ELECTROCHEMISTRY

The study of the conversion of the energy of chemical reactions into electrical energy.
The major topics studied in this unit are:
 Balancing Oxidation-Reduction (redox) reactions
 Galvanic/Voltaic (spontaneous) cells
 Electrolytic (non-spontaneous) cells

BALANCING REDOX REACTIONS

Electrochemistry is the study of redox reactions and their practical applications. A redox
reaction involves both oxidation (loss of electrons, an increase in oxidation number),
and reduction (gain of electrons, a decrease in oxidation number). Essentially a redox
reaction involves the transfer of an electron(s) from one species to another- the species
that is oxidized is the reducing agent, and the species that was reduced is the oxidizing
agent.

Oxidation numbers are actual (ex: Al3+ has an oxidation number of +3) or theoretical
charges (ex: Oxygen has an oxidation number of -2 in H2O) that are used to identify if
the reaction is a redox reaction, and if so, which species are reduced and oxidized.
Oxidation numbers are derived from Lewis structures using the following reasoning: the
more electronegative element in a compound "owns" all of the bonding and non-bonding
electrons surrounding it. Subtract these electrons from the valence electrons of the
element and you get the oxidation number. A simpler method for oxidation numbers is
to apply the summarized rules:

 A pure element has an oxidation number of zero (ex: Na, Cl2, etc.)
 The oxidation number of a monoatomic ion equals the charge of the ion (ex: Al3+
has an oxidation number of +3)
 The oxidation number of hydrogen is generally +1, except when it is a hydride
(ex: LiH) it is -1
 The oxidation number of oxygen is generally -2 (some exceptions include OF2,
H2O2)
 In covalent compounds, the more electronegative element is assigned an
oxidation number that equals the negative charge it usually has in ionic
compounds (ex: Cl is -1 in PCl3)
 The sum of the oxidation numbers of all of the elements in a compound is equal
to the total charge of the compound.
Balancing Redox Reactions – Half-Reaction Method

When balancing redox reactions, both mass and charge must be balanced. There
are generally three different situations where redox reactions must be balanced:
neutral reactions, reactions in acidic solution, and reactions in basic solution. The
half-reaction method generally works in all situations, and it involves the following
steps:

 Assign oxidation numbers to each element in the reaction and identify the
species being oxidized and reduced
 Write separate half-reactions for the oxidation and reduction processes.
There are always 2 half-reactions, one for just the species being oxidized,
and one for just the species being reduced. The half-reaction shows a gain
or loss of electrons, and it must be balanced for mass and charge.
 Multiply each half-reaction by a factor (if necessary) so as to make the
number of electrons transferred in each half-reaction EQUAL
 Recombine the half-reactions back into the original reaction
 Balance the net charge by either adding OH- to one side of the equation (for
basic solutions only) or H+ (for acidic solutions only)
 Balance the O and H atoms by adding H2O

(example)

Balancing Redox Reactions – Oxidation Number Method

As per the half-reaction method, an equation is only balanced when both mass
and charge are balanced. The oxidation number method focuses on identifying
and then balancing the total change in oxidation number, which is essentially the
same as the total transfer of electrons. Use the following steps:

 Determine the oxidation numbers of each of the species in the chemical

equation
 Identify those species whose oxidation numbers changed from reactant to
product (there should only be one species which has been oxidized, which is
an increase in oxidation number, and one species that has been reduced,
which is a decrease in oxidation number)
 Determine the total change in oxidation numbers (for the changing species)
on a per atom basis
 Determine the lowest common multiple (LCM) for the changing species on a
per atom basis (to ensure that the total increase in oxidation numbers equals
the total decrease in oxidation numbers). Use these LCMs as the coefficients
for the changing species.
 Balance the other elements by inspection
 Balance the oxygen atoms using H2O and the H atoms using H+ for acidic or
other aqueous solutions. For basic solutions, add enough OH- ions (to both
sides) to cancel out the amount of H+ ions, combine H+ and OH- on the same
side to form H2O and cancel the same number of H2O on both sides of the
equation.
(example)
ELECTROCHEMICAL CELLS

There are two types of electrochemical cells: 1) voltaic/galvanic cells, which

spontaneously convert chemical energy into electrical energy, and 2) electrolytic cells,
which non-spontaneously convert electrical energy into chemical energy.

VOLTAIC/GALVANIC CELLS

This type of cell involves the physical separation of two separate half-reactions from
each other, into two separate half-cells, in order to "re-route" the electrons that
spontaneously move from the oxidized species to the reduced species (Figure 1). The
re-routing of the electrons is through an external wire that is connected to both the
oxidized species (the negatively charged anode) and the reduced species (the positively
charged cathode), as this wire provides the path of least resistance. The purpose of this
is to take advantage of the electrical energy that is generated by moving electrons and
have it do useful work (such as power an electrical device).

