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 Electrochemical cells

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Standard electrode potential

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From Wikipedia, the free encyclopedia

English chemist John Daniell (left) and physicist Michael

Faraday (right), both credited as founders of electrochemistry.

Electrochemistry is the branch of physical chemistry concerned with the

relationship between electrical potential difference and identifiable chemical change.
These reactions involve electrons moving via an electronically-conducting phase
(typically an external electrical circuit, but not necessarily, as in electroless plating)
between electrodes separated by an ionically conducting and electronically insulating
electrolyte (or ionic species in a solution).
When a chemical reaction is driven by an electrical potential difference, as
in electrolysis, or if a potential difference results from a chemical reaction as in
an electric battery or fuel cell, it is called an electrochemical reaction. Unlike in other
chemical reactions, in electrochemical reactions electrons are not transferred directly
between atoms, ions, or molecules, but via the aforementioned electronically-
conducting circuit. This phenomenon is what distinguishes an electrochemical
reaction from a conventional chemical reaction.[1]
History[edit]
Main article: History of electrochemistry

German physicist Otto von Guericke beside his electrical

generator while conducting an experiment.

16th–18th century[edit]
Understanding of electrical matters began in the sixteenth century. During this
century, the English scientist William Gilbert spent 17 years experimenting
with magnetism and, to a lesser extent, electricity. For his work on magnets, Gilbert
became known as the "Father of Magnetism." He discovered various methods for
producing and strengthening magnets.[2]
In 1663, the German physicist Otto von Guericke created the first electric generator,
which produced static electricity by applying friction in the machine. The generator
was made of a large sulfur ball cast inside a glass globe, mounted on a shaft. The
ball was rotated by means of a crank and an electric spark was produced when a
pad was rubbed against the ball as it rotated. The globe could be removed and used
as source for experiments with electricity.[3]
By the mid-18th century the French chemist Charles François de Cisternay du
Fay had discovered two types of static electricity, and that like charges repel each
other whilst unlike charges attract. Du Fay announced that electricity consisted of
two fluids: "vitreous" (from the Latin for "glass"), or positive, electricity;
and "resinous," or negative, electricity. This was the two-fluid theory of electricity,
which was to be opposed by Benjamin Franklin's one-fluid theory later in the century.
[4]

Late 1780s diagram of Galvani's experiment on frog legs.

In 1785, Charles-Augustin de Coulomb developed the law of electrostatic attraction

as an outgrowth of his attempt to investigate the law of electrical repulsions as stated
by Joseph Priestley in England.[5]
 Italian physicist Alessandro Volta showing
his "battery" to French emperor Napoleon Bonaparte in the early 19th century.

In the late 18th century the Italian physician and anatomist Luigi Galvani marked the
birth of electrochemistry by establishing a bridge between chemical reactions and
electricity on his essay "De Viribus Electricitatis in Motu Musculari
Commentarius" (Latin for Commentary on the Effect of Electricity on Muscular
Motion) in 1791 where he proposed a "nerveo-electrical substance" on biological life
forms.[6]
In his essay Galvani concluded that animal tissue contained a here-to-fore neglected
innate, vital force, which he termed "animal electricity," which
activated nerves and muscles spanned by metal probes. He believed that this new
force was a form of electricity in addition to the "natural" form produced
by lightning or by the electric eel and torpedo ray as well as the "artificial" form
produced by friction (i.e., static electricity).[7]
Galvani's scientific colleagues generally accepted his views, but Alessandro
Volta rejected the idea of an "animal electric fluid," replying that the frog's legs
responded to differences in metal temper, composition, and bulk.[6][7] Galvani refuted
this by obtaining muscular action with two pieces of the same material. Nevertheless,
Volta's experimentation led him to develop the first practical battery, which took
advantage of the relatively high energy (weak bonding) of zinc and could deliver an
electrical current for much longer than any other device known at the time.
19th century[edit]

Sir Humphry Davy's portrait in the 19th century.

