Electrochemistry

Electrochemistry is a branch of chemistry that studies the reactions which take place at
the interface of an electronic conductor (the electrode composed of a metal or a
semiconductor, including graphite) and an ionic conductor (the electrolyte).
If a chemical reaction is caused by an external voltage, or if a voltage is caused by a
chemical reaction, as in a battery, it is an electrochemical reaction. In general,
electrochemistry deals with situations where an oxidation and a reduction reaction are
separated in space. The direct charge transfer from one molecule to another is not the
topic of electrochemistry.

Principles
Redox reactions
Electrochemical processes are redox reactions where energy is produced by a
spontaneous reaction which produces electricity, or where electrical current stimulates a
chemical reaction. In a redox reaction, an atom's or ion's oxidation state (basically, its
charge) changes as a result of an electron transfer.

Oxidation and Reduction

The elements involved in an electrochemical reaction are characterized by the number of
electrons each has. The oxidation state of an ion is the number of electrons it has
accepted or donated compared to its neutral state (which is defined as having an
oxidation state of 0). If an atom or ion donates an electron in a reaction its oxidation
state is increased, if an element accepts an electron its oxidation state is decreased.
For example when sodium reacts with chlorine, sodium donates one electron and gains
an oxidation state of +1. Chlorine accepts the electron and gains an oxidation state of
1. The sign of the oxidation state (positive/negative) actually corresponds to the value

of each ion's electronic charge. The attraction of the differently charged sodium and
chlorine ions is the reason they then form an ionic bond.
The loss of electrons of a substance is called oxidation, and the gain of electrons is
reduction. This can be easily remembered through the use of mnemonic devices. Two of
the most popular are "OIL RIG" (Oxidation Is Loss, Reduction Is Gain) and "LEO" the
lion says "GER" (Lose Electrons: Oxidization, Gain Electrons: Reduction).
The substance which loses electrons is also known as the reducing agent, or reductant,
and the substance which accepts the electrons is called the oxidizing agent, or oxidant.
The oxidizing agent is always being reduced in a reaction; the reducing agent is always
being oxidized.
The gain of oxygen, loss of hydrogen and increase in oxidation number is also considered
to be oxidation, while the inverse is true for reduction.
A reaction in which both oxidation and reduction is occurring is called a redox reaction.
These are very common; as one substance loses electrons the other substance accepts
them.
Oxidation requires an oxidant. Oxygen is an oxidant, but not the only one. Despite the
name, an oxidation reaction does not necessarily need to involve oxygen. In fact, even
fire can be fed by an oxidant other than oxygen: fluorine fires are often unquenchable, as
fluorine is an even stronger oxidant (it has a higher electronegativity) than oxygen.

Balancing redox reactions

Electrochemical reactions in water are better understood by balancing redox reactions
using the Ion-Electron Method where H+ , OH- ion, H2O and electrons (to compensate the
oxidation changes) are added to cell's half reactions for oxidation and reduction.

Acid medium
In acid medium H+ ions and water are added to half reactions to balance the overall
reaction. For example, when Manganese reacts with Sodium bismuthate.

Finally the reaction is balanced by multiplying the number of electrons from the
reduction half reaction to oxidation half reaction and vice versa and adding both half
reactions, thus solving the equation.

Reaction balanced:

Basic medium
In basic medium OH- ions and water are added to half reactions to balance the overall
reaction. For example on reaction between Potassium permanganate and Sodium sulfite.

The same procedure as followed on acid medium by multiplying electrons to opposite

half reactions solve the equation thus balancing the overall reaction.

Equation balanced:

Neutral medium
The same procedure as used on acid medium is applied, for example on balancing using
electron ion method to complete combustion of propane gas.

As in acid and basic medium, electrons which were used to compensate oxidation
changes are multiplied to opposite half reactions, thus solving the equation.

