Electrochemical Terms and Concepts

From Electricity to Electrochemistry

Many significant chemical reactions are electrochemical in nature. In order to
understand electrochemical reactions, it is necessary to understand the terms and
concepts of electricity and extend these to apply to electrochemical relationships.
Electrochemical reactions are chemical reactions in which electrons are transferred.
The most fundamental quantity used in the study of electricity is electrical current
(symbol I. Electrical current is measured in one of the base units of the International
!ystem, the ampere (unit symbol ". There are two types of electrical current# direct
current ($%, in which the current flows in only one direction, and alternating current
("%, in which the current flows alternately in opposite directions. Most &orth
"merican homes are supplied with '()*+ "% current, which re,erses its flow e,ery
-.'( of a second. " home or apartment is usually wired for a total input current of -((
to -/( ". This current is distributed to different rooms in six to ten circuits, each
protected by a separate fuse or circuit brea0er of -/ " or 1( " capacity.
Electrical charge (symbol 2 is the product of electrical current and time3 2 4 It.
Electrical charge is measured in coulombs (unit symbol %. %hemists use the coulomb,
which is a !I unit, extensi,ely in the calculations of electrochemical stoichiometry. "
charge of one coulomb is passed when a current of one ampere flows for a time of one
second, so the coulomb is the ampere)second.
Energy must be expended in order to force electrical current to flow through matter. The
amount of energy expended in doing so depends upon the electrical resistance (symbol
5 of the particular matter through which the current passes. The electrical resistance of
matter is measured in ohms (unit symbol 6ree0 capital omega. 7hen one 8oule of
energy is expended in dri,ing a current of one ampere through a resistance, the
electrical resistance is one ohm.
9ne of the most useful of the laws of electricity is the law of 9hm, E 4 I5. This law
lin0s the electrical quantities of current I and resistance 5 with the electrical potential or
potential difference (symbol E which is dri,ing the current through the resistance. The
!I unit for the electrical potential difference is the ,olt (unit symbol :. " potential
difference of one ,olt will dri,e one ampere of current through one ohm of resistance,
expending as it does so one 8oule of energy and passing in the process one coulomb of
charge. The 8oule is also the ,olt)coulomb.
7hen current flows through an electrical resistance, the energy expended appears as
heat. This process is 0nown as ;oule heating because it was first studied quantitati,ely
by ;ames <rescott ;oule. %hemists ma0e use of the ;oule heating relationship q 4 I
=
5t to
calibrate calorimeters, because electrical heating pro,ides an easily measurable and
precisely controllable source of heat. 7hen the law of 9hm is used in con8unction with
the ;oule heating relationship, we see that the heat q produced is EIt, the product of the
current which flows, its dri,ing electrical potential, and the time for which it flows.
The electrical relationships introduced in this section are used by chemists in the
explanation of electrochemical beha,ior, and we will require them throughout this
section. 9ne of the problems students encounter in electrochemistry is the use of E for
electrical potential when they are more familiar with it as the symbol for energy. To
minimi+e this confusion, E is used only for electrical potential throughout this section
and no symbol whate,er is used for energy.
Oxidation and Reduction
Electrons are always transferred from one atom or molecule to another in an
electrochemical reaction, e,en though electrons may not appear explicitly in the
simplest balanced equation for the reaction. In the reaction Fe
1>
(aq > 1e
)
))? Fe
electrons do appear explicitly, while in the reaction =Fe
=
9
1
> 1% ))? 1%9
=
(g > @Fe they
do not, yet both are electrochemical reactions. The presence of electrons in the second
reaction is implicit. In both reactions, iron originally in oxidation state >1 acquires
electrons and becomes neutral iron metal.
The concept of oxidation state, which was used in an earlier section to name
compounds, arose from early studies of electrochemical reactions. !ince these reactions
usually in,ol,ed oxygen from the air, the name oxidation state was used. Modern
