ELECTROCHEMISTRY

CHEMICAL CHANGE and ELECTRICAL WORK

Electrochemistry is the branch of chemistry that deals

with the study of the relationships between electricity and
chemical reactions. It is the study of the relationship
between chemical change and electrical work. It deals with
the inter conversion of chemical energy and electrical
energy. These inter conversion takes place in an
electrochemical cell.

Electrochemical cells are systems that incorporate an

oxidation-reduction reaction also called redox reaction to
produce or utilize electrical energy.

Redox Reactions and Electrochemical Cells

Whether an electrochemical process releases or absorbs
free energy, it always involves the movement of
electrons from one chemical species to another in an
oxidation-reduction (redox) reaction.

Two Types of Electrochemical Cells

1. Voltaic Cell or Galvanic Cell
It is a cell that does work by releasing free energy from a
spontaneous reaction to produce electricity, i.e., it uses a
spontaneous reaction (G < 0) to generate electrical
energy.

In the cell reaction, the difference in chemical potential

energy between higher energy reactants and lower energy
products is converted into electrical energy. This energy is
used to operate the load — flashlight bulb, CD player, car
starter motor, or other electrical device.

Thus, the system does work on the surroundings.

All batteries contain voltaic cells.

2. Electrolytic Cell
It is a cell that does work by absorbing free energy from a
source of electricity to drive a nonspontaneous reaction,
i.e., it uses electrical energy to drive a nonspontaneous
reaction (G > 0).

In the cell reaction, electrical energy from an external

power supply converts lower energy reactants into higher
energy products.

Thus, the surroundings do work on the system.

Electroplating and recovering metals from ores involve
electrolytic cells.

The two types of cell have certain design features in

common. Two electrodes, which conduct the electricity
between cell and surroundings, are dipped into an
electrolyte, a mixture of ions (usually in aqueous solution)
that are involved in the reaction or that carry the charge.
An electrode is identified as either anode or cathode
depending on the half-reaction that takes place there:
• The oxidation half-reaction occurs at the anode.
Electrons are lost by the substance being oxidized
(reducing agent) and leave the cell at the anode.
• The reduction half-reaction occurs at the cathode.
Electrons are gained by the substance being reduced General characteristics of voltaic and electrolytic
(oxidizing agent) and enter the cell at the cathode. cells. A voltaic cell generates energy from a spontaneous
reaction (G < 0), whereas an electrolytic cell requires
Memory Aid energy to drive a nonspontaneous reaction (G > 0). In
AN OX and a RED CAT both types of cell, two electrodes dip into electrolyte
ANode OXidation ; REDuction CAThode solutions, and an external circuit provides the means for
LEO the lion lives in a GER electrons to flow between them. Most important, notice
FAT CAT that oxidation takes place at the anode and reduction takes
place at the cathode, but the relative electrode charges are
opposite in the two cells.

Page 1 of 7
REDOX REACTIONS AND ELECTROCHEMICAL CELLS
Whether an electrochemical process releases or absorbs
free energy, it always involves the movement of electrons
from one chemical species to another in an oxidation-
reduction (redox) reaction.
In electrochemical reactions, as in any redox process,
oxidation is the loss of electrons, and reduction is
the gain of electrons. An oxidizing agent is the species
that does the oxidizing, taking electrons from the substance
being oxidized. A reducing agent is the species that does
the reducing, giving electrons to the substance being
reduced.
After the reaction, the oxidized substance has a higher
(more positive or less negative) oxidation number, and the
reduced substance has a lower (less positive or more
negative) oxidation number.
Keep in mind three key points:
• Oxidation (electron loss) always accompanies re.duction
(electron gain).
• The oxidizing agent is reduced, and the reducing agent is
oxidized.
• The total number of electrons gained by the atoms/ions
of the oxidizing agent always equals the total number lost
by the atoms/ions of the reducing agent.
Consider the spontaneous reaction that occurs when Zn is
added to HCl.
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
ions will not react with other ions in the cell or with the
electrode materials. As oxidation and reduction proceed at
the electrodes, ions from the salt bridge migrate to
neutralize charge in the cell compartments. Anions
migrate toward the anode, and cations toward the
cathode.
NOTE
No measurable electron flow will occur through the external
circuit unless a means is provided for ions to migrate
through the solution from one electrode compartment to
another, thereby completing the circuit.
Because the negatively charged electrons flow from the
anode to the cathode, the anode in a voltaic cell is labeled
with a negative sign and the cathode with a positive
sign. We can envision the electrons as being attracted to
the positive cathode from the negative anode through the
external circuit.
NOTE
Although the anode and cathode are labeled with (-) and
(+) signs respectively, you should not interpret the labels
as charges on the electrodes. The labels simply tell us the
electrode at which the electrons are released to the
external circuit, the anode, and received from the external
circuit, the cathode. The actual charges on the electrodes
are essentially zero.
Example : consider a Zn – Cu electrochemical cell

