ELECTROCHEMICAL CELLS- devices that use redox reactions to either produce or use electricity.

Electrons enter and exit electrochemical cells with the help of ELECTRODES. Electrodes are made of
electrical conductors such as metals or graphite, and they provide the surfaces on which oxidation and
reduction occurs.

There are two types of electrochemical cells, those that produce electricity and those that use
electricity. Those that produce electricity as the result of spontaneous redox reactions are called
VOLTAIC CELLS. A battery consists of one or more voltaic cells. For example, a common flashlight battery
consists of a single voltaic cell that generates 1.5 volts, whereas a 12-volt automobile battery consists of
six voltaic cells that each generate 2 volts. Voltaic cells make use of spontaneous redox reactions that
release energy. When a flashlight is turned on, a spontaneous redox reaction takes place in the flashlight
battery generating a flow of electrons through the lightbulb. A spontaneous reaction can occur on its
own and releases energy as it proceeds. The reverse of a spontaneous reaction (a nonspontaneous
reaction) cannot take place on its own, and requires an input of energy for it to occur.
Electrochemical cells can also be used to drive redox reactions that do not occur of their own
accord. Electrochemical cells in which electrical energy drives nonspontaneous redox reactions are
called ELECTROLYTIC CELLS. Electrolytic cells are used to plate precious metals onto jewelry, to purify
metals, and to obtain active metals from their compounds. For example, both aluminum and
magnesium metals are obtained from their compounds using electrolytic cells.

VOLTAIC CELLS
In 1800, Alessandro Volta, successfully built the first battery, a device consisting of alternating
disks of dissimilar metals separated by pieces of leather that had been soaked in salt water. Volta
discovered that any two metals and any electrolyte could be used to produce electricity. Indeed, if you
stick two metals, such as zinc and copper, into a lemon, and connect them in the wire, the assembly will
produce an electric current. An electric current is also produced if you have metal dental fillings, and you
bite down on a piece of aluminum foil. In fact, you then have a voltaic cell in your mouth. The result is a
very unpleasant shock as electrons move from the aluminum to your fillings and from the fillings to the
nerve endings in your teeth.

VOLTAIC CELL SETUP

All voltaic cells operate in a similar fashion and share certain common features. We will use the
spontaneous redox reaction between zinc metal and a solution of copper sulfate to illustrate the main
ideas.
Zn (s) + CuSO4 (aq) ZnSO 4 (aq) + Cu (s)

If a strip of metallic zinc is dipped into a solution of copper (II) sulfate, zinc goes into solution (is
eaten away) as zinc ion (zinc is more active than copper) and metallic copper is formed. This may be
represented by

Cu2+ + Zn Cu + Zn 2+

In this redox reaction, zinc metal is oxidized and copper ions are reduced.

Oxidation: Zn Zn 2+ + 2e-
Reduction: Cu2+ + 2e- Cu
Electrons are transferreddirectly from zinc to copper ions. No electric current has been generated in this
case, but if the oxidation and reduction reactions could be made to take place at electrode surfaces in
contact with the solution, and the transfer of electrons were made through a metallic conductor, then at
least a part of the chemical energy would be transformed into electrical energy.

A voltaic cell can be visualized as consisting of two half cells, one corresponding to the oxidation
half reaction and one corresponding to the reduction half reaction. As the zinc is oxidized in one-half
cell, the electrons that are given up pass through the wire to the copper electrode that is located in the
other half-cell. These electrons become available to reduce the Cu 2+ ions that are in contact with that
electrode.

The electrode at which oxidation occurs is called the anode. In the zinc-copper cell, the zinc
electrode is the anode because zinc is oxidized as the cell operates. The electrode at which reduction
occurs is called the cathode. The copper electrode is the cathode in this voltaic cell.

As you know, all batteries are marked with + and – signs indicating the positive and negative
electrodes. The negative electrode of a battery, or a voltaic cell, is the anode because that is where the
negatively charged electrons are released. These electrons move spontaneously from the negative
electrode (the anode) to the positive electrode (the cathode). In a zinc-copper cell, the zinc electrode,
the anode, is the negative electrode and the copper electrode, the cathode, is the positive electrode.
 An important feature of the voltaic cell illustrated in the figure above is the tube connecting the
two half-cells. This tube, a SALT BRIDGE, contains an electrolyte solution. The salt bridge allows ions to
move from one compartment to another but prevents the solutions from mixing totally. Other devices
such as porous clay barrier between solutions can be used in place of the salt bridge to allow the flow of
ions between half-cells. The movement of ions between half-cells keeps the number of positive and
negative ions equal in each half-cell and is essential to complete the electrical circuit. Without this flow
of ions within the cell, charge will begin to accumulate in each half-cell.