The half-cells must be physically connected via a salt bridge in order to complete the
circuit. A salt bridge is composed of a medium (such as a glass tube or a saturated
piece of paper) which contains a non-reactive salt solution (ex: KNO3) that is able to
slowly migrate between the two half-cells in order to balance/neutralize any buildup of
charge. The half-cells themselves consist of the electrodes (anode or cathode) in a
solution of their respective cation (ex: Mg(s) in a solution of MgSO4). It should be noted
that voltaic/galvanic cells are often represented by their shorthand notation, for example
Mg(s) | Mg2+(aq) || Al3+(aq) | Al(s)

Figure 1: A galvanic/Voltaic cell with a Magnesium as the anode and aluminum as the
cathode.
Voltaic/galvanic cells are essentially simple cells or what are commonly referred to as
batteries (technically a battery is a combination of cells). How do you know which
metals are the anode or cathode? How do you design a "better" or higher voltage
battery? The answer lies in the standard reduction potential of the metals (Figure 2).
Some metals are more reactive than others (refer to the activity series), and therefore
will more readily lose their electrons. The greater the potential difference between two
metals, or the greater their cell potential (E°), the greater the voltage and therefore the
more energy the cell can provide (as well, cells can be connected in series to increase
their voltage). The metal that has the more negative reduction potential is the one that is
oxidized and the metal that has the greater (more positive) reduction potential is
reduced. Electrons will always spontaneously flow towards the half-cell/electrode with
the higher/more positive E° value.

The standard cell potential of the voltaic cell can be calculated using a table of standard
reduction potentials and the relationship: E°cell = E°red + E°ox
When performing these calculations, you need to note the following:

 All reduction potentials are written as reductions. To convert them into oxidations,
reverse the reaction and reverse the sign
 Reduction potentials are intensive quantities. This is to say that their values do not
depend on the amounts of matter involved in the reaction, therefore do not multiply
reduction potentials by any factors
 Reduction potentials are measured at standard states. If experimental conditions are
not standard, the reduction potential values will vary and the reduction potential is
indicated as E rather than E°

(example)
Figure 2: Standard Reduction Potentials at SATP. Note that these are all written as
reductions by convention, and they can be easily reversed to be written as oxidations
(and the sign of the potential will therefore reverse also).
ELECTROLYTIC CELLS

These types of electrochemical cells are essentially the exact opposite of a

galvanic/voltaic cell, in that they convert electrical energy into chemical energy, and are
non-spontaneous, and therefore have a negative cell potential. Electrolytic cells consist
of two electrodes (the anode, which is the site of oxidation but has a positive value, and
the cathode, which is the site of reduction and has a negative value), electrolyte(s), and
an external circuit that includes an external power supply (to provide the electrical
energy input). Some electrolytic cells include a salt bridge or porous barrier, while some
do not.

Figure 1: Galvanic Cell vs. an Electrolytic Cell

Notice that oxidation occurs at the anode and reduction occurs at the cathode, just like in
a galvanic cell, however, the signs of the electrodes are reversed as well the metals that
comprise the electrodes are reversed (indicating that the electron flow is now reversed,
as compared to the original galvanic cell).

It should be noted that the external voltage needed for an electrolytic cell is always
greater than the calculated value (using reduction potentials); this is referred to as
overvoltage and it depends on the materials in the electrodes and the nature of the
substances to be electrolyzed (particularly significant when dealing with gases).

Electrolysis of Aqueous Solutions

The electrolysis of water is a common non-spontaneous application of electrolytic cells.
Because it is generally impractical to use 1 M concentrations of water (the standard state
value), the reduction potential of E, rather than E◦ is used, with a concentration of 1 x10-
14
M for water, and the reduction potential values:

O2(g) + 4H+(aq) + 4e- ↔ 2H2O(l) E= 0.815 V

2H2O(l) + 2e- ↔ H2(g) + 2OH-(aq) E= -0.414 V

Since water is a universal solvent, most substances to be electrolyzed are dissolved in

water, and this leads to a practical issue that needs to be identified and corrected for.
When electrolyzing a substance, such as a dissolved salt, it is not always the case that
the intended salt will actually be electrolyzed. Instead, it can be the case that water or
part of the water is electrolyzed, rather than the intended salt. To evaluate which
species are actually electrolyzed in aqueous solution, use the following process:
 Write the half-reactions for water (see two reactions above) and for the desired
salt (this should give you a total of 4 half-reactions)
 Combine all possible pairs of half-reactions obtain overall reactions (this will
produce four different possibilities)
 The overall reaction that requires the lowest external voltage will be the reaction
that actually occurs
(example)

Faraday’s Law

Faraday’s Law is useful to precisely control/quantify the process of electrolysis, as it

bridges the concepts of stoichiometry and electrochemistry, and it states that the amount
of a substance produced or consumed in an electrolysis reaction is directly proportional
to the quantity of electricity that flows through the circuit.

In order to solve electrochemical stoichiometry problems, some basic concepts of

electricity, their units, and a fundamental ratio need to be introduced. Electric charge
(units: Coulombs (C) or Amperes (A) x seconds (s)) is a measure of the quantity of
electricity, electric current (units: Amperes(A)) is a measure of the flow of electrons past
a given point, and potential difference or voltage (units: Volt (V)) is a measure of the
energy that a moving electron(s) has measured by the difference of potential energy
between two points. The charge on one mole of electrons (units: 1 Faraday (F)) is equal
to 96 500 C/mol, and is derived by taking the product of the charge of one electron
(1.602 x 10-19 C) and one mole of electrons (6.02 x1023 electrons).

(example)