OXIDATION Electrodes : anode – Zn metal cathode – Cu metal

One reactant loses Zinc loses electrons.
Electrolyte solutions : anode – Zn(NO3)2(aq)
electrons.
Reducing agent is oxidized. Zinc is the reducing agent cathode – Cu(NO3)2(aq)
and becomes oxidized.
The oxidation number of Zn External circuit: wire that connects the Zn and Cu strips
Oxidation number increases.
increases from 0 to +2. Electrodic reactions :

REDUCTION anodic oxidation : Zn(s)  Zn2+(aq) + 2e-

One reactant gains Hydrogen ion gains cathodic reduction : Cu2+(aq) + 2e-  Cu(s)
electrons. electrons.
Oxidizing agent is reduced. Hydrogen ion is the
oxidizing agent and
becomes reduced.
Oxidation number The oxidation number of H
decreases. decreases from +1 to 0.

VOLTAIC CELLS or GALVANIC CELLS: USING

SPONTANEOUS REACTIONS TO GENERATE
ELECTRICAL ENERGY

In a voltaic cell the oxidation and reduction half-reactions

occur in separate compartments. Each compartment has a
solid surface called an electrode, at which the half-reaction
occurs. We can think of the voltaic cell as two “half-cells, ”
one corresponding to the oxidation half-reaction and one
corresponding to the reduction half-reaction. The electrode
at which oxidation occurs is called the anode; the
electrode at which reduction occurs is called the
cathode.
The anode and the cathode are connected to each other by
means of a wire that serves as an external circuit where
electrons flow. The electrons released at the anode flow
through the external circuit, where they do electrical work,
to the cathode.
Reduction of Cu2+ can occur only by a flow of electrons
through an external circuit. Electrons become available as
zinc metal is oxidized at the anode. They flow through the
external circuit to the cathode, where they are consumed
as Cu2+(aq) is reduced to Cu(s) and is deposited on the
cathode.
Because Zn(s) is oxidized in the cell, the zinc electrode
loses mass, and the concentration of the Zn 2+ solution
increases as the cell operates. Similarly, the Cu electrode
gains mass, and the Cu2+ solution becomes less
concentrated as Cu2+ is reduced to Cu(s).

Electrical neutrality in the solution is maintained by the
migration of ions between the two compartments through a
device such as a salt bridge.
A salt bridge consists of a U-shaped tube that contains an
electrolyte solution, such as KCl(aq) or NaNO 3(aq), whose
As the voltaic cell operates, oxidation of Zn introduces
additional Zn2+ ions into the anode compartment. Unless a
means is provided to neutralize this positive charge, no
further oxidation can take place. Similarly, the reduction of
Cu2+ at the cathode leaves an excess of negative charge in
solution in that compartment.