In 1800, William Nicholson and Johann Wilhelm Ritter succeeded in decomposing

water into hydrogen and oxygen by electrolysis using Volta's battery. Soon thereafter
Ritter discovered the process of electroplating. He also observed that the amount of
metal deposited and the amount of oxygen produced during an electrolytic process
depended on the distance between the electrodes.[8] By 1801, Ritter
observed thermoelectric currents and anticipated the discovery of thermoelectricity
by Thomas Johann Seebeck.[9]
By the 1810s, William Hyde Wollaston made improvements to the galvanic cell.
Sir Humphry Davy's work with electrolysis led to the conclusion that the production of
electricity in simple electrolytic cells resulted from chemical action and that chemical
combination occurred between substances of opposite charge. This work led directly
to the isolation of metallic sodium and potassium by electrolysis of their molten salts,
and of the alkaline earth metals from theirs, in 1808.[10]
Hans Christian Ørsted's discovery of the magnetic effect of electric currents in 1820
was immediately recognized as an epoch-making advance, although he left further
work on electromagnetism to others. André-Marie Ampère quickly repeated Ørsted's
experiment, and formulated them mathematically.[11]
In 1821, Estonian-German physicist Thomas Johann Seebeck demonstrated the
electrical potential between the juncture points of two dissimilar metals when there is
a temperature difference between the joints.[12]
In 1827, the German scientist Georg Ohm expressed his law in this famous
book "Die galvanische Kette, mathematisch bearbeitet" (The Galvanic Circuit
Investigated Mathematically) in which he gave his complete theory of electricity.[12]
In 1832, Michael Faraday's experiments led him to state his two laws of
electrochemistry. In 1836, John Daniell invented a primary cell which solved the
problem of polarization by introducing copper ions into the solution near the positive
electrode and thus eliminating hydrogen gas generation. Later results revealed that
at the other electrode, amalgamated zinc (i.e., zinc alloyed with mercury) would
produce a higher voltage.

Swedish chemist Svante Arrhenius portrait circa 1880s.

William Grove produced the first fuel cell in 1839. In 1846, Wilhelm Weber developed
the electrodynamometer. In 1868, Georges Leclanché patented a new cell which
eventually became the forerunner to the world's first widely used battery, the zinc–
carbon cell.[8]
Svante Arrhenius published his thesis in 1884 on Recherches sur la conductibilité
galvanique des électrolytes (Investigations on the galvanic conductivity of
electrolytes). From his results the author concluded that electrolytes, when dissolved
in water, become to varying degrees split or dissociated into electrically opposite
positive and negative ions.[13]
In 1886, Paul Héroult and Charles M. Hall developed an efficient method (the Hall–
Héroult process) to obtain aluminium using electrolysis of molten alumina.[14]
In 1894, Friedrich Ostwald concluded important studies of the conductivity and
electrolytic dissociation of organic acids.[15]

German scientist Walther Nernst portrait in the 1910s.

Walther Hermann Nernst developed the theory of the electromotive force of the
voltaic cell in 1888. In 1889, he showed how the characteristics of the voltage
produced could be used to calculate the free energy change in the chemical reaction
producing the voltage. He constructed an equation, known as Nernst equation, which
related the voltage of a cell to its properties.[16]
In 1898, Fritz Haber showed that definite reduction products can result from
electrolytic processes if the potential at the cathode is kept constant. In 1898, he
explained the reduction of nitrobenzene in stages at the cathode and this became
the model for other similar reduction processes.[17]
20th century[edit]
In 1902, The Electrochemical Society (ECS) was founded.[18]
In 1909, Robert Andrews Millikan began a series of experiments (see oil drop
experiment) to determine the electric charge carried by a single electron.[19] In 1911,
Harvey Fletcher, working with Millikan, was successful in measuring the charge on
the electron, by replacing the water droplets used by Millikan, which quickly
evaporated, with oil droplets. Within one day Fletcher measured the charge of an
electron within several decimal places.[20]
In 1923, Johannes Nicolaus Brønsted and Martin Lowry published essentially the
same theory about how acids and bases behave, using an electrochemical basis.[21]
In 1937, Arne Tiselius developed the first sophisticated electrophoretic apparatus.
Some years later, he was awarded the 1948 Nobel Prize for his work in
protein electrophoresis.[22]
A year later, in 1949, the International Society of Electrochemistry (ISE) was
founded.[23]
By the 1960s–1970s quantum electrochemistry was developed by Revaz
Dogonadze and his students.
Principles[edit]
Oxidation and reduction[edit]
Main article: Redox