chemists no longer restrict the use of oxidation states to compounds in,ol,ing oxygen.
&ow, the oxidation state of an atom is the charge an atom is presumed to ha,e in one or
more of its compounds or ions.
The procedures used to assign oxidation states to atoms in electrochemistry are the same
procedures used for chemical nomenclature. *owe,er, in electrochemistry we extend
the use of oxidation states to describe the chemical reactions in which oxidation states
are changed. Electrons are transferred in all electrochemical reactions. The transfer of
electrons, with their charge of )-, must change the oxidation state of one or more atoms
on one or more of the compounds or ions in,ol,ed in an electrochemical reaction.
There are three different types of electrochemical reactions which are distinguished by
the changes of oxidation state which occur in them. They are called oxidation reactions,
reduction reactions, and redox reactions3 the term redox is an abbre,iation for
oxidation)reduction reactions, since both oxidation and reduction occur in redox
reactions. Electrons appear explicitly in oxidations or reductions but appear only
implicitly in redox reactions.
In an oxidation reaction, electrons are lost by atoms of the element(s in,ol,ed in the
reaction. The charge on these atoms must then become more positi,e. The electrons are
lost from the species undergoing oxidation and so electrons appear as products in an
oxidation reaction. "n oxidation is ta0ing place in the reaction Fe
=>
(aq ))? Fe
1>
(aq > e
)
because electrons are lost from the species being oxidi+ed, Fe
=>
(aq, despite the apparent
production of electrons as AfreeA entities in oxidation reactions. 9xidation reactions are
reactions in which the oxidation state(s of the atoms of the element(s in,ol,ed
increases. The increase is intended in the sense of becoming more positi,e.
" reduction reaction is the re,erse of an oxidation reaction. In a reduction reaction,
electrons are gained by atoms of the elements in,ol,ed. Their charge becomes less
positi,e. The electrons are gained by the species undergoing reduction and so electrons
appear as reactants in a reduction reaction. " reduction is ta0ing place in the reaction
%d
=>
> =e
)
))? %d(s because electrons are being gained by the species which is being
reduced, %d
=>
(aq, despite the apparent loss of electrons as AfreeA entities in reduction
reactions. 5eduction reactions are reactions in which the oxidation state(s of the atoms
of the element(s in,ol,ed decreases. The decrease is intended in the sense of becoming
less positi,e.
" redox reaction is an electrochemical reaction in which both reduction and oxidation
ta0e place together. The electrons lost in an oxidation component are gained in a
reduction component. ("s a consequence, some chemists call a redox reaction a full
reaction and its constituent oxidation and reduction components half)reactions. The
stoichiometry of a redox reaction is such that all of the electrons lost in the oxidation are
gained in the reduction, so electrons can appear only implicitly in a redox reaction.
!pecies that participate in redox reactions are often described as reducing agents or
oxidi+ing agents. " reducing agent is a species which reduces something else (and is
itself oxidi+ed in the process3 an oxidi+ing agent is a species which oxidi+es something
else (and is itself reduced in the process.
Electrolytes, Electrodes, and Electrochemical Cells
The !wedish chemist !,ante "rrhenius was the first to use the term electrolyte to
describe a salt which in solution dissociates into ions. "n ion is an atom or molecule
which has acquired an electrical charge. "n ion which carries a positi,e charge is called
a cation and an ion which carries a negati,e charge is called an anion. %ompounds,
molecules, and atoms which are uncharged are referred to as neutral species.
" solution which contains ions is called an electrolyte solution (sometimes simply an
electrolyte. Electrolyte solutions conduct electricity because the charged ions can mo,e
through them. Electrolyte solutions are ionic conductors as distinguished from the
electronic conductors, such as metallic wires, in which charge is carried by mo,ement
of electrons. "n electrolyte solution may be used for this purpose alone. "n example of
this is the salt bridge, which electrochemists use to permit the flow of ionic charge
between different electrolyte solutions. " salt bridge is a tube containing a relati,ely