Page 2 of 7
NOTE
The flow of electrons from the anode to the cathode is
possible only if ions are transferred through the salt bridge
in order to maintain overall charge balance for each of the
two compartments.
To balance charges the cation in the salt bridge migrate
toward the cathode and the anions migrate toward the
anode.
Illustration
CELL EMF
Electrons flow from the anode of a voltaic cell to the
cathode because of a difference in potential energy. The
potential energy of electrons is higher in the anode than in
the cathode, and they spontaneously flow through an
external circuit from the anode to the cathode.
The difference in potential energy per electrical charge or
the potential difference between two electrodes is
measured in units of volts. One volt, V, is the potential
difference required to impart 1 J of energy to a charge of 1
coulomb, C, i.e.,
1V = 1J/C
The potential difference between the two electrodes of a
voltaic cell provides the driving force that pushes electrons
through the external circuit. Therefore, we call this
potential difference the electromotive force or emf.
(electromotive means “causing electron motion”)
The emf of a cell, Ecell, is also called the cell potential.
Because Ecell is measured in volts, we also refer to it as the
cell voltage.
For any cell reaction that proceeds spontaneously, like that
in a voltaic cell, the cell potential will be positive.
The emf of a particular voltaic cell depends on the
following:
1. specific reactions that occur at the anode and cathode
2. concentrations of reactants and products
3. temperature (assume to be 25C unless otherwise
noted)
Under standard conditions the emf is called the standard
emf or the standard cell potential, E cell.
Standard conditions include 1 M concentrations for
reactants and products in solution and 1 atm pressure for
gases.
e.g. the standard cell potential at 25C for the Zn – Cu
voltaic cell is +1.10 V
Zn(s) + Cu2+(aq, 1 M)  Zn2+(aq, 1 M) + Cu(s) Ecell = +1.10 V
Standard Reduction Potentials
The cell potential of a voltaic cell depends on the particular
cathode and anode half – cells involved. The cell potential
is the difference between two electrode potentials, one
associated with the cathode and the other associated with
the anode.
By convention, the potential associated with each electrode
is chosen to be the potential for reduction to occur at that
electrode.
Thus, standard electrode potentials are tabulated for
reduction half – reactions and are called standard
reduction potentials, E red.
The standard cell potential, Ecell, is given by the standard
reduction potential of the cathode reaction, Ered(cathode)
minus the standard reduction potential of the anode
reaction, Ered(anode), i.e.,
E cell = E red (cathode) - E red (anode)
Because every voltaic cell involves two half – cells, it is not
possible to directly measure the standard reduction
potential of a half – reaction. However, if we assign a
standard reduction potential to a certain reference half –
reaction, we can then determine the standard reduction
potentials of other half – reactions relative to that
reference.
The reference half – reaction is the reduction of H +(aq) to
H2(g) under standard conditions, called the standard
hydrogen electrode, SHE. SHE is assigned a standard
reduction potential of exactly 0 V.
2H+(aq, 1 M) + 2e-  H2(g, 1 atm) Ered = 0 V
SHE consists of an electrode with finely divided Pt in
contact with H2(g) at 1 atm pressure and an acidic solution
with [H+] = 1 M. The platinum wire is connected to a piece
of platinum foil covered with finely divided platinum that
serves as an inert surface for the reaction. The electrode is
encased in a glass tube so that hydrogen gas under
standard conditions (1 atm) can bubble over the platinum,
and the solution contains H +(aq) under standard (1 M)
conditions.
When the SHE is the cathode of a cell, 2 H + ions accept an
electron from the Pt electrode and are reduced to H atoms.
