| If a chemical reaction is caused by an external voltage or if
a voltage is caused by a chemical reaction, e.g. in a Battery (electricity), it is an electrochemical
reaction. In general, electrochemistry deals with situations where an oxidation and a reduction reaction is separated in
space. The direct charge transfer from one molecule to another is not the topic of electrochemistry.
The following is a definition of electrochemistry:
Electrochemistry is the science of the reactions that can take place at the interface of an electronic conductor (the electrode, which can be a metal or a semiconductor including graphite)
and an ionic conductor (the electrolyte).
Oxidation and Reduction are the Basis of Electrochemistry, but not the Main Point!
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 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.
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).
In the 1960s–1970s quantum electrochemistry was developed by Revaz Dogonadze and his pupils.
The International
Society of Electrochemistry (ISE) was founded in 1949.
Spontaneity
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.
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