The term "redox" stands for reduction-oxidation. It refers to electrochemical

processes involving electron transfer to or from a molecule or ion, changing
its oxidation state. This reaction can occur through the application of an
external voltage or through the release of chemical energy. Oxidation and reduction
describe the change of oxidation state that takes place in the atoms, ions or
molecules involved in an electrochemical reaction. Formally, oxidation state is the
hypothetical charge that an atom would have if all bonds to atoms of different
elements were 100% ionic. An atom or ion that gives up an electron to another atom
or ion has its oxidation state increase, and the recipient of the negatively charged
electron has its oxidation state decrease.
For example, when atomic sodium reacts with atomic chlorine, sodium donates one
electron and attains an oxidation state of +1. Chlorine accepts the electron and its
oxidation state is reduced to −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 from an atom or molecule 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: Oxidation, Gain
Electrons: Reduction). Oxidation and reduction always occur in a paired fashion such
that one species is oxidized when another is reduced. For cases where electrons are
shared (covalent bonds) between atoms with large differences in electronegativity,
the electron is assigned to the atom with the largest electronegativity in determining
the oxidation state.
The atom or molecule which loses electrons is known as the reducing agent,
or reductant, and the substance which accepts the electrons is called the oxidizing
agent, or oxidant. Thus, the oxidizing agent is always being reduced in a reaction;
the reducing agent is always being oxidized. Oxygen is a common oxidizing agent,
but not the only one. Despite the name, an oxidation reaction does not necessarily
need to involve oxygen. In fact, a 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 weaker bond and higher electronegativity, and thus accepts electrons even
better) than oxygen.
For reactions involving oxygen, the gain of oxygen implies the oxidation of the atom
or molecule to which the oxygen is added (and the oxygen is reduced). In organic
compounds, such as butane or ethanol, the loss of hydrogen implies oxidation of the
molecule from which it is lost (and the hydrogen is reduced). This follows because
the hydrogen donates its electron in covalent bonds with non-metals but it takes the
electron along when it is lost. Conversely, loss of oxygen or gain of hydrogen implies
reduction.
Balancing redox reactions[edit]
Main article: Chemical equation
Electrochemical reactions in water are better analyzed by using the ion-electron
method, where H+, OH− ion, H2O and electrons (to compensate the oxidation
changes) are added to the cell's half-reactions for oxidation and reduction.
Acidic medium[edit]
In acidic medium, H+ ions and water are added to balance each half-reaction. For
example, when manganese reacts with sodium bismuthate.
Unbalanced reaction: Mn2+(aq) + NaBiO3(s) → Bi3+(aq) + MnO−
4(aq)

Oxidation: 4 H2O(l) + Mn2+(aq) → MnO−

4(aq) + 8 H (aq) + 5 e
+ −

Reduction: 2 e− + 6 H+(aq) + BiO−

3(s) → Bi (aq) + 3 H2O(l)
3+

Finally, the reaction is balanced by multiplying the stoichiometric

coefficients so the numbers of electrons in both half reactions match
8 H2O(l) + 2 Mn2+(aq) → 2 MnO−
4(aq) + 16 H (aq) + 10 e
+ −

10 e− + 30 H+(aq) + 5 BiO−
3(s) → 5 Bi (aq) + 15 H2O(l)
3+

and adding the resulting half reactions to give the balanced

reaction:
14 H+(aq) + 2 Mn2+(aq) + 5 NaBiO3(s) → 7 H2O(l) + 2 MnO−
4(aq) + 5 Bi (aq) + 5 Na (aq)
3+ +

Basic medium[edit]
In basic medium, OH− ions and water are added to balance
each half-reaction. For example, in a reaction
between potassium permanganate and sodium sulfite:
Unbalanced reaction: KMnO4 + Na2SO3 + H2O → MnO2 + Na2SO4 + KOH
Reduction: 3 e− + 2 H2O + MnO−
4 → MnO2 + 4 OH
−

Oxidation: 2 OH− + SO2−

3 → SO
2−

4 + H 2O + 2 e
−

Here, 'spectator ions' (K+, Na+) were omitted from the

half-reactions. By multiplying the stoichiometric
coefficients so the numbers of electrons in both half
reaction match:
6 e− + 4 H2O + 2 MnO−
4 → 2 MnO2 + 8 OH
−