high concentration of an ionic salt such as potassium chloride. The electrolyte solution
of the salt bridge may be held as a semisolid agar gel to ma0e it easier to use.
In all oxidation or reduction reactions, AfreeA electrons must be present as products or as
reactants. These electrons must be pro,ided by or gi,en to a source or sin0 of electrons
other than the reaction itself. The electrons can be pro,ided through a metallic
conductor leading to an external source or sin0, and the metallic conductor on contact
with the electrolyte constitutes an electrode. Two or more electrodes form an
electrochemical cell from which two external wires can lead to an external electrical
de,ice. "n oxidation or reduction reaction ta0es place at one electrode, while a redox
reaction can ta0e place either in an electrochemical cell or directly in a solution.
For this reason, electrochemical reactions in which electrons appears explicitly are also
called electrode reactions or, since two electrodes ma0e up a cell, half)reactions. " half)
reaction can be either a reaction in which electrons appear as products (an oxidation
reaction or a reaction in which electrons appear as reactants (a reduction reaction. "
combination of two electrode reactions forms a cell reaction or, since one electrode
must be carrying out an oxidation while the other is carrying out a reduction, a redox
reaction. " redox reaction may ta0e place in a cell or by direct combination of the
reactants in the absence of a cell. In either case, the o,erall stoichiometry of the redox
reaction is such that electrons appear explicitly neither as products nor as reactants. This
implicit number of electrons, which is defined by the stoichiometry of the redox
reaction e,en though the number of electrons is not explicitly written in the reaction, is
called the charge number of the redox reaction. " balanced electrochemical half)
reaction is a reaction in which all atoms appearing on one side are balanced, in type and
number, by atoms appearing on the other. The total charge on one side of a half)reaction
is equal to the total charge on the other, but at least one electron appears on one side not
balanced by an electron on the other.
!ince electrons carry a single negati,e charge, charged species usually appear in
electrochemical reactions. These charged species may be the electrons themsel,es, or
they may be ions. Electrons are not normally found in aqueous solutions because they
react with water3 they mo,e through electronic conductors which are generally metallic
wires. Ions, howe,er, are quite stable in aqueous solutions and can carry charge as they
mo,e through it.
!ingle half)reactions can physically occur only at electrodes, because only at electrodes
do you ha,e sources or sin0s of electrons )) the metallic wires. (9ne definition of an
electrode is a point of contact between an electronic conductor, usually a metal, and an
ionic conductor, the electrolyte solution. 7hen an oxidation reaction ta0es place at an
electrode, that electrode is called an anode3 when a reduction reaction ta0es place at an
electrode, that electrode is called a cathode.
!ums of two half)reactions ta0en so that their electrons cancel out ma0e up redox
reactions. 5edox reactions can physically occur in two ways# in a full cell, made up of
two electrodes (in which case one half)reaction occurs at each electrode, and the
cancelling electron flow occurs through the wire connecting them or in a single
solution containing no electrodes (in which case the cancelling electron flow ta0es place
directly between ions or molecules in the solution.
Example. The reaction Fe
=>
(aq > =e
)
))? Fe(s is an electrode reaction. It is also a
cathode reaction, since the process which occurs is reduction. If this reaction were
written bac0wards, it would be an anode reaction and the process ta0ing place would be
oxidation.
Example. In the redox reaction %l
=
(aq > =I
)
(aq ))? =%l
)
(aq > I
=
(aq, chlorine is the
oxidi+ing agent and is itself reduced from oxidation state ( to oxidation state )-, while
iodide ion is the reducing agent and is itself oxidi+ed from oxidation state )- to
oxidation state (.
Example. In the redox reaction =%u9 > % ))? =%u > %9
=
(g, carbon is the reducing
agent and is itself oxidi+ed from oxidation state ( to oxidation state >@, while copper
oxide is the oxidi+ing agent in which copper is reduced from oxidation state >= to
oxidation state (.
Electrochemical Stoichiometry