The H atoms bond together to form H2. When the SHE is
the anode of a cell, the reverse process occurs: an H 2
molecule at the electrode surface loses 2 electrons and is
oxidized to H+. The H+ ions in solution are hydrated to
H3O+ ions.
e.g. consider the oxidation of Zn and the reduction of H +
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g) Ecell = + 0.76 V
to calculate for the cell potential of Zn
Ecell = Ered (cathode) - Ered (anode)
Ered (anode) = Ered (cathode) - Ecell
= 0 V – (+ 0.76 V)
= - 0.76 V
Therefore, the standard reduction potential for the
reduction of Zn2+ to Zn is –0.76 V , i.e.,
Zn2+(aq, 1 M) + 2e-  Zn(s) Ered = - 0.76 V
Whenever we assign a potential to a half – reaction,
we write the reaction as a reduction.
The standard reduction potentials for other half – reactions
can be established from other cell potentials in a fashion
analogous to that used for the Zn2+/Zn half –reaction.
Page 3 of 7
Standard Reduction Potentials in Water at 25C occur. The more positive the value of E red the
greater the driving force for reduction.
Standard Reduction Half - Reaction
Potential (V) In any voltaic cell the reaction at the cathode has a more
positive value of Ered than does the reaction at the anode.
+ 2.87 F2 (g) + 2 e－  2 F－ (aq) The greater driving force of the cathode half – reaction is
+ 1.51 MnO4- (aq) + 8 H+ (aq) + 5 e －  Mn2+ (aq) + used to force the anode reaction to occur “in reverse ”, as
4 H2O (l) an oxidation.
+ 1.36 Cl2 (g) + 2 e－  2 Cl- (aq)
+ 1.33 Cr2O72－ (aq) + 14 H+ (aq) + 6 e－  2 Cr3+ (aq) Ecell is the “net driving force” that pushes the electrons
+ 7 H2O (l) through an external circuit.
+ 1.23 O2 (g) + 4 H+ (aq) + 4 e－  2 H2O (l)
+ 1.06 Br2 (l) + 2 e－  2 Br－(aq) Sample Exercise
+ 0.96 NO3 － (aq) + 4 H+ (aq) + 3 e －  NO (g) + H2O 3. A voltaic cell is based on the following standard half –
(l) reactions:
+ 0.80 Ag+ (aq) + e－  Ag (s) Cd2+(aq) + 2e-  Cd(s) Ered = - 0.403 V
+ 0.77 Fe3+ (aq) + e－  Fe2+ (aq) Sn2+(aq) + 2e-  Sn(s) Ered = - 0.136 V
+ 0.68 O2 (g) + 2 H+ (aq) + 2 e－  H2O2 (aq) Determine the half – reactions that occur at the cathode
+ 0.59 MnO4 － (aq) + 2 H2O (l) + 3 e －  MnO2 (s) + and the anode. Determine the standard cell potential.
4 OH－ (aq) (0.267 V)
+ 0.54 I2 (s) + 2 e－  2 I－ (aq)
+ 0.40 O2 (g) + 2 H2O (l) + 4 e－  4 OH－ (aq) Practice Exercise
+ 0.34 Cu2+ (aq) + 2 e－  Cu (s) 3. A voltaic cell is based on a Co2+/Co half – cell (Ered =
0.00 2H+ (aq) + 2 e－  H2 (g) - 0.277) and a AgCl/Ag half – cell (E red = +0.222V).
- 0.28 Ni2+ (aq) + 2 e－  Ni (s) What reactions occur at the anode and cathode? What
- 0.44 Fe2+ (aq) + 2 e－  Fe (s) is the standard cell potential?
- 0.76 Zn2+ (aq) + 2 e－  Zn (s) (+0.499 V)
- 0.83 2 H2O (l) + 2 e－  H2 (g) + 2 OH－ (aq)
- 1.66 Al3+ (aq) + 3e－  Al (s) The more positive the E red, the greater is the
- 2.71 Na+ (aq) + e－  Na (s) tendency for reduction (gain of e-) to occur and the
- 3.05 Li+ (aq) + e－  Li (s) electrode has greater tendency to be a cathode. The
more negative the E red, the greater is the tendency
These standard reduction potentials, often called half for oxidation (loss of e-) to occur and the electrode
– cell potentials, can be combined to calculate the emfs of has greater tendency to be an anode.
a large variety of voltaic cells. Oxidizing and Reducing Agents
The more positive the E red value for a half –
Standard reduction potentials are intensive properties reaction, the greater the tendency for the reactant
because electrical potential measures potential energy per of the half – reaction to be reduced, and, therefore,
electrical charge. Thus, changing the stoichiometric to oxidize another species.
coefficient in a half – reaction does not affect the Examination of the standard cell potentials shows that F2
value of the standard reduction potential. with the highest positive voltage (+ 2.87 V) is the most
easily reduced species and is consequently the strongest
e.g. Zn2+(aq, 1 M) + 2e－  Zn(s) Ered = - 0.76 V oxidizing agent listed.