CELL POTENTIAL

The ability of a cell reaction to move electrons through a wire from one electrode of a voltaic
cell to another is described by a quantity called the electrical potential of the cell or merely the cell
potential. As you might expect, the CELL POTENTIAL represents the difference in the electrical potential
energy between the two electrodes of the cell. Because cell potential is measured in units of volts, it is
often referred to as CELL VOLTAGE. You can measure the voltage of a cell by connecting one terminal of
a voltmeter to one electrode and the other terminal to the other electrode. The voltage of a cell
represents the force with which each electron is pushed as it moves from one electrode to the other. It
is a measure of the cell’s ability to drive an electric current through a wire and thereby do work.

In the zinc-copper cell, electrons in the zinc electrode have a higher electrical potential energy
than electrons in the copper electrode. Thus the electrons move spontaneously from zinc to copper
when a path or wire is provided between them.

STANDARD CELL POTENTIALS

As you have just read, the magnitude of the cell potential represents the driving force of the
redox reaction. The cell potential can also be related to the energy released as the cell reaction
proceeds, and to the electrical work that the cell can perform.

The magnitude of a voltaic cell’s potential depends largely on the nature of the cell reaction
itself. It also depends on the ion concentration in solution, the pressure of any gases involved, and the
reaction temperature. In order to compare the potentials of different voltaic cells, a set of standard
conditions has been defined for electrochemical measurements. In a cell reaction at standard-state
conditions, the concentration of solutions is 1 M, and the partial pressure of gases is 1 atmosphere.
Although standard-state measurements can be made at any temperature, they are usually made at
25oC. the voltage of a zinc-copper cell at 25 oC is +1.10 volts under standard-state conditions (that is,
when the concentration of both zinc ions and copper ions is 1 M.

STANDARD ELECTRODE POTENTIALS

Each electrode of a voltaic cell makes a characteristic contribution to the cell potential. Thus, the
cell potential, designated by E cell, can be considered to be the sum of the contributions from the
oxidation reaction at the anode, Eoxidation, and the reduction reaction at the cathode, E reduction.

Ecell = Eoxidation + Ereduction

Ecell = Eoxi + Ereduction

These contributions are called electrode potentials. To more specifically indicate the type of half
reaction occurring at each electrode, the electrode potential for a reduction half reaction is commonly
called a REDUCTION POTENTIAL. In a similar way, the electrode potential for an oxidation half reaction
is called an OXIDATION POTENTIAL.

When a cell is operated under standard-state conditions, the cell potential and electrode
potentials are called standard cell potentials and standard electrode potentials, respectively. The
standard-state conditions are indicated by a superscript o. The symbol used for standard electrode
potential is Eo (called E zero).

Electrode potentials may be written two ways:

(1) Zn ↔ Zn2+ + 2 e- E = +0.7628 V

(2) Zn2+ + 2 e- ↔ Zn E = -0.7628 V
The first equation is an oxidation reaction and the electrode potential is called the oxidation potential.
The second equation is written as the reverse of the first and is a reduction. The E value is called the
reduction potential.

Eo cell = Eo oxi + Eo red

Table 17.1 lists some common standard electrode potentials. The table contains the reduction half
reactions and the corresponding E oat standard conditions. The position of a substance in the table gives
an indication of the tendency of the half reaction to occur, those higher in the table being more readily
oxidized, those lower being more readily reduced. In table 17.1, for example, Li metal at the top of the
table has the greatest tendency to be oxidized to Li + (or is the strongest reducing agent) and has the
highest negative Eovalue. On the other hand F2 at the bottom of the table has the greatest tendency to
be reduced (and is the strongest oxidizing agent). It has the highest positive E ovalue.

Sample Problem #1

Calculate the voltage produced under standard conditions by a voltaic cell composed of a silver
electrode in an Ag+ solution in one-half cell and an aluminum electrode in an Al 3+ solution in the other
half-cell.

Solution:
From Table 17.1, the Eo values are:

Ag+ + 1e- ↔ Ag Eo= +0.7991 V

Al3+ + 3e- ↔ Al Eo= - 1.66 V
Looking at the position of Ag and Al, Al is located higher than Ag, therefore Al has the greater tendency
to be oxidized. Thus, Ag is reduced.