Faraday's Laws of Electrolysis
7hen an electric current is made to pass through a cell, the current may cause chemical
reactions to occur at its electrodes. This process is called electrolysis and the cell in
which it occurs is called an electrolytic cell. In the -B1(s, the English scientist Michael
Faraday studied the reactions which ta0e place at the electrodes of electrolytic cells.
Faraday showed that electrochemical reactions follow all normal chemical
stoichiometric relations, but in addition follow certain stoichiometric rules related to
charge. These are 0nown as FaradayCs laws of electrolysis. In his experimental form, but
using modern terms, they are as follows#
The mass of an element discharged at an electrode m is directly proportional to
the amount of electrical charge 2 passed through the electrode.
If the same amount of electrical charge 2 is passed through se,eral electrodes,
the mass of an element m discharged at each will be directly proportional to both
(a the atomic mass of the element, and (b the number of moles of electrons +
required to discharge one mole of the element from whate,er material is being
discharged at the electrode.
Moles and Couloms
FaradayCs empirical laws of electrolysis relate to the number of electrons required to
discharge one mole of an element. !uppose that the charge required were one electron
per molecule, as in the case of a reaction such as the electroplating of sil,er, "g
>
(aq >
e
)
))? "g(s. To discharge one mole of sil,er would therefore require one mole of
electrons, or ",ogadroCs number of electrons. The charge carried by one mole of
electrons is 0nown as one Faraday (symbol F. The Faraday is related to other electrical
units because the charge on a single electron is -.'(=DD11... x -(
)-E
%.electron.
Multiplying the electronic charge by the ",ogadro number '.(==-1'D... x -(
>=1
electrons.mole electrons tells us that one Faraday equals E',@B/.1(E... %.
The original studies of Faraday used only elements, but modern chemists ha,e extended
them to electrochemical reactions in,ol,ing compounds and ions. %ombination of the
principles of Faraday with an electrochemical reaction of 0nown stoichiometry permits
us to write FaradayCs laws of electrolysis as a single equation#
n ! "#$F ! %t#$F
The symbol + represents the charge number of the electrochemical reaction, which is the
number of electrons in,ol,ed in the balanced half)cell (electrode reaction.
Many electrochemical reactions, including those ta0en up in this section and the
sections which follow, are or can be carried out under conditions in which a constant
current flows through the electrochemical cell for some period of time. If the current is
not constant, then the charge 2 would ha,e to be obtained by integrating the current
o,er the time for which it flows. Electrochemists use integrating instruments called
coulometers to measure the total charge when the current is not constant.
&alancin' Electrode Reactions
In any stoichiometric half)cell (electrode reaction, the charge on both sides is balanced
explicitly by electrons. The balanced equation gi,es the ratio of moles of electrons to
moles of other species, and the number of moles of electrons can be con,erted into
coulombs using the ,alue of the faraday. %harge is the product of current and time for
direct current. "lternating current produces no net electrochemical reaction (no Faradaic
reaction because any chemical change effected on one half)cycle of the current is
undone on the next half)cycle, so it is not used to produce electrode or cell reactions.
!toichiometric oxidation or reduction reactions are reactions in which both atoms and
charge must be balanced. !imple reductions or oxidations are easily balanced. *owe,er,
in aqueous solutions these reactions may not be simple because the sol,ent water can
become in,ol,ed in the reaction. In acidic aqueous solution, an electrode reaction is
most easily balanced by carrying out the following steps in order#
-. balance all elements except hydrogen and oxygen using stoichiometric
coefficients3
=. balance oxygen by adding water as necessary3
1. balance hydrogen by adding hydrogen ions as necessary3
@. balance charge by adding electrons as necessary. The number of electrons
necessary to balance the charge is the charge number of the electrode reaction, +.
Example. The reduction of iodate ion to iodide ion in acidic aqueous solution is
balanced as follows using the abo,e four steps#
%O
(
)
))* %
)