2 Zn2+(aq, 1 M) + 4e－  2Zn(s) Ered = - 0.76 V F2(g) + 2e-  2F-(aq) Ered = + 2.87 V

Sample Exercise
1. For the Zn – Cu2+ voltaic cell, Ecell = 1.10 V and the Zn
electrode is the anode. Given that the standard
reduction potential of Zn2+ is – 0.76 V, calculate the
Ered for the reduction of Cu2+ to Cu:
Cu2+(aq, 1 M) + 2e-  Cu(s)
(1.10 V)
2. Using standard reduction potentials, calculate the
standard emf for the cell reaction
Cr2O72-(aq) + 14H+(aq) + 6I-(aq)  2Cr3+(aq) + 3I2(s)
+ 7H2O(l)
(0.79 V)
Practice Exercises
1. A voltaic cell is based on the following half – reactions:
In+(aq)  In3+(aq) + 2e-
Br2(l) + 2e-  2Br-(aq)
The standard emf for this cell is 1.46 V. Calculate
Ered for the reduction of In3+ to In+.
(- 0.40 V)
2. Calculate the standard emf for a cell that employs the
following overall cell reaction:
2Al(s) + 3I2(s)  2Al3+(aq) + 6I-(aq)
(+ 2.20 V)
For each of the half – cells, the standard reduction potential
provides a measure of the driving force for reduction to
Among the most frequently used oxidizing agents are the
halogens, O2, and oxyanions such as MnO 4-, Cr2O72-, and
NO3-, whose central atoms have high positive oxidation
states. All of these species undergo reduction with large
positive values of Ered.
Lithium ion, Li+, with the highest negative voltage
(- 3.05 V) is the most difficult species to reduce and is
therefore the poorest oxidizing agent.
Li+(aq) + e-  Li(s) Ered = - 3.05 V
The fact that Li+ is so difficult to reduce tells us that the
reverse reaction, the oxidation of Li(s) to Li+(aq), is a
highly favorable reaction. Lithium metal has a great
tendency to transfer electrons to other species; in water it
is the strongest reducing agent among the substances
listed.
Commonly used reducing agents include H 2 and the active
metals such as the alkali metals and the alkaline earth
metals. Zn and Fe are also used as reducing agents.
Solutions of reducing agents are difficult to store for
extended periods because of the ubiquitous presence of O 2,
a good oxidizing agent.
e.g. Developer solutions used in photography are mild
reducing agents; they have only a limited shelf life because
they are readily oxidized by O2 from the air.
Page 4 of 7
The standard reduction potentials, Ered are related to the
ability of substances to serve as oxidizing or reducing
agents. Species on the left side of the half – reactions can
act as oxidizing agents, and those on the right side can
serve as reducing agents. As Ered becomes more positive,
the oxidizing strength of the species on the left increases.
As Ered becomes more negative, the reducing strength of
the species on the right increases.
Most positive values of Ered
F2(g) + 2e-  2F (aq)
-
 
 
2H+(aq) + 2e-  H2(g)
 