Equation balanced:

Electrochemical cells

A modified version of Daniells Cells, a UShaped tube is replaced with a porous disk
acting as saline bridge thus electric current is produced.
An electrochemical cell is a device capable of producing electric current from energy
released by a spontaneous redox reaction. This kind of cell is also known as Galvanic
cell or Voltaic cell, named after Luigi Galvani and Alessandro Volta, both scientists who
conducted several experiments on chemical reactions and electric current during the late
18th century.
In a Galvanic cell the anode is defined as the electrode where oxidation occurs and the
cathode is the electrode where the reduction takes place.
The Galvanic cell's metals dissolve in the electrolyte at two different rates, leaving some
electrons in the rest of the metal, which makes it negative with respect to the electrolyte.
Each metal in the Galvanic cell undergoes a different half-reaction. This causes the
metals to have different dissolving rates, leading to an unequal number of electrons in the
two metals. This results in a different electrode potential between the electrolyte and each
metal. If an electrical connection, such as a wire or direct contact, is formed between the
two, an electric current flows between the metals.
An electrochemical cell whose electrodes are Zinc and Copper submerged in Zinc sulfate
and Copper sulfate, respectively, is known as a Daniells cell.
Half reactions for a Daniells cell are these:

A modern cell stand for electrochemical research. The electrodes attach to high-quality
metallic wires, and the stand is attached to a potentiostat/galvanostat (not pictured). A
shotglass-shaped container is aerated with a noble gas and sealed with the teflon block.
In order to avoid positive charges accumulating on the anode's compartment, an inverted
Ushaped tube called a salt bridge filled with an electrolytic solution is placed on the
cell, thus allowing flow of ions, producing an electric current.
A voltmeter is capable of measuring the change of electrical potential between the anode
and the cathode.
Electrochemical cell voltage is also referred to as electromotive force or emf.
A cell diagram can be used to trace the path of the electrons in the electrochemical cell.
For example, here is a cell diagram of a Daniells cell:

First, the reduced form of the metal to be oxidized at the anode (Zn) is written . This is
separated from its oxidized form by a vertical line, which represents the limit between the
phases (oxidation changes). The double vertical lines represent the saline bridge on the
cell. Finally, the oxidized form of the metal to be reduced at the cathode, is written,
separated from its reduced form by the vertical line.

Standard electrode potential

Standard electrode potential is the value of the standard emf of a cell in which molecular
hydrogen under standard pressure (105 Pa) is oxidized to solvated protons at the lefthand electrode.
The cell potential depends on the difference between each half cell potential.
Conventionally the potential associated with each electrode is chosen as the reduction
takes place on the chosen electrode, hence standard electrode potential are tabulated on
reduction potentials, thus tables are built on standard reduction potentials noted as
.
Standard cell potential is calculated by the difference between the standard reduction
potentials of each electrode.

It is impossible to measure directly half cell standard reduction potential, to avoid this
problem a standard reduction potential is assignated to a reference acting as an electrode
equivalent to

. Cell's half reaction used for this procedure is hydrogen which

in standard temperature and pressure conditions (105 Pa, 298.15 K, 1 mol. L-1) acts as a
zero volt electrode.
The standard hydrogen electrode or (SHE) consists on an inverted glass tube similar to a
laboratory test tube, where a light and fine platinum wire is connected to a thin platinum
blade. This setup is placed in a solution of Hydrochloric acid, plenty of H+ ions, gaseous
hydrogen enter through the tube and react over the platinum blade thus allowing
reduction and oxidation processes to occur.
SHE operates exactly as the same way as conventional electrodes on Daniells cell's
work; in order to measure the standard reduction potential, SHE replaces one of the
electrodes in the electrochemical cell acting as cathode or anode, thus electric current

generated on the cell represents the standard reduction potential for the element which is
measured.
For example on Copper standard reduction potential:

At standard temperature pressure conditions cell's emf (measured by a multimeter) is

0.34 V, conventionally SHE has a zero value, thus replacing on previous equation gives:

Electrochemical cell's emf value is used to predict whether redox reaction is a

spontaneous process or not. A positive sign for overall cell's standard potential is
considered to be spontaneous reaction, a negative sign would predict a spontaneous
reaction on the opposite direction.
Changes over stoichiometric coefficients on balanced cell equation will not change
value because standard electrode potential are intensive properties.

Spontaneity of Redox systems

thematically as the product between cell's emf by electrical charge in Coulombs.

Electrochemical cell's total charge is determined by multiplying the number of moles by

Faraday's constant (F).

Faraday's constant is the electrical charge in 1 mole of electrons, it has been measured
experimentally and is equivalent to 96 485.3 coulombs.
Cell's emf measured is the maximum voltage produced, this value is used to calculate the
maximum electrical energy which is obtained from a chemical reaction, this energy is
referred to as electrical work and is expressed on the following equation,

,thus free energy is the amount of mechanical (or other) work that can be extracted from
a system, replacing this value on previous equation with

gives the relation between

spontaneity and electrochemical cells.