6 OH− + 3 SO2−
3 → 3 SO
2−

4 + 3 H 2O + 6 e
−

the balanced overall reaction is obtained:

2 KMnO4 + 3 Na2SO3 + H2O → 2 MnO2 + 3 Na2SO4 + 2 KOH
 Neutral medium[edit]
The same procedure as used in acidic
medium can be applied, for example, to
balance the complete
combustion of propane:
Unbalanced reaction: C3H8 + O2 → CO2 + H2O
Reduction: 4 H+ + O2 + 4 e− → 2 H2O
Oxidation: 6 H2O + C3H8 → 3 CO2 + 20 e− + 20 H+
By multiplying the
stoichiometric coefficients so
the numbers of electrons in
both half reaction match:
20 H+ + 5 O2 + 20 e− → 10 H2O
6 H2O + C3H8 → 3 CO2 + 20 e− + 20 H+
the balanced equation
is obtained:
C3H8 + 5 O2 → 3 CO2 + 4 H2O
Electrochem
ical cells[edit]
Main
article: Electrochemic
al cell

An electrochemical
cell is a device that
produces an
electric current
from energy
released by
a spontaneous red
ox reaction. This
kind of cell includes
the Galvanic cell or
Voltaic cell, named
after Luigi
Galvani and Alessa
ndro Volta, both
scientists who
conducted
experiments on
chemical reactions
and electric current
during the late 18th
century.
Electrochemical
cells have two
conductive
electrodes (the
anode and the
cathode).
The anode is
defined as the
electrode where
oxidation occurs
and the cathode is
the electrode where
the reduction takes
place. Electrodes
can be made from
any sufficiently
conductive
materials, such as
metals,
semiconductors,
graphite, and
even conductive
polymers. In
between these
electrodes is
the electrolyte,
which contains ions
that can freely
move.
The galvanic cell
uses two different
metal electrodes,
each in an
electrolyte where
the positively
charged ions are
the oxidized form of
the electrode metal.
One electrode will
undergo oxidation
(the anode) and the
other will undergo
reduction (the
cathode). The
metal of the anode
will oxidize, going
from an oxidation
state of 0 (in the
solid form) to a
positive oxidation
state and become
an ion. At the
cathode, the metal
 ion in solution will
accept one or more
electrons from the
cathode and the
ion's oxidation state
is reduced to 0.
This forms a solid
metal
that electrodeposits
on the cathode.
The two electrodes
must be electrically
connected to each
other, allowing for a
flow of electrons
that leave the metal
of the anode and
flow through this
connection to the
ions at the surface
of the cathode. This
flow of electrons is
an electric current
that can be used to
do work, such as
turn a motor or
power a light.
A galvanic cell
whose electrodes a
re zinc and copper
submerged in zinc
sulfate and copper
sulfate,
respectively, is
known as a Daniell
cell.[24]
The half reactions
in a Daniell cell are
as follows:[24]
Zinc electrode (anode): Zn(s) → Zn2+(aq) + 2 e−
Copper electrode (cathode): Cu2+(aq) + 2 e− → Cu(s)
A modern cell
stand for
electrochemi
cal research.
The
electrodes
attach to
high-quality
metallic
wires, and
the stand is
attached to
a potentiostat
/galvanostat (
not pictured).
A shot glass-
shaped
container
is aerated wit
h a noble gas
and sealed
with
the Teflon blo
ck.
In this
example,
the anode is
the zinc
metal which
is oxidized
(loses
electrons) to
form zinc
ions in
solution,
and copper
ions accept
electrons
from the
copper
metal
electrode
and the ions
deposit at
the copper
cathode as
an
electrodepo
sit. This cell
forms a
simple
battery as it
will
spontaneou
sly generate
a flow of
electric
current from
the anode to
the cathode
through the
external
connection.
This
reaction can
be driven in
reverse by
applying a
voltage,
resulting in
the
deposition
of zinc
metal at the
anode and
formation of
copper ions
at the
cathode.[24]
To provide a
complete
electric
circuit, there
must also
be an ionic
conduction
path
between the
anode and
cathode
electrolytes
in addition
to the
electron
conduction
path. The
simplest
ionic
conduction
path is to
provide a
liquid
junction. To
avoid mixing
between the
two
electrolytes,
the liquid
junction can
be provided
through a
porous plug
that allows
ion flow
while
minimizing
electrolyte
mixing. To
further
minimize
mixing of
the
electrolytes,
a salt
bridge can
be used
which
consists of
an
electrolyte
saturated
gel in an
inverted U-
tube. As the
negatively
charged
electrons
flow in one
direction
around this
circuit, the
 positively
charged
metal ions
flow in the
opposite
direction in
the
electrolyte.
A voltmeter i
s capable of
measuring
the change
of electrical
potential bet
ween the
anode and
the cathode.
The
electrochem
ical cell
voltage is
also
referred to
as electrom
otive
force or
emf.
A cell
diagram can
be used to
trace the
path of the
electrons in
the
electrochem
ical cell. For
example,
here is a
cell diagram
of a Daniell
cell:
Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)
First, the
reduced
form of
the
metal to
be
oxidized
at the
anode
(Zn) is
written.
This is
separate
d from
its
oxidized
form by
a vertical
line,
which
represen
ts the
limit
between
the
phases
(oxidatio
n
changes
). The
double
vertical
lines
represen
t the
saline
bridge
on the
cell.
Finally,
the
oxidized
form of
the
metal to
be
reduced
at the
cathode,
is
written,
separate
d from
its
reduced
form by
the
vertical
line. The
electrolyt
e
concentr
ation is
given as
it is an
importan
t
variable
in
determin
ing the
exact
cell
potential
.
Stand
ard
electr
ode
poten
tial[ed
it]
Main
article: St
andard
electrode
potential