 
Li+(aq) + e-  Li(s)
Most negative values of Ered
Sample Exercise
4. Which of the following species is the strongest
oxidizing agent: NO3-(aq), Ag+(aq), Cr2O72-?
Practice Exercise
4. Which of the following species is the strongest reducing
agent: I-(aq), Fe(s), Mn2+(aq)?
The reduced form of any element will reduce the oxidized
form of any element above it in the table.
The oxidized form of any element will oxidize the reduced
form of any element below it in the table.
SPONTANEITY OF REDOX REACTIONS
Voltaic cells use redox reactions that proceed
spontaneously. Any reaction that can occur in a voltaic cell
to produce a positive emf must be spontaneous.
For a general redox reaction,
E = E red (reduction process) - E red (oxidation process)
In general,
A positive value of E indicates a spontaneous
process, and a negative value of E indicates a
nonspontaneous process.
NOTE
E represents the emf under nonstandard conditions
E represents the standard emf
Sample Exercise
5. Using the standard reduction potentials, determine
whether the following reactions are spontaneous under
standard conditions:
(a) Cu(s) + 2H+(aq)  Cu2+(aq) + H2(g)
(b) Cl2(g) + 2I-(aq)  2Cl-(aq) + I2(s)
n represents the number of electrons transferred in the
reaction
F is the Faraday’s constant – the quantity of electrical
charge on 1 mol of electrons
- named after Michael Faraday
This quantity of charge is called a faraday, F:
1 F = 96,500 C/mol = 96,500 J/V-mol
NOTE
“Per mole” unit means “per mole of reaction as written ”.
A positive value of E and a negative value of G both
indicate that a reaction is spontaneous.
At standard conditions, i.e., when the reactants and
products are all in their standard states
G = - nFE
Sample Exercise
6. Use the standard reduction potentials to calculate the
standard free-energy change, G, for the following
reaction:
4Ag(s) + O2(g) + 4H+(aq)  4Ag+(aq) + 2H2O(l)
Suppose the above reaction was written as
2Ag(s) + ½O2(g) + 2H+(aq)  2Ag+(aq) + H2O(l)
what are the values of E and G?
( -170 kJ/mol ; +0.43 V ; -83 kJ/mol)
Practice Exercise
6. Consider the following reaction:
3 Ni2+(aq) + 2 Cr(OH)3(s) + 10 OH-(aq)  3 Ni(s) + 2
CrO42-(aq) + 8 H2O(l)
What is the value of n for this reaction? Calculate G
for this reaction given that Ered = - 0.13 V for the half-
cell reaction:
CrO42-(aq) + 4H2O(l) + 3e-  Cr(OH)3(s) + 5OH-(aq)
(6 ; +87 kJ/mol)
EFFECT OF CONCENTRATION ON CELL EMF
As a voltaic cell is discharged, the reactants of the reaction
are consumed and the products are generated, so the
concentrations of these substances change. The emf
progressively drops until E = 0, at which point we say the
cell is “dead”.
At that point the concentrations of the reactants and
products cease to change; they are at equilibrium.
Under nonstandard conditions the emf generated by a cell
can be calculated using the Nernst equation that was first
derived by Walther Nernst, a German chemist who
established many of the theoretical foundations of
electrochemistry.

Practice Exercise The Nernst Equation

5. Using the standard reduction potentials, determine E = E - (R T / n F) ln Q
which of the following reactions are spontaneous under
standard conditions: or
(a) I2(s) + 5Cu (aq) + 6H2O(l)  2IO3 (aq) + 5Cu(s)
2+ -
E = E - (2.303 R T / n F) log Q
+ 12H+(aq)
At 298 K
(b) Hg2+(aq) + 2I-(aq)  Hg(l) + I2(s)
E = E - (0.0592 V / n) log Q
(c) H2SO3(aq) + 2Mn(s) + 4H+(aq)  S(s) + 2Mn2+
(aq) + 3H2O(l) e.g. consider the Daniell cell
(nonspontaneous ; spontaneous ; spontaneous) Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s) Ecell = 1.10 V
EMF and FREE-ENERGY CHANGE
n = 2 and log Q = log ([Zn2+] / [Cu2+])
G = - nFE
Thus, at 298 K
where
E = 1.10 V - (0.0592 V / 2) log ([Zn 2+] / [Cu2+])

