ELECTROCHEMISTRY

ELECTROCHEMISTRY is the branch of chemistry that

deals with the relationship between electrical
energy and chemical energy.

ELECTROCHEMICAL PROCESSES – are (redox)

oxidation–reduction reactions in which the energy
released by a spontaneous reaction is converted to
electricity

REDOX (oxidation-reduction) reactions –occurs

when electrons are transferred from an atom that is
oxidized to an atom that is reduced.
OXIDATION NUMBER (OXIDATION STATE) – signifies
the number of charges the atom would have in a
molecule or in an atomic compound if electrons
were transferred completely.
RULES IN ASSIGNING OXIDATION NUMBERS

• The oxidation number of a free element is always 0.

• The oxidation number of a monatomic ion equals the charge of the ion.
• Fluorine in compounds is always assigned an oxidation number of -1.
• The alkali metals (group I) always have an oxidation number of +1.
• The alkaline earth metals (group II) are always assigned an oxidation number of
+2.
• Oxygen almost always has an oxidation number of -2, except in peroxides (H2O2)
where it is -1 and in compounds with fluorine (OF2) where it is +2.
• Hydrogen has an oxidation number of +1 when combined with non-metals, but
it has an oxidation number of -1 when combined with metals.
• The algebraic sum of the oxidation numbers of elements in a compound is zero.
• The algebraic sum of the oxidation states in an ion is equal to the charge on the
ion.

• Source: www.periodni.com
OXIDATION REACTION – refers to the half-reaction that
involves the loss of electrons

REDUCTION REACTION – refers to the half-reaction that

involves the gain of electrons

OXIDIZING AGENT - the one that accepts electrons; the one

that is reduced

REDUCING AGENT – the one that donates electrons; the one

that is oxidized

OILRIG: Oxidation Is Loss (of electrons). Reduction Is Gain (of

electrons).

LEOGER: Loss Electron – Oxidation. Gain Electron - Reduction

EXERCISE (01)
Identify the oxidizing and reducing agents in the
reaction
BALANCING REDOX REACTIONS

1. The amount of each element must be the same on

both sides of the equation.
2. The gains and losses of electrons must be balanced.

HALF-REACTIONS – equations that show either

oxidation or reduction alone.

ll
BALANCING REDOX REACTIONS BY THE METHOD OF
HALF-REACTIONS

A. For balancing of redox reaction that occurs in acidic

aqueous solution.

1. Divide the equation into one oxidation half-reaction

and one reduction half-reaction.
2. Balance each half-reaction.
(a) Balance elements other than H and O.
(b) Balance O atoms by adding H2O as needed.
(c) Balance H atoms by adding H+ as needed.
(d) Balance charge by adding e- as needed.
3. Multiply half-reactions by integers as needed to
make the number of electrons lost in the oxidation half-
reaction equal the number of electrons gained in the
reduction half-reaction.

4. Add half-reactions and, if possible, simplify by

cancelling species appearing on both sides of the
combined equation.

5. Check to make sure the atoms and charges are

balanced.
EXERCISE (2)

Balance the following equations occurring in an

acidic medium:
B. For balancing of redox reaction that occurs in basic
aqueous solution.

1. Divide the equation into one oxidation half-reaction and

one reduction half-reaction.
2. Balance each half-reaction.
(a) Balance elements other than H and O.
(b) Balance O atoms by adding H2O as needed.
(c) Balance H atoms by adding H+ as needed.
(d) Balance charge by adding e- as needed.
(e) Count the number of H+ in each half-reaction and add
the same number of OH- to each side of the reaction.
(f) Neutralize H+ and OH- by forming H2O when they are
on the same side of either half-reaction.
(g) Cancel water molecules that both appear in the
product and reactant sides.
3. Multiply half-reactions by integers as needed to
make the number of electrons lost in the oxidation half-
reaction equal the number of electrons gained in the
reduction half-reaction.

4. Add half-reactions and, if possible, simplify by

cancelling species appearing on both sides of the
combined equation.

5. Check to make sure the atoms and charges are

balanced.
EXERCISE (3)

Balance the following equations occurring in a basic

medium:
The energy released in a
spontaneous redox reaction can
be used to perform electrical
work.

GALVANIC (VOLTAIC) CELL – a

device in which the transfer of
electrons takes place in an
external pathway rather than
directly between the reactants
present in the same reaction
vessel.
ANODE – the electrode in a galvanic cell is the
electrode in which oxidation occurs

CATHODE – electrode at which reduction occurs

HALF-CELL REACTION
Anions always migrate toward
the anode and cations toward
the cathode through an external
circuit.