To allow
predictio
n of the
cell
potential
,
tabulatio
ns
of stand
ard
electrod
e
potential
are
available
 . Such
tabulatio
ns are
referenc
ed to the
standard
hydroge
n
electrod
e (SHE).
The stan
dard
hydroge
n
electrod
e underg
oes the
reaction
2 H+(aq) + 2 e− → H2
whic
h is
show
n as
a
redu
ction
but,
in
fact,
the
SHE
can
act
as
eithe
r the
anod
e or
the
cath
ode,
depe
ndin
g on
the
relati
ve
oxida
tion/r
educ
tion
pote
ntial
of
the
other
elect
rode/
elect
rolyt
e
com
binati
on.
The
term
stan
dard
in
SHE
requi
res a
suppl
y of
hydr
ogen
gas
bubb
led
throu
gh
the
elect
rolyt
e at
a
pres
sure
of 1
atm
and
an
acidi
c
elect
rolyt
e
with
H+ ac
tivity
equa
l to 1
(usu
ally
assu
med
to be
[H+] =
1 mo
l/liter,
i.e. p
H=
0).
The
SHE
elect
rode
can
be
conn
ecte
d to
any
other
elect
rode
by a
salt
bridg
e
and
an
exter
nal
circui
t to
form
a
cell.
If the
seco
nd
elect
rode
is
also
at
stan
dard
condi
tions,
then
the
mea
sure
d cell
pote
ntial
is
calle
d the
stan
dard
elect
rode
pote
ntial
for
the
elect
rode.
The
stan
dard
elect
rode
pote
ntial
for
the
SHE
is
zero,
by
defini
tion.
The
polar
ity of
the
stan
dard
elect
rode
pote
ntial
provi
des
infor
mati
on
abou
t the
relati
ve
redu
ction
pote
ntial
of
the
elect
rode
com
pare
d to
the
SHE.
If the
elect
rode
has
a
positi
ve
pote
ntial
with
resp
ect
to
the
SHE,
then
that
mea
ns it
is a
stron
gly
redu
cing
elect
rode
whic
h
force
s the
SHE
to be
the
anod
e (an
exa
mple
is Cu
in
aque
ous
CuS
O4 wi
th a
stan
dard
elect
rode
pote
ntial
of
0.33
7 V).
Conv
ersel
y, if
the
mea
sure
d
pote
ntial
is
nega
tive,
the
elect
rode
is
more
oxidi
zing
than
the
SHE
(suc
h as
Zn in
ZnS
O4 w
here
the
stan
dard
elect
rode
pote
ntial
is
−0.7
6 V).
[24]