The relation between Gibbs free energy and maximum electrical work may predict (at
standard temperature and pressure conditions) whether cell's redox system is a
spontaneous process or not.
A spontaneous electrochemical reaction can be used to generate an electrical current, in
electrochemical cells. This is the basis of all batteries and fuel cells. For example,
gaseous oxygen (O2) and hydrogen (H2) can be combined in a fuel cell to form water and
energy (a combination of heat and electrical energy, typically).
Conversely, non-spontaneous electrochemical reactions can be driven forward by the
application of a current at sufficient voltage. The electrolysis of water into gaseous
oxygen and hydrogen is a typical example.
The relation between equilibrium constant and spontaneity based on Gibbs free energy
terms on electrochemical cells is expressed as follows:

Solving both equations express cell's mathematical relation between standard potential,
and equilibrium constant.

Previous equation can use Briggsian logarithm as shown below:

Cell emf dependency on changes in concentration

Nernst Equation
Calculating cell's potential is not always possible at standard temperature and pressure
conditions. However in 1900s German chemist Walther Hermann Nernst proposed a
mathematical model to determine electrochemical cell potential where standard
conditions cannot be reached.
In the mid 1800s Willard Gibbs formulated an equation for spontaneous process at any
conditions,
,
Where:
G = change in Gibbs free energy, T = absolute temperature, R = gas constant, ln =
natural logarithm, Q = reaction quotient.

Willard stated Q's dependency over reactants and products activity and designated it as
their respective chemical activity.
Walther based on Willard Gibbs work during the mid 19th century, formulated a new
equation where replaced

's value with cell's respective maximum electrical work,

on Gibbs equation.

Where:
n = number of electrons/mole product, F = Faraday constant (coulombs/mole), and E
= electrical potential of the reaction.

Finally he replaced

's value with electrochemical cell potential, thus

formulating a new equation which now bears his name.

Assuming standard conditions (

) and R =

the equation above can be expressed on Base10 logarithm as shown

below:

Concentration cells

A concentration cell is an electrochemical cell whose electrodes are from the same
material differing in ionic concentrations on both half-cells.
For example an electrochemical cell, where two copper electrodes are submerged on
blue vitriol's solution, whose concentrations are 0.05 M and 2.0 M , while connected
through wire and saline bridge.

Le Chatelier's principle indicates reaction is favourable to reduction as concentration of

ions increases. Reduction will take place in cell's compartment where
concentration is higher and oxidation will occur on the diluted side.
The following cell diagram describes the cell mentioned above:

Where both half cell reactions for oxidation and reduction are:

Where cell's emf is calculated through Nernst equation as follows:

's value of this kind of cell is zero, as electrodes and ions are the same in both halfcells. After replacing values from case mentioned is possible to calculate cell's potential:

However, this value is only approximate, because the potential difference is given from
the ratio of activities of the ions, not the ratio of concentrations.
Concentration cell's are often a significant biologist's matter of investigation hence they
are present on biological cells where membrane potential is responsible of nerve
synapses and cardiac beat.

Battery
A battery is an electrochemical cell or a group of them, where if combined together, may
produce direct current at a constant voltage. Electrochemical principles which made
batteries work are the same as on electrochemical cells, however a battery doesn't need
auxiliary components such as saline bridge on Daniell cells.

Dry cell

Zinc carbon battery diagram.

Dry cells don't have a fluid electrolyte instead they use a moist electrolyte paste.
Leclanch's cell is a good example of this, where cell's anode is a zinc container
surrounded by a thin layer of manganese dioxide and a moist electrolyte paste of
ammonium chloride and zinc chloride mixed with starch to have a pale and flabby
consistency and avoiding flees. The cell's cathode is represented by a carbon bar inserted
on cell's electrolyte, usually placed in the middle.
Leclanch's simplified half reactions are shown below:

The voltage obtained from the zinc-carbon battery is 1.5 V approximately.

Mercury battery

Cutaway view of a Mercury battery diagram.