%O
(
)
))* %
)
+ (,
-
O
.,
+
+ %O
(
)
))* %
)
+ (,
-
O
/e
)
+ .,
+
+ %O
(
)
))* %
)
+ (,
-
O
If the reaction ta0es place in a basic aqueous solution rather than an acidic one, protons
will not be a,ailable. &e,ertheless, it is easier to balance a reduction or oxidation
reaction in basic solution as if it were in acidic solution, then use a formal con,ersion
procedure to gi,e the basic stoichiometry. The formal con,ersion to basic solution is
made by#
-. adding to both sides of the equation the number of hydroxide ions equal to the
number of hydrogen (*
>
ions appearing on the only side that has any3
=. combining hydrogen and hydroxide ions to form water where,er possible3 and
then
1. cancelling any water which now appears on both sides of the reaction equation.
Example. The iodate reduction in acidic solution shown in the pre,ious example would
be con,erted to basic solution as follows using the three steps abo,e#
/e
)
+ .,
+
+ .O,
)
+ %O
(
)
))* %
)
+ (,
-
O + .O,
)

/e
)
+ .,
-
O + %O
(
)
))* %
)
+ (,
-
O + .O,
)

/e
)
+ (,
-
O + %O
(
)
))* %
)
+ .O,
)

"lthough this procedure will gi,e a formally balanced equation in basic aqueous
solutions, the actual reaction in basic solutions may in,ol,e different species than the
reaction in acidic solutions.
9nce a balanced electrode reaction has been obtained, stoichiometric calculations
in,ol,ing electrode reactions can be made using FaradayCs laws in equation form or as a
unit analysis as shown below.
Example. If one 0ilogram of copper is to be deposited by means of the electrochemical
reaction %u
=>
> =e
)
))? %u, we can calculate how many coulombs will be be required. If
a constant current of -( amperes is used to carry out this deposition, we can calculate
how long it will ta0e.
9ne 0ilogram of %u is -(((.'1.@/' moles %u3 since one mole %u requires two moles of
electrons, we need -((( x =.'1.@/' 4 1-./= moles of electrons. !ince one mole of
electrons equals one faraday or E',@B/ coulombs, E',@B/ x 1-.' 4 1.(@- x -('
coulombs are needed.
9ne ampere is one coulomb.sec, so -( " 4 1.@- x -(' %.t s, therefore t 4 1.(@- x -(
>/
seconds. !ince - hour 4 '( x '( 4 1'(( s, the electrolysis will ta0e 1.(@- x -(
>/
.1.' x
-(
>1
4 B@.@D hours.
Example. " current of -.1D/ " flows for E' s through a sil,er cathode in an aqueous
solution of sil,er nitrate. The mass of sil,er deposited on the cathode is calculated as
follows.
The electrical charge 2 used is -.1D/ " times E' s 4 -1= %, which is -1=.E'@B/ 4 -.1'B
mmol of electrons. !ince the deposition reaction is "g
>
> e
)
))? "g, this corresponds to
-.1'B mmol of sil,er metal whose mass is (-(D.B'B g.mol((.((-1'B mol 4 (.-@D' g.
Falancing Electrons in 5edox 5eactions
"lthough electrochemical reactions often occur in solutions which are not aqueous or in
fused salts, we will restrict the discussion in this and the following sections to aqueous
solutions. "queous electrolyte solutions are often strongly acidic, and electrochemical
reactions in neutral solutions often occur in much the same way as do reactions in acidic
aqueous solutions. For basic solutions, it is more straightforward for most reactions to
balance the reaction as if it were in acidic solution and then ma0e the changes indicated
at the end of this section.
The easiest way to balance full redox reactions, which can be quite complicated, can be
di,ided into two steps )) a chemistry step and the machinery step(s. The following
problem is an example of this approach.
Example. Get us complete and balance the following reaction in aqueous acid solution#
MnO
0
)
+ ,
-
C
-
O
0
+111 ))* Mn
-+
+ CO
-
+111
%*EMI!T5H !TE<# Ising your chemical 0nowledge (and some common
sense, di,ide the reaction into two half)reactions. %ommon sense tells you that
you arenCt going to con,ert one element into another, and therefore any element
(except hydrogen and oxygen, which you can get from water as neededin
aqueous solutions must appear on both sides of the same half)reaction.
MnO
0
)
))* Mn
-+
2 ,
-
C
-
O
0
))* CO
-

M"%*I&E5H !TE<!#
-. Falance all elements except hydrogen and oxygen by proper
multiplication of compounds or ions.
MnO
0
)
))* Mn
-+
2 ,
-
C
-
O
0
))* -CO
-