Stan
dard
elect
rode
pote
ntials
are
usual
ly
tabul
ated
as
redu
ction
pote
ntials
.
How
ever,
the
react
ions
are
rever
sible
and
the
role
of a
parti
cular
elect
rode
in a
cell
depe
nds
on
the
relati
ve
oxida
tion/r
educ
tion
pote
ntial
of
both
elect
rode
s.
The
oxida
tion
pote
ntial
for a
parti
cular
elect
rode
is
just
the
nega
tive
of
the
redu
ction
pote
ntial.
A
stan
dard
cell
pote
ntial
can
be
deter
mine
d by
looki
ng
up
the
stan
dard
elect
rode
pote
ntials
for
both
elect
rode
s
(som
etim
es
calle
d
half
cell
pote
ntials
).
The
one
that
is
small
er
will
be
the
anod
e
and
will
unde
rgo
oxida
tion.
The
cell
pote
ntial
is
then
calcu
lated
as
the
sum
of
the
redu
 ction
pote
ntial
for
the
cath
ode
and
the
oxida
tion
pote
ntial
for
the
anod
e.
E°cell = E°red (cathode) – E°red (anode) = E°red (cathode) + E°oxi (anode)
F
o
r
e
x
a
m
pl
e
,
t
h
e
st
a
n
d
a
r
d
el
e
ct
r
o
d
e
p
o
t
e
n
 ti
al
f
o
r
a
c
o
p
p
e
r
el
e
ct
r
o
d
e
is
:
C
el
l
di
a
g
r
a
m
Pt(s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu(s)
E°cell = E°red (cathode) – E°red (anode)
At
stand
ard
temp
eratu
re,
press
ure
and
conc
entrat
ion
condi
tions,
the
cell's
emf (
 meas
ured
by
a mul
timet
er) is
0.34
V. By
defini
tion,
the
electr
ode
poten
tial
for
the
SHE
is
zero.
Thus,
the
Cu is
the
catho
de
and
the
SHE
is the
anod
e
givin
g
Ecell = E°(Cu2+/Cu) – E°(H+/H2)
Or,
E°(Cu2+/Cu) = 0.34 V
Changes in
the stoichio
metric
coefficients
of a
balanced
cell equation
will not
change
the E°red valu
e because
the standard
 electrode
potential is
an intensive
property.
Spontan
eity of
redox
reaction
[edit]
Main
article: Spont
aneous
process

During
operation of
an electroch
emical
cell, chemica
l energy is
transformed
into electrica
l energy.
This can be
expressed
mathematica
lly as the
product of
the cell's
emf Ecell mea
sured in
volts (V) and
the electric
charge Qele,trans
transferred
through the
external
circuit.
Electrical energy = EcellQele,trans
Qele,trans is the ce
current
integrated ove
time and
measured in
coulombs (C);
can also be
determined by
multiplying the
 total
number ne of
electrons
transferred
(measured in
moles)
times Faraday
constant (F).
The emf of the
cell at zero
current is the
maximum
possible emf.
can be used to
calculate the
maximum
possible
electrical ener
that could be
obtained from
a chemical
reaction. This
energy is
referred to
as electrical
work and is
expressed by
the following
equation:

,
where work is
defined as pos
when it increa
the energy of
system.
Since the free
energy is the
maximum amo
of work that ca
extracted from
system, one c
write:[25]

A positive cell
gives a negati
change in Gib
energy. This is
consistent with
production of
an electric cur
the cathode to
anode through
external circui
current is drive
opposite direc
imposing an e
potential, then
done on the ce
drive electroly
A spontaneou
hemical reacti
(change in Gib
energy less th
can be used to
generate an e
current in
electrochemic
This is the bas
batteries and f
For example,
oxygen (O2) an
hydrogen (H2)
combined in a
to form water
energy, typica
combination o
and electrical
Conversely, n
spontaneous
electrochemic
reactions can
forward by the
application of
at sufficient vo
The electrolys
water into gas
oxygen and hy
is a typical exa
The relation b
the equilibrium
constant, K, a
Gibbs free ene
an electrochem
is expressed a
.
Rearranging to
relation betwe
potential and e
constant yield

.
At T = 298 K,
equation can b
using the Brig
logarithm as fo

Cell emf d
on chang
concentra
Nernst equa
Main article: Ne

The standard
electrochemic
standard cond
the reactants.
concentrations
standard cond
potential will d
standard pote
century Germa
Nernst propos
model to deter
reactant conce
electrochemic
In the late 19th
Willard Gibbs
theory to pred
chemical reac
based on the f

