An electrochemical cell consists of two electrodes,
which are simply metallic conductors, in contact with an ionic
conductor called the electrolyte.
(Though the most commonly encountered electrolytes are ionic
solutions, they may also be liquids, e.g. molten potassium bromide,
or solids, e.g. solid silver iodide. The only criterion is that
the substance must be an ionic conductor.)
A single electrode and its electrolyte makes up an electrode
compartment. The two electrodes in a cell may share the same
compartment, if they have the same electrolyte. Otherwise the
two compartments are joined by a salt
bridge, typically a concentrated electrolytic
solution in a matrix such as agar jelly.
The purpose of the salt bridge is
purely to complete the electrical circuit and allow the cell
to function.
The various kinds of electrode/electrolyte combination are
tabulated below, with explanatory notes following:
| Electrode type |
Notation |
Redox Couple |
Half-reaction |
| Metal/metal ion |
M(s)|M+(aq) |
M+/M |
M+(aq)
+ e- => M(s) |
| Gas electrode (i) |
Pt(s)|X2(g)|X+(aq) |
X+/X2 |
X+(aq)
+ e- => ½X2(g) |
| Gas electrode (ii) |
Pt(s)|X2(g)|X-(aq) |
X2/X- |
½X2(g) + e-
=> X-(aq) |
| Metal/insoluble salt |
M(s)|MX(s)|X-(aq) |
MX/M,X- |
MX(s) + e-
=> M(s) + X-(aq) |
| Redox |
Pt(s)|M+(aq),M2+(aq) |
M2+/M+ |
M2+(aq)
+ e- => M+(aq) |
Note that by convention, half-reactions are written as reduction
(electron gain) processes.
However, depending upon the redox potential of the other electrode
in the cell, it may actually be the reverse, oxidation process
which occurs at the electrode. (The oxidation process occurs
at the electrode composed of the more easily oxidised metal,
and vice versa.)
The metal/metal ion electrode system is usually the first type
people encounter. A typical example would be a metal electrode
dipped into an aqueous solution of a salt of that metal. Electron
transfer occurs between the metal atoms of the electrode and
the metal ions in solution.
The gas electrodes are essentially very alike. They typically
consist of a platinum electrode dipped into a solution containing
the anion or cation of the gas in question. The gas is bubbled
slowly over the surface of the platinum electrode. Electron
transfer occurs between the gas and the ions in solution. The
platinum is present to catalyse the reaction by providing a
surface area for it to take place on, and to act as a source
or acceptor of electrons. Platinum (or a similar inert metal)
is chosen to avoid the possibility of reaction with the gas
or solution.
The metal/insoluble salt electrode normally consists of a metal
electrode in contact with (partially coated with a thin layer
of) an insoluble salt of the metal. This assembly is then held
in contact with a solution containing the anion of the insoluble
salt. Electron transfer occurs between the metal atoms of the
electrode and the metal ions in the insoluble salt.
The redox electrode consists of a solution containing ions
of a metal in two different oxidation states. e.g. an
aqueous solution with one mole of Fe(NO3)2
and one mole of Fe(NO3)3 dissolved in
it would be suitable, as it contains both Fe (II) and Fe (III)
ions. An inert metal electrode must be dipped into the solution
to act as a source or acceptor of electrons and allow the electrode
system to be linked to another electrode to create a complete
cell.
There are two basic types of electrochemical cell. A galvanic
cell is one which generates electricity as a result of
the cell reaction, which is a spontaneous (thermodynamically
favourable) process. In an electrolytic
cell, a non-spontaneous cell reaction is driven to occur
by the application of an external source of current. These two
types of cell are in many ways direct opposites - the cell reaction
of a galvanic cell can be reversed in an electrolytic cell with
a sufficient source of external current.
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