Oxidation: Al ↔ Al3+ + 3e- therefore Eo= +1.66 V

Reduction: Ag+ + 1e- ↔ Ag Eo= +0.7991 V

Solving for the standard electrode potential:

Eo cell = Eo oxi + Eo red

= +1.66 V + ( +0.7991 V) = +2. 4591 V

Sample Problem #2

Consider the reaction:

Pb2+ + Zn → Pb + Zn2+

Find the standard electrode potential produced under standard conditions.

Solution:

Zn2+ + 2e- ↔ Zn Eo = - 0.763 V

Pb2+ + 2e- ↔ Pb Eo = - 0.126 V

Looking at the position of Zn and Pb:

Oxidation: Zn ↔ Zn2+ + 2e- Eo = + 0.763 V
Reduction: Pb2+ + 2e- ↔ Pb Eo = - 0.126 V

Solving for the standard electrode potential:

Eo= + 0.763 V + (- 0.126 V) = + 0.673 V

Sample Problem #3:

Given:
Zn (s) | Zn2+ (1 M) ‖ Cu2+ (1 M) | Cu (s)
Determine the standard electrode potential produced under standard conditions.

Solution:
Let us interpret first the given. By convention, the anode is given first followed by the active ion
concentration in the anode compartment, the ion concentration in the cathode compartment, and
finally the cathode. The single vertical lines represent phase boundaries and the double vertical lines
denote the porous diaphragm or salt bridge separating the two solutions.

Zn2+ + 2e- ↔ Zn Eo = - 0.763 V

Cu2+ + 2e- ↔ Cu Eo = + 0.337 V
Oxidation: Zn ↔ Zn2+ + 2e- Eo = + 0.763 V
Reduction: Cu2+ + 2e- ↔ Cu Eo = + 0.337 V

Solving for the standard electrode potential:

Eo= + 0.763 V + (+ 0.337 V) = + 1.1 V

Sample Problem #4

If F2 is added to Ag, (1) Will the reaction be spontaneous? (2) What will be the E o value? (3) What
are the anode and cathode?

Solution:
2 Ag ↔ 2 Ag+ + 2 e- Eo = - 0.7991 V
- - o
F2 + 2 e ↔ 2 F E = + 2.87 V__
2 Ag + F2 ↔ 2 Ag+ + 2 F- + 2.0709 V

Note that if the half reaction with the lower E o value is written first (higher in the table) and then
reversed, followed by the half reaction with the higher E o value, when the electrons in the two half
reactions are made the same and the two equations are added, the E cell will always be positive—
indicating a spontaneous reaction as written. Ag is the anode (oxidation occurs) and F 2 is the cathode
(reduction).
OVERALL REACTIONS

Sample Problems on how to write the overall reactions given the half reactions:

1. Pb → Pb2+ + 2 e-
Pb2+ + SO42- → PbSO4 (s)
Pb + SO42- → PbSO4 (s) + 2 e-

2. 2 e- + NiO2 + 2H2O → Ni(OH)2 + 2 OH-

Cd + 2 OH- → Cd(OH)2 + 2 e-_______
Cd + NiO2 + 2H2O → Ni(OH)2 + Cd(OH)2
Questions/Self-Assessment:

1. What is the purpose of the salt bridge?

2. What is the standard cell potential of a voltaic cell composed of magnesium electrode in
contact with Mg2+ ions and a tin electrode in contact with Sn2+ ions?

3. A voltaic cell is constructed using electrodes based on the following half reactions:

Pb2+ (aq) + 2e- ↔ Pb (s)

Mn2+ (aq) + 2e- ↔ Mn (s)

a. What is the anode and what is the cathode in this cell?

b. What is the standard cell potential?
c. Will the reaction be spontaneous? Why?

4. Will Ag+ oxidize Au? In other words, will the following reaction occur?

Au + 3 Ag+ → Au3+ + 3 Ag
Hint: Solve first the standard electrode potential

5. Using Table 17.1, 1) determine the standard electrode potentials of the following cells (all
cells are at “standard” conditions) and 2) is the reaction spontaneous?
a. Mg|Mg2+ ‖ Ag+|Ag
b. Sn|Sn2+ ‖ Cu2+|Cu
c. Ca|Ca2+ ‖ Zn2+|Zn
d. Fe|Fe2+ ‖ H+|H2

6. Given the following half reactions, write the overall reactions:

a. Fe + 2 OH- → Fe(OH)2 + 2 e-
2 e- + Ni2O3 + 3 H2O → 2 Ni(OH)2 + 2 OH-

b. 5 As4O6 + 50 H2O → 20 H3AsO4 + 40 H+ + 40 e-

8 MnO4- + 64 H+ + 40 e- → 8 Mn2+ + 32 H2O_
7.