=. Falance oxygen by adding water, *
=
9, as necessary.
MnO
0
)
))* Mn
-+
+ 0,
-
O2 ,
-
C
-
O
0
))* -CO
-

1. Falance hydrogen by adding hydrogen ions, *
>
, as necessary.
3,
+
+ MnO
0
)
))* Mn
-+
+ 0,
-
O2 ,
-
C
-
O
0
))* -CO
-
+ -,
+

@. Falance charge by adding electrons, e
)
, as necessary.
3,
+
+ MnO
0
)
+ /e
)
))* Mn
-+
+ 0,
-
O2 ,
-
C
-
O
0
))* -CO
-
+ -,
+
+ -e
)

/. The two half)reactions (electrode reactions are balanced separately at
this point, and now must be combined. To do so, multiply each equation
by the number of electrons appearing in the other.
4.,
+
+ -MnO
0
)
+ 45e
)
))* -Mn
-+
+ 3,
-
O2 /,
-
C
-
O
0
))* 45CO
-
+ 45,
+
+ 45e
)

To complete the combination, add the two equations together, then cancel
out anything appearing on both sides. The number of electrons cancelled
in this step is the charge number of the redox reaction, +.
4.,
+
+ -MnO
0
)
+ 45e
)
+ /,
-
C
-
O
0
))* -Mn
-+
+ 3,
-
O + 45CO
-
+ 45,
+
+ 45e
)

.,
+
+ -MnO
0
)
+ /,
-
C
-
O
0
))* -Mn
-+
+ 3,
-
O + 45CO
-

"t this point the redox reaction is balanced3 no electrons should be left in the reaction. It
is also desirable to chec0 that the equation can no longer be simplified by di,iding it
through by a simple integer such as = or 1. &o species should appear on both sides of
the equation.
If you are required to balance an equation in basic solution rather than acidic or neutral
solution, proceed in the manner abo,e. "fter balancing the reaction as if it too0 place in
acidic solution, reali+e that protons are not readily a,ailable in basic solutions. !o
remo,e any protons by#
-. adding to both sides of the equation a certain number of hydroxide ions, 9*
)
3
that number equals the number of protons, *
>
, appearing on the only side that
has any.
.,
+
+ -MnO
0
)
+ /,
-
C
-
O
0
+ .O,
)
))* -Mn
-+
+ 3,
-
O + 45CO
-
+ .O,
)

=. combining, when they appear on the same side of the equation, hydrogen ions
(protons and hydroxide ions to form water.
.,
-
O + -MnO
0
)
+ /,
-
C
-
O
0
))* -Mn
-+
+ 3,
-
O + 45CO
-
+ .O,
)

1. remo,ing any water which appears on both sides of the final equation.
-MnO
0
)
+ /,
-
C
-
O
0
))* -Mn
-+
+ -,
-
O + 45CO
-
+ .O,
)

This procedure, balancing aqueous redox equations first as if they were in acidic
solution and then con,erting formally to a basic solution, will always gi,e a formally
correct balanced equation for a redox reaction in basic aqueous solutions, but the actual
species in basic solutions may well be different from those in acidic solutions. In the
abo,e example, neither permanganate ion nor oxalic acid will actually exist in aqueous
basic solutions. The permanganate ion is unstable in basic solution and oxalic acid will
ioni+e to oxalate ion.
Redox Reaction Stoichiometry
!toichiometric calculations in,ol,ing redox reactions always begin with the balanced
redox reaction. 9nce the balanced redox reaction has been obtained, the mole ratios will
gi,e the desired stoichiometric information.
Example. 7e can calculate the mass of JMn9
@
needed to oxidi+e -/.( g of "s
@
9
'
in
acidic solution, gi,en that the products of the reaction are Mn
=>
and arsenic acid,
*
1
"s9
@
. It is first necessary to obtain the balanced redox reaction. The balanced half)
reactions or electrode reactions are#
/e
)
+ 3,
+
+ 6MnO
0
))* Mn
-+
+ 6
+
+ 0,
-
O
45,
-
O + 7s
0
O
.
))* 0,
(
7sO
0
+ 3,
+
+ 3e
)