Mercury battery has many applications on medicine and electronics. The battery consists
of a steelmade container with the shape of a cylinder acting as the cathode, where an
amalgamated anode of mercury and zinc is surrounded by a stronger alkaline electrolyte
and a paste of Zinc oxide and Mercury(II) oxide .
Mercury battery half reactions are shown below:

There are no changes in the electrolyte's composition when the cell works. Such
Mercurium batteries provide 1.35 V of direct current.

Lead-acid battery

The Lead-acid battery used on automobiles, consists on a series of six identical cells in
line assembled, each cell has a lead anode and a cathode made from lead dioxide packed
in a metal plaque. Cathode and anode are submerged in a solution of sulfuric acid acting
as the electrolyte.
Lead-acid battery half cell reactions are shown below:

At standard conditions, each cell may produce a direct current of 2 V, hence overall
voltage produced is 12 V. Lead-acid batteries, differing from Mercury and Zinc-carbon
batteries, are rechargeable. If an external voltage is supplied to the battery it will
produce an electrolysis of the products in the overall reaction (discharge), thus
recovering initial components which made the battery work.

Solid state Lithium battery

Most of the batteries work using an aqueous electrolyte or a moist electrolyte paste
instead, however a solid state battery operates using a solid electrolyte. Solid state
lithium batteries are an example of this, where a solid Lithium bar acts as the anode, a
bar of Lithium sulfide or Vanadium oxide acts as the cathode and a polymer, allowing the
passage of ions and not electrons, serves as the electrolyte. The advantage of this kind of
battery from others is that Lithium possess the highest negative value of standard
reduction potential. It is also a light metal and therefore less mass is required to generate
1 mole of electrons. This battery is not rechargeable and it can provide a direct current
with a potential of about 3 V.

Flow battery/ Redox flow battery

Most batteries have all of the electrolyte and electrodes within a single housing. A flow
battery is unusual in that the majority of the electrolyte, including dissolved reactive
species, is stored in separate tanks. The electrolytes are pumped through a reactor, which
houses the electrodes, when the battery is charged or discharged.
These types of batteries are typically used for large-scale energy storage (kWh - multi
MWh). Of the several different types that have been developed, some are of current
commercial interest, including the vanadium redox battery and zinc bromine battery.

Fuel cells
Fossil fuels are used in power plants to supply electrical needs, however their conversion
into electricity is an inefficient process. The most efficient electrical power plant may
only convert about 40% of the original chemical energy into electricity when burned or
processed.
To enhance electrical production, scientists developed fuel cells where combustion
reactions are stimulated by electrochemical methods, thus requiring continuous
replenishment of the reactants consumed.
The most popular is the oxygen-hydrogen fuel cell, where two inertelectrodes (porous
electrodes of Nickel and Nickel oxide) are placed in an electrolytic solution such as hot
caustic potash, in both compartments (anode and cathode) gaseous hydrogen and oxygen
are bubbled into solution.
Oxygen-hydrogen fuel cell reactions are shown bellow:

The overall reaction is similar to hydrogen combustion, differing on oxidation and

reduction took place in anode and cathode separately, similar to the electrode used in the
cell for measuring standard reduction potential having a double function acting as
electrical conductors providing a surface required to decomposition of the molecules into
atoms before electron transferring, thus named electrocatalysts. Platinum, nickel,
rhodium are good electrocatalysts.

Electrolysis
Spontaneous redox reactions produces electricity, thus passage of electrons through a
wire in the electric circuit. Electrolysis requires an external source of electrical energy to
induce a chemical reaction, this process takes place in a compartment called electrolytic
cell. Principles involved on electrolysis are the same as featured on electrochemical cells.

Electrolysis of molten sodium chloride

When molten, sodium chloride can be electrolysed to yield metallic sodium and gaseous
chlorine. Industrially this process takes place in a special cell named Down's cell. The
cell is connected to a battery, allowing electrons migration from the battery to the
electrolytic cell.
Reactions that take place at Down's cell are the following:

This process can yield industrial amounts of metallic sodium and gaseous chlorine, and
is widely used on mineral dressing and metallurgy industries.
Standard emf for this process is approximately -4 V indicating a non-spontaneous
process. In order this reaction to occur the battery should provide at least a potential of

4V. However, on mineral refining industry, higher voltages are used, due to low efficiency
of the process.

Electrolysis of water

Diagram of a Hofmann voltameter, showing electrolysis of water.