Here ΔG is ch
energy, ΔG° is
when Q is equ
absolute temp
the gas consta
quotient, whic
dividing conce
those of reacta
power of its st
using only tho
reactants that
gaseous.
Gibbs' key con
formalize the u
effect of reacta
spontaneity.
Based on Gibb
extended the t
contribution fro
charged speci
previous secti
free energy fo
can be related
Thus, Gibbs' t

Here ne is the
of electrons (in
constant (in co
the cell potent
Finally, Nerns
amount of cha
a new equatio
name:

Assuming stan
25 °C) and R =
equation abov
10 logarithm a

Note that RT/F

voltage VT and
and semicond
0.05916 V in t
thermal voltag
multiplied by t
Concentrati
Main article: Co
 A concentratio
where the two
the electrolyte
same ions, bu
differs betwee
An example is
two copper ele
two copper(II)
concentrations
through a salt
generate a po
Nernst equatio
chemistry (alth
reverse at the
Cu2+(aq) + 2 e− → Cu(s)
Le Chatelier's
more favorabl
Cu2+ ions incre
cell's compartm
and oxidation
The following
concentration
Cu(s) | Cu2+ (0.05 M) || Cu2+ (2.0 M) | Cu(s)
where the half
are:
Oxidation: Cu(s) → Cu2+ (0.05 M) + 2 e−
Reduction: Cu2+ (2.0 M) + 2 e− → Cu(s)
Overall reaction: Cu2+ (2.0 M) → Cu2+ (0.05 M)
The cell's emf

The value of E
the same in bo
After replacing
calculate cell's

or by:

However, this
terms of ion ac
calculated her
The Nernst eq
in cells and or
beat as well a
Battery[ed
Main article: Ba

Many types of
practical appli
first telegraph
for electroplati
non-spillable b
practical. The
levels of powe
devices, but h
mercury pollut
The lead–acid
that could hav
electrochemic
reversible, allo
as needed. Co
water, as well
acid. One prob
lead plates of
of 3 years with
be functional a
automobiles.
All the preced
maximum volt
performance.
water in the el
rechargeable
The flow batte
energy capaci
reservoirs. Th
gases or hydro
higher efficien
many spacecr
power system
Corrosion
Main article: Co

Corrosion is a
on metals like
Iron corrosio
For iron rust to
The chemical
 them are com
Electron trans
One area on the surface of the metal acts as the anode, which is where the oxidation
(corrosion) occurs. At the anode, the metal gives up electrons.
Fe(s) → Fe2+(aq) + 2 e−
Electrons are transferred from iron, reducing oxygen in the atmosphere into water on
the cathode, which is placed in another region of the metal.
O2(g) + 4 H+(aq) + 4 e− → 2 H2O(l)
Global reaction for the process:
2 Fe(s) + O2(g) + 4 H+(aq) → 2 Fe2+(aq) + 2 H2O(l)
Standard emf for iron rusting:
E° = E° (cathode) − E° (anode)
E° = 1.23V − (−0.44 V) = 1.67 V
Iron corrosion
dioxide in the
following this e
4 Fe2+(aq) + O2(g) + (4+2x) H2O(l) → 2 Fe2O3·xH2O + 8 H+(aq)
Iron(III) oxide
varies, thus th
An electric circ
present it will f
Corrosion o
Coinage meta
blue copper ca
dioxide in the
the low levels
Gold and plati
exposure to a
Some commo
instantaneous
of oxidized me
protects the un
These metals
has an oxide t
therefore does
will continue to
Prevention
Attempts to sa
dissolve and d
While it is alm
covers the me
Coating[edit]
Main article: Co
 See also: Anod

Metals can be
metal surface
result in corros
reaction.
Sacrificial anode
Main article: Sa

A method com
than the meta
corrosion. It is
periodically.
Zinc bars are
The zinc bars
but zinc is the
To protect pip
the pipeline an
a cathode and
At intervals ne
Electroly
Main article: Ele

The spontane
different reduc
requires an ex
takes place in
Electrolysis
Main article: Do