Multiplying by eight and by fi,e, adding the reactions, and cancelling electrons,
protons, and water to the extent they appear on both sides of the equation gi,es#
-0,
+
+ 36MnO
0
+ 43,
-
O + /7s
0
O
.
))* 3Mn
-+
+ 36
+
+ -5,
(
7sO
0

The molar mass of JMn9
@
is -/B.(@ g.mol3 in the balanced reaction there appears B x
-/B.(@ g. The molar mass of "s
@
9
'
is 1E/.' g.mol3 in the balanced reaction there
appears / x 1E/.' g. The molar ratio in the reaction between them is B JMn9
@
to /
"s
@
9
'
. 7ritten out, this ratio is B x -/B.(@ # / x 1E/.' 4 x # -/.(. "s a consequence x 4
-/.( g "s
@
9
'
(B x -/B.(@ g JMn9
@
.(/ x 1E/.' g "s
@
9
'
4 E./B g JMn9
@

Electrochemical Cells
"n electrochemical cell, or full cell, can either dri,e an external electrical de,ice or be
dri,en by it, depending upon the relati,e electromoti,e forces (potentials, ,oltages
applied by the cell and the de,ice. In addition to external electrochemical de,ices,
external de,ices may be strictly electrical such as motor)generators or incandescent
lights. !ome strictly electrical de,ices, such as incandescent lights, cannot dri,e
electrochemical cells but can only be dri,en by them. 9thers, such as motor)generators,
can both dri,e electrochemical cells and be dri,en by them.
7hen the electromoti,e forces of a cell and a de,ice are opposed and the electromoti,e
force exerted by the de,ice is the stronger, the cell will be dri,en by the de,ice3 the cell
is then called an electrolytic cell. Electrolytic cells are discussed in other sections. 7hen
the electromoti,e forces of the cell and a de,ice are opposed and the electromoti,e force
exerted by the cell is the stronger, the de,ice will be dri,en by the cell3 the cell is then
called a gal,anic cell (after Guigi 6al,ani or a ,oltaic cell (after "lessandro :olta. In
either of these two cases a net current will flow. The current which flows will produce
an electrochemical reaction that follows the principles of electrochemical stoichiometry
)) FaradayCs laws of electrolysis. *owe,er, when the electromoti,e force of the cell is
exactly equal to that of the de,ice and the forces are opposed, no net current will flow.
The electromoti,e force, or electrical potential difference, of the cell is then called its
re,ersible potential difference.
"n electrochemical cell can be described as gal,anic, re,ersible, or electrolytic. These
terms are not normally used to describe electrodes, although the term re,ersible
electrode is sometimes used to describe an electrode operating under no)current or
re,ersible conditions. " gal,anic cell is a cell in which current flows, power is
produced, and the cell reaction is proceeding spontaneously. "n electrolytic cell is a cell
in which current flows, power is consumed, and the cell reaction being dri,en is the
re,erse of the spontaneous cell reaction. " re,ersible cell is a cell in which no current
flows (and therefore no power is in,ol,ed, since P 4 EI. The cell reaction in a
re,ersible cell is neither spontaneous nor nonspontaneous3 it is called re,ersible because
an infinitesimal change in the cell potential can cause it to proceed in either direction.
7hen cells are operated under re,ersible conditions, the potential difference or
electromoti,e force across them can be measured without any loss due to I5 drop (the
re,ersible potential difference is the same as the open)circuit potential difference.
Moreo,er, there cannot be any effects due to Faradaic processes which ta0e place in the
cell as current is passed. For this reason chemists find it much simpler to ma0e
quantitati,e calculations using re,ersible potentials and to measure cell potentials under
conditions as close to re,ersible as is experimentally feasible. 7e shall confine
oursel,es to re,ersible potentials in this and subsequent sections. It is perfectly possible
to measure, or calculate, the potential difference across a gal,anic or electrolytic cell
through which an appreciable current is flowing. *owe,er, the resistance of the cell is
then not constant but depends upon the potential, the current being passed through the
cell, and the nature of the Faradaic processes))complications we defer to later sections,
and e,en then will deal with only in part.
Electrode and Cell Structures and 8otations
Electrode Structures and 8otations