Water at standard temperature and pressure conditions doesn't decompose into hydrogen
and oxygen spontaneously as the Gibbs free energy for the process at standard conditions
is about 474.4 kJ
However, special laboratory glassware has been designed for this purpose- the Hofmann
voltameter. In it, a pair of inert electrodes usually made of platinum act as anode and
cathode in the electrolytic process. After the water (if pure) has been placed in the
apparatus, nothing happens, hence there are not enough ions to let the passage of
electrons occur. To start the electrolysis an electrolyte should be placed in, usually
sodium chloride or sulfuric acid (most used 0.1 M).
Bubbles from the gases will be seen near both electrodes. The following half reactions
describe the process mentioned above:

Although strong acids may be used in the apparatus, the reaction will not net consume
the acid.

Electrolysis of aqueous solutions

Electrolysis in an aqueous is a similar process as mentioned in electrolysis of water.
However, it is considered to be a complex process because the contents in solution have
to be analyzed in half reactions, whether reduced or oxidized.
Electrolysis of a solution of Sodium chloride
The presence of water in a solution of sodium chloride must be examined in respect to its
reduction and oxidation in both electrodes. Usually, water is electrolysed as mentioned in
electrolysis of water yielding gaseous oxygen in the anode and gaseous hydrogen in the
cathode. On the other hand, sodium chloride in water dissociates in Na+ and Cl- ions,
anion will be attracted to the cathode, thus reducing the sodium ion. The cation will then
be attracted to the anode oxidizing chloride ion.
The following half reactions describes the process mentioned:

Reaction 1 is discarded as it has the most negative value on standard reduction potential
thus making it less thermodynamically favorable in the process.
When comparing the reduction potentials in reactions 2 & 4, the reduction of chloride
ion is favored. Thus, if the Cl- ion is favored for reduction, then the water reaction is
favored for oxidation producing gaseous oxygen, however experiments shown gaseous
chlorine is produced and not oxygen.

Although the initial analysis is correct, there is another effect that can happen, known as
the overvoltage effect. Additional voltage is sometimes required, beyond the voltage
predicted by the

. This may be due to kinetic rather than thermodynamic

considerations. In fact, it has been proven that the activation energy for the chloride ion
is very low, hence favorable in kinetic terms. In other words, although the voltage applied
is thermodynamically sufficient to drive electrolysis, the rate is so slow that to make the
process proceed in a reasonable time frame, the voltage of the external source has to be
increased (hence, overvoltage).
Finally, reaction 3 is favorable because it describes the proliferation of OH- ions thus
letting a probable reduction of H+ ions less favorable an option.
The overall reaction for the process according to the analysis would be the following:

As the overall reaction indicates, the concentration of chloride ions is reduced in

comparison to OH- ions (whose concentration increases). The reaction also shows the
production of gaseous hydrogen, chlorine and aqueous sodium hydroxide.

Quantitative electrolysis & Faraday Laws

Quantitative aspects of electrolysis were originally developed by Michael Faraday in
1834. Faraday is also credited to have coined the terms electrolyte, electrolysis, among
many others while he studied quantitative analysis of electrochemical reactions. Also he
was an advocate of the law of conservation of energy.
First law
Faraday concluded after several experiments on electrical current in non-spontaneous
process, the mass of the products yielded on the electrodes was proportional to the value

of current supplied to the cell, the length of time the current existed, and the molar mass
of the substance analyzed.
In other words, the amount of a substance deposited on each electrode of an electrolytic
cell is directly proportional to the quantity of electricity passed through the cell.
Below a simplified equation of Faraday's first law:

Where,
m is the mass of the substance produced at the electrode (in grams),
Q is the total electric charge that passed through the solution (in coulombs),
n is the valence number of the substance as an ion in solution (electrons per ion),
M is the molar mass of the substance (in grams per mole).
Second law
Faraday devised the laws of chemical electrodeposition of metals from solutions in 1857.
He formulated the second law of electrolysis stating "the amounts of bodies which are
equivalent to each other in their ordinary chemical action have equal quantities of
electricity naturally associated with them." In other terms, the quantities of different
elements deposited by a given amount of electricity are in the ratio of their chemical
equivalent weights.
An important aspect of the second law of electrolysis is electroplating which together
with the first law of electrolysis, has a significant number of applications in the industry,
as when used to protect metals to avoid corrosion.