Because of this directional flow,

the anode in a voltaic cell is
labeled with a negative sign and
the cathode is labeled with a
positive sign.
EXERCISE (4)

The two half-reaction in a voltaic cell are

(a) Indicate which reaction occurs at the anode and

which at the cathode.
(b) Which electrode is consumed in the cell
reaction?
(c) Which electrode is positive?
Cell diagram – the conventional notation for
representing galvanic cells

CELL POTENTIALS UNDER STANDARD CONDITIONS

• Potential energy is higher at the anode than at

the cathode; thus, electrons flow spontaneously
toward the electrode with the more positive
electrical potential.
One volt (V) is the potential difference required to
impart 1 Joule of energy to a charge of 1 coulomb, C

Cell potential (Ecell) is the potential difference

between the two electrodes of a voltaic cell. Also
called the electromotive force, emf and voltage of
the cell.

The magnitude of the cell potential depends on the

reactions that occur at the cathode and anode, the
concentrations of reactants and products and the
temperature.
Standard cell potential or standard emf, E°cell, is the cell
potential under standard conditions (1M
concentrations of products and reactants in solution, 1
atm pressure and 26°C.

Standard reduction potentials are intensive properties.

The more positive the value of E°red, the greater

tendency for reduction under standard conditions.
EXERCISE (5)

The standard cell potential is 1.46V for a voltaic cell

based on the following half-reactions:

Using Table 20.1, calculate E°red for the reduction of

In3+ to In+.
EXERCISE (6)

Using date in Table 20.1, calculate the standard emf

for a cell that employs the overall cell reaction:
EXERCISE (7)

A voltaic cell is based on Co2+/Co half-cell and an

AgCl/Ag half cell.

a. What half reaction occurs at the anode?

b. What is the standard cell potential?
EXERCISE (8)

Using Table 20.1, rank the following species from

the strongest to the weakest reducing agent:

I-(aq), Fe(s), Al(s)

FREE ENERGY AND REDOX REACTIONS

A positive value of E indicates a spontaneous

process; a negative value of E indicates a non-
spontaneous process.

*E is used to represent the emf under non-standard

conditions.
EXERCISE (9)

Using the standard potentials listed in Appendix E,

determine which of the following reactions are
spontaneous under standard conditions:
Emf, Energy and the equilibrium constant

n = a positive number without units that represents

the number of moles of electrons transferred
according to the balanced equation for the reaction
F = Faraday’s constant

At standard conditions:
EXERCISE (10)

For the reaction

a) What is the value of “n”?

b) Use the data in Appendix E to calculate ∆G°.
c) Calculate K at T=298K
Electrical work
CELL POTENTIAL UNDER NON-STANDARD CONDITIONS

As voltaic cell is discharged, reactants are consumed

and products are generated, so concentrations change.
The emf progressively drops until E = 0, at which point,
the cell is “dead”.

Nernst Equation:

Q = reaction quotient
EXERCISE (11)

Calculate the emf generated by the cell described in

the given reaction when [Al3+]=4.0x10-3 and
[I-]=0.010M.
CONCENTRATION CELLS – cells based solely on the
emf generated because of a difference in a
concentration
Lead-Acid Battery

A 12-V lead-acid automotive battery

consists of six voltaic cells in series,
each producing 2V. The cathode of
each cell is lead dioxide (PbO2)
packed on a lead grid. The anode of
each cell is lead. Both electrodes are
immersed in sulfuric acid.
ALKALINE BATTERY – the most common non-rechargeable
battery. The anode is a powdered zinc metal immobilized in a
gel in contact with a concentrated KOH. The cathode is a
mixture of MnO2 and graphite, separated from the anode by
a porous fabric. The battery is sealed with in a steel can to
reduce the risk of any of the concentrated KOH escaping.
NICKEL-CADMIUM, NICKEL-METAL-HYDRIDE,
LITHIUM-ION BATTERIES

HYDROGEN FUEL CELLS

CORROSION REACTIONS are spontaneous redox
reactions in which a metal is attacked by some
substance in its environment and converted to an
unwanted compound
ELECTROLYSIS –

It is possible for nonspontaneous redox reaction to

occur by using electrical energy to drive them.
EXERCISE (12)

a) The half-reaction for formation of magnesium

metal upon electrolysis of molten MgCl2 is given
in the above reaction. Calculate the mass of
magnesium formed upon passage of a current of
60.0 A for a period of 4.00 x103 s.
b) How many second would be required to produce
50.0g of Mg from MgCl2 if the current is 100.0A?