Page 5 of 7
When [Zn2+] = 1.00 M and [Cu2+] = 0.100 M
E = 1.0704 V
When [Zn2+] = 0.100 M and [Cu2+] = 1.00 M
E = 1.1296 V
In general, if the concentrations of reactants increase
relative to those of products, the cell reaction becomes
more spontaneous and the emf increases. If the
concentrations of products increase relative to reactants,
the emf decreases. As voltaic cell operates, reactants are
converted into products, which increases the value of Q
and causes the emf to decrease.
Sample Exercise
7. Calculate the emf at 298 K generated by the cell
Cr2O72-(aq) + 14H+(aq) + 6I-(aq)  2Cr3+(aq) + 3I2(s)
+ 7H2O(l)
when [Cr2O7 ] = 2.0 M; [H ] = 1.0 M; [I ] = 1.0 M ;
2- + -
[Cr3+] = 1.0 x 10-5 M
(0.89 V)
8. Consider a Zn – H+ cell described by the reaction
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
If the voltage of the cell is 0.45 V at 25C when [Zn2+]
= 1.0 M and PH2 = 1.0 atm, what is [H+]?
(6 x 10-6 M)
Practice Exercise
7. Calculate the emf generated by the cell
2Al(s) + 3I2(s)  2Al3+(aq) + 6I-(aq) Ecell = 2.20 V
when [Al3+] = 4.0 x10-3 M and [I-] = 0.010 M
(+2.36 V)
38. What is the pH of the solution in the cathode
compartment of the cell
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
when PH2 = 1.0 atm ; [Zn2+] = 0.10 M and the cell emf
is 0.542 V?
(4.18)
Concentration Cells
A concentration cell is a cell based solely on the emf
generated because of a difference in concentration. It is
constructed using the same species in both the anode and
cathode compartments but with different concentrations.
e.g. consider a Ni2+ - Ni concentration cell
One compartment consists of a strip of nickel metal
immersed in a 1.00 M solution of Ni 2+(aq). The other
compartment also has a Ni(s) electrode, but immersed in a
1.00 x 10-3 M solution of Ni2+(aq). The two compartments
are connected by a salt bridge and by an external wire with
a voltmeter. The half – cell reactions are the reverse of
one another:
Anode : Ni(s)  Ni2+(aq) + 2e- Ered = -0.28 V
Cathode : Ni2+(aq) + 2e-  Ni(s) Ered = -0.28 V
The standard emf for this cell is
Ecell = Ered (cathode) - Ered (anode) = 0 V
This cell operates under nonstandard conditions because of
the difference in concentration of Ni 2+(aq) in the two
compartments. The driving force for the cell is provided by
the difference in concentration. Operation of the cell tends
to equalize the concentrations of Ni 2+ in both
compartments.
Therefore, the compartment with the more dilute solution
will be the anode compartment; oxidation of Ni(s) at the
anode increases [Ni2+] in the more dilute solution. The
compartment with the more concentrated solution will be
the cathode compartment, for the reduction of Ni 2+(aq) at
the cathode decreases [Ni2+] in that compartment.
The overall cell reaction is
Anode : Ni(s)  Ni2+(aq ; dilute) + 2e-
Cathode : Ni2+(aq ; concentrated) + 2e-  Ni(s)
Overall : Ni2+(aq ; concentrated)  Ni2+(aq ; dilute)
The emf of the cell at 298 K is
E = E - (0.0592 / n) log Q
= 0 - (0.0592 / 2) log ([Ni 2+]dilute / [Ni2+]concentrated)
E = +0.0888 V
The difference in concentration provides the driving force
for the cell. As the cell operates, the concentration of the
dilute solution in the anode compartment increases and
that of the concentrated solution in the cathode
compartment decreases.
When the concentrations in the two compartments
become equal, Q = 1 and E = 0.
Sample Exercise
9. A voltaic cell is constructed with 2 H electrodes.
Electrode 1 has PH2 = 1.00 atm and an unknown [H +].
Electrode 2 is a SHE, [H+] = 1.00 M and PH2 = 1 atm.
At 298 K, the cell voltage is measured to be 0.211 V
and the electrical current is observed to flow from
electrode 1 through the external circuit to electrode 2.
What is [H+] for the solution in electrode 1? What is its
pH?
(2.8 x 10-4 ; 3.56)
Practice Exercise
9. A concentration cell is constructed with 2 Zn(s) – Zn 2+
(aq) half – cells. The first cell has [Zn 2+] = 1.35 M and
the second cell has [Zn2+] = 3.75 x 10-4 M. Determine
the emf of the cell.
(0.105 V)
Cell EMF and Chemical Equilibrium
The emf of a voltaic cell drops as it is discharged. As
reactants are converted to products, the value of Q
increases, so the value of E decreases. Eventually the cell
emf reaches E = 0. When E = 0 , G = 0 and the cell
reaction has reached equilibrium; no net reaction is
occurring in the voltaic cell.
At equilibrium, E = 0 and Q = K, thus at 298 K
E = E - (0.0592 / n) log Q
0 = E - (0.0592 / n) log K
or
log K = (n E / 0.0592)
Sample Exercise
10. Using the standard reduction potentials, calculate the
equilibrium constant for the oxidation of Fe 2+ by O2 in
acidic solution. The reaction is
O2(g) + 4H+(aq) + 4Fe2+(aq)  4Fe3+(aq) + 2H2O(l)
(1.2 x 1031)
Practice Exercise
10. Using standard reduction potentials, calculate the
equilibrium constant at 25C for the reaction
Br2(l) + 2Cl-(aq)  Cl2(g) + 2Br-(aq)
(7.3 x 10-11)
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C5ell Notation
Cell notation is a shorthand method of constructing a
galvanic cell without taking the trouble to draw the actual
picture of the cell.
Conventions:
 a salt bridge is represented by a //
 boundaries between different phases are represented
by a /
 boundaries between 2 different species in the same
phase are indicated by a ,
 to represent the complete cell, anode is written first
before the cathode using a salt bridge to separate
them
 to represent the anode, oxidation, write the solid first
then the ion, electrolyte, separated by a single bar
e.g. anode of Zn metal in a solution of Zn 2+ : Zn / Zn2+
e.g. anode consisting of solid Pt in contact with H 2
immersed in an aqueous solution of an acid solution like
HCl or H2SO4 : Pt / H2 / H+
 to represent the cathode, write the electrolyte first then
the solid last
e.g. cathode of Zn metal immersed in a solution containing
Zn2+ : Zn2+ / Zn
e.g. solid Pt with Cl2 adsorbed in the Pt surface immersed in
another solution containing Cl- ions :
Cl- / Cl2 / Pt
Sample Exercise
11. Write the cell notation for the Daniell cell
Practice Exercise
11. Write the half - cell reactions and the cell notations for
the following reactions:
(a) Ni(s) + Cu2+(aq)  Ni2+(aq) + Cu(s)
(b) Zn(s) + 2Fe3+(aq)  Zn2+(aq) + 2Fe2+(aq)
(c) Cl2(g) + 2I-(aq)  2Cl-(aq) + I2(g)
Preventing the Corrosion of Iron
Iron is often covered with a coat of paint or another metal
such as tin or zinc to protect its surface against corrosion.
Covering the surface with paint or tin is a means of
preventing O2(g) and H2O(l) from reaching the iron surface.
If the coating is broken and the iron is exposed to O 2(g)
and H2O(l) , corrosion will begin.
e.g. galvanized iron - iron coated with a thin layer of Zn
From the standard reduction potentials, the Ered for the
reduction of Fe2+ is less (-) than the reduction of Zn 2+, so
Fe2+ is easier to reduce than Zn2+ and Zn(s) is easier to
oxidize than Fe(s). Thus, even if the zinc coating is broken
and the galvanized iron is exposed to O 2(g) and H2O(l), the
zinc serves as the anode and is corroded instead of the
iron. The iron serves as the cathode at which O 2(g) is
reduced.
cathodic protection - protection of a metal by making it
the cathode in an electrochemical cell
sacrificial anode - the metal that is oxidized while
protecting the cathode
Sample Exercise
12. Predict the nature of the corrosion that would take
place if an iron gutter were nailed to a house using
aluminum nails.
Practice Exercise
12. Using the standard reduction potential, indicate which
of the following metals could provide cathodic
protection to iron: Al, Cu, Ni, Zn
(Al ; Zn)