When molten,
gaseous chlor
cell is connect
supply to the e
Reactions tha
Anode (oxidation): 2 Cl−(l) → Cl2(g) + 2 e−
Cathode (reduction): 2 Na+(l) + 2 e− → 2 Na(l)
Overall reaction: 2 Na+(l) + 2 Cl−(l) → 2 Na(l) + Cl2(g)
This process c
in mineral dres
The emf for th
this reaction to
larger voltages
Electrolysis
Main article: Ele
 Water can be
external voltag
energy change
of water into h
inert electrode
process. The e
process will no
chloride or sul
Bubbles from
process menti
Anode (oxidation): 2 H2O(l) → O2(g) + 4 H+(aq) + 4 e−
Cathode (reduction): 2 H2O(g) + 2 e− → H2(g) + 2 OH−(aq)
Overall reaction: 2 H2O(l) → 2 H2(g) + O2(g)
Although stron
will work at an
formation, allo
Electrolysis
Electrolysis in
considered to
reduced or ox
Electrolysis of a
Main article: Ch

The presence
both electrode
the anode and
Cl− ions. The c
The chloride a
The following

1. Cathode: N
2. Anode: 2 Cl
3. Cathode: 2
4. Anode: 2 H2
Reaction 1 is d
thermodynam
When compar
water, thus ch
Although the i
sometimes req
than thermody
low, hence fav
drive electroly
external sourc
The overall re
Anode (oxidation): 2 Cl−(aq) → Cl2(g) + 2 e−
Cathode (reduction): 2 H2O(l) + 2 e− → H2(g) + 2 OH−(aq)
Overall reaction: 2 H2O + 2 Cl−(aq) → H2(g) + Cl2(g) + 2 OH−(aq)
As the overall
increases). Th
Quantitative
Main article: Fa

Quantitative a
coined the term
Also he was a
First law[edit]
Faraday concl
yielded on the
the molar mas
electrolytic cel
Below is a sim

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[edi
Main article: Ele

Faraday devis
amounts of bo
them." In othe
weights.[32]
An important a
applications in
Applicati
There are vari
electrodeposit
alcohol in drun
electrochemic
amount of gluc
batteries) ther
and super-cap
analysis of min
applications in
the determina
See also[e

 Science

 Bioelectrom
 Bioelectroch
 Bipolar elec
 Contact ten
 Corrosion e
 Cyclic volta
 Electrochem
 Electroanaly
 Electrocatal
 Electrochem
 Electrochem
 Electrodeion
 Electropolis
 Electroplatin
 Electrochem
 Electrochem
 Electrosynth
 Frost diagra
 Fuel cells
 ITIES
 List of elect
 Important p
 Magnetoele
 Nanoelectro
 Photoelectr
 Plasma elec
 Pourbaix dia
 Protein film
 Reactivity s
 Redox titrat
 Standard el
 Voltammetr
Referenc
1. ^ Brett, Chris
2. ^ Richard P. O
3. ^ R. Hellborg
4. ^ Steven Wei
5. ^ J. A. M. Ble
6. ^ Jump up to:
7. ^ Jump up to:
8. ^ Jump up to:
9. ^ The New E
10. ^ Charles Kn
11. ^ William Ber
 12. ^ Jump up to:
13. ^ Nobel Lectu
14. ^ Polmear, I.J
15. ^ Nobel Lectu
16. ^ Nobel Lectu
17. ^ Nobel Lectu
18. ^ "About ECS
19. ^ Millikan, Ro
397. Bibcode
20. ^ Perry, Mich
21. ^ William L. M
22. ^ The Nobel P
23. ^ The Interna
24. ^ Jump up to:
25. ^ Jump up to:
26. ^ Wiberg, pp.
27. ^ Badwal, Su
technologies
28. ^ Jump up to:
29. ^ Jump up to:
30. ^ Jump up to:
31. ^ Wiberg, p. 6
32. ^ Faraday, M
33. ^ "What is Ele
34. ^ S.P.S BADW
79. Bibcode:2
35. ^ Stock, John
36. ^ Hollaender,
626. doi:10.10
37. ^ Mabrook, M

Bibliogra

 Kreysa, Ger
4419-6996-
 Ebbing, Dar
 Nobel Lectu
 Swaddle, Th
 Brett CMA,
 Wiberg, Ego
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