reactions; they are listed in your textbook, in Table 24 of the data booklet, and are also easily
available on-line.

For the magnesium and copper reduction half-reactions above, the standard reduction potentials
are -2.37 V for magnesium and +0.34 V for copper. The more positive (or less negative) the
reduction potential, the greater is the tendency for the reduction to occur. So Cu2+ has a greater
tendency to be reduced than Mg2+. Furthermore, Mg has a greater tendency to be oxidized than
Cu. The values of E° for the oxidation half-reactions are opposite in sign to the reduction
potentials: +2.37 V for Mg and -0.34 V for Cu.

A voltaic cell is a device in which a redox reaction spontaneously occurs and produces an
electric current. For the transfer of electrons in a redox reaction to produce an electric current
and be useful, the electrons must pass through an external wire instead of being directly
transferred between the oxidizing and reducing agents. The design of a voltaic cell (shown in
Figure 1) allows this to occur. In a voltaic cell, two solutions, one containing the ions of the
oxidation half-reaction and the other containing the ions of the reduction half-reaction, are
placed in separate beakers called half-cells. For each half-cell, the metal, which is called the
electrode, is placed in the solution, and connected to an external wire. The electrode at which
oxidation occurs is called the anode (Zn in this case) and the electrode at which reduction
occurs is called the cathode (Cu in this case). The two half-cells are connected by a salt-bridge
that allows a "current" of ions to flow from one half-cell to the other to complete the circuit of
electron current in the external wires. When the two electrodes are connected to an electric load
(such as a light bulb or voltmeter) the circuit is completed, the oxidation-reduction reaction
occurs, and electrons move from the anode (-) to the cathode (+), producing an electric current.

Figure 1. Diagram of a Voltaic Cell

The cell potential, Ecell, which is a measure of the voltage that the battery can provide, is
calculated from the half-cell reduction potentials:
Ecell = Ecathode – Eanode

At standard conditions (indicated by the superscript o), the standard cell potential, E°cell, is based
on the standard reduction potentials.
E°cell = E°cathode – E°anode

Based on the values for the standard reduction potentials for the two half-cell (-2.37 V for a
magnesium anode and +0.34 V for a copper cathode), the standard cell potential E°cell for the
voltaic cell in Figure 1 (that uses Mg rather than Zn at the anode) would be:
E°cell = +0.34 V – (-2.37 V) = +2.71 V

The positive voltage for E°cell indicates that at standard conditions the reaction is spontaneous.
Recall that
 ∆G° = - nFE°cell

so that a positive E°cell results in a negative ∆G°. Thus, this redox reaction would spontaneously
produce an electric current when set up as a voltaic cell.

When conditions are not standard, the Nernst equation can be used to calculate the potential of
a cell. In the Nernst equation, R is the universal gas constant with a value of 8.314 J/(°K.mol),
T is the temperature in °K, and n is the number of electrons transferred in the redox reaction (2
in this case). Q is the reaction quotient for the ion products/ion reactants of the cell. The solid
electrodes have constant "concentrations" and so do not appear in Q. F is the Faraday constant
with a known value of 96,500 J/(V.mol). 
Ecell = E°cell – (RT/nF) InQ

For our example, 

Mg(s) + Cu 2+(aq)  Mg2+(aq) + Cu(s)

so, Q is: 
Q = [Cu2+] / [Mg2+] 

Expanding,
 
Ecell = E°cell – (RT/2F) In [Mg2+] + (RT/2F) In [Cu2+]

In a series of experiments in which [M 2+] is kept constant while [Cu2*] is varied, Ecell can be
measured and will be found to vary with ln [Cu 2+]. A plot of the data in which the y-axis is
Ecell and the x-axis is ln [Cu2+] will result in a straight line: y = mx+ b. 

In the Nernst equation above, the terms E°celld and -(RT/2F) In [Zn2+] are constant, and together
they equal the intercept, b, of the line. (RT/2F) will be the constant slope, m, provided that the
temperature remains constant. 
Thus, a plot can be generated by measuring the cell potential for different values of [Cu2+] while
keeping [Mg2+] constant (at 1.0 M for standard conditions). The equation of the line in this plot
can then be used to determine in [Cu2+] in a solution of unknown concentration from its measured
Ecell, as long as [Mg2+] remains at 1.0 M and the temperature at 25°C. This is the same principle
used in a pH meter for the determination of [H+]. Notice that as the concentration of Cu 2+ ion
reactant increases (or In[Cu2+] becomes less negative), the potential of the cell increases.

Objective:
This experiment will take multiple measurements of the voltaic cell potential as the concentration
of the copper sulfate solution (in the cathode side) decreases by known amounts. This will create
a graph of cell potential vs. In [Cu2+].

Pre-Experiment Preparation:
1. Calculate the amount of CuSO4 needed to prepare 100 mL of 1.5M CuSO4 solution for
the cathode.
2. Calculate the amount of FeSO4 needed to prepare 200 mL of 1M FeSO4 solution for the
anode. If the reagent is a hydrated crystal, be sure to account for the hydrated water.

Procedure:
1. Prepare CuSO4 and FeSO4 solutions for use in the cathode and anode, respectively.
2. Prepare about 50 mL of K2SO4 solution for use in the salt bridge. Roll up and soak a
paper towel in the solution while constructing voltaic cell.