CORROSION
Corrosion reactions are spontaneous undesirable redox
reactions in which a metal is attacked by some substance in
its environment and converted to an unwanted compound.

Corrosion of Iron
- rusting of iron
- requires O2(g) and H2O(l)
- the pH of the solution, the presence of salts,
contact with metals more difficult to oxidize
than iron, and stress on iron can accelerate
rusting

electrode reactions:
anode : Fe(s)  Fe2+(aq) + 2e-
cathode : O2(g) + 4H+(aq) + 4e-  2H2O(l)

A region on the surface of iron metal can serve as an anode

at which the oxidation of Fe to Fe 2+ occurs. The electrons
produced migrate through the metal to another portion of
the surface that serves as the cathode, at which O 2 is
reduced. Reduction of O2 requires H+. As the [H+] is
decreased or pH is increased, the reduction of O 2 becomes
less favorable. Iron in contact with a solution whose pH is
above 9 does not corrode.

The Fe2+ formed at the anode is oxidized further to Fe 3+,

which forms the hydrated iron(III) oxide or rust.

4Fe2+(aq) + O2(g) + 4H2O(l) + 2xH2O(l)  2Fe2O3xH2O(s)

+ 8H+(aq)

Rust often deposits in the cathode because it is generally

the area having the largest supply of O2.

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