" half)reaction, or electrode reaction, can always in principle (and usually in practice
be set up as an actual physical half)cell. It must be remembered, in doing so, that a half)
cell contains one electrode. "n electrode is a point at which conduction changes from
ionic to electronic. " half)cell reaction as written may contain no electronic conductor
explicitly, but the actual physical half)cell corresponding to that reaction must contain
an electronic conductor which ma0es external electrical contact. The electronic
conductor can be an acti,e part of the electrochemical reaction, as copper electrodes are
in aqueous copper sulfate cells, or it may be an inert conductor which does not ta0e an
acti,e part in the electrode reaction. In aqueous solutions, platinum metal is generally
employed for inert electrodes. In those cases where platinum cannot be employed, other
materials such as carbon or tungsten are used. It is necessary to ensure that the inert
electrode material is truly inert, in the sense that it does not react, either chemically or
electrochemically, under the conditions which will be imposed during its use.
7hen writing a physically real half)cell, we usually specify the physical state of all
components (s, l, g, aq, etc. and denote phase boundaries by a slash, .. " salt bridge, an
electrolytic conductor used to separate two electrolyte solutions while allowing the
passage of ionic charge between them, is designated by .., one slash for the phase
boundary at each end3 the contents of the salt bridge are usually omitted, since it ser,es
only as an ionic conductor. The half)cell notation includes more information than does
the shorter form in which the redox couple of an electrode is usually written. " few
examples follow#
Fe
-+
+ -e
)
9))* Fe2 ##Fe
-+
:a;<#Fe:s<
Cr
(+
+ e
)
9))* Cr
-+
2 ##Cr
(+
:a;<, Cr
-+
:a;<#=t:s<
7'Cl + e
)
9))* Cl
)
+ 7'2 ##7'Cl:s<, Cl
)
:a;<#7':s<
Cl
-
+ -e
)
9))* -Cl
)
2 ##Cl
-
:a;, sat1<, Cl
)
:a;<#C:s<
7hen writing half)reactions, or their corresponding physically real half)cells, it is
necessary to use a consistent style, writing them all either as oxidations or reductions.
!ince -E/B, all chemists ha,e agreed to use the reduction style for both half)cell
reactions and for physically real half)cells. 9nly when two half)reactions are combined
to gi,e a full cell reaction, or when two physically real half)cells are connected together
to form a full cell, are both oxidation and reduction necessarily present and only then
may both styles be used. Electrode reactions are therefore written with a single or
double arrow in the right, or reduction, direction. In an electrode reaction the reduced
species are considered to be products and the oxidi+ed species are considered to be
reactants. In either physically real half)cells or half)reactions, then, the reaction
direction is left to right.
The slash)phase notation may seem odd for reactions such as the e,olution of chlorine
gas, but in fact both the chlorine gas and the chloride ion from which it is produced are
in the same solution. It is only the chlorine gas which exceeds the solubility of chlorine
that is actually e,ol,ed as a gas. Gi0ewise, "g%l(s is in equilibrium with the aqueous
solution containing "g> and %l) ions. "lthough some chemists distinguish these as
separate phases (with additional phase boundaries indicated by slashes or ,ertical bars,
most do not.
Cell Structures and 8otations
"n electrochemical cell is made up of two electrodes whose ionic and electronic
conductors are connected so as to form a complete circuit through which charge can
mo,e. The charge is carried by electrons in part of the circuit and by ions in the
electrolyte as shown in the Figure below.
7hether a cell is gal,anic or electrolytic, electrons flow into cathodes from the
electronic conductors leading to external wires in order to carry out the reduction
reaction. The cell electrode into which electrons flow is the most positi,e electrode of
the cell and it is con,entionally written on the right. This is the Aplus rightA rule.
9ne of the two electrodes of any operating cell is carrying out an oxidation while the
other is carrying out a reduction. The cathode, at which reduction is ta0ing place, is the
most positi,e electrode so the cathode is written on the right. Then the electrons in the
external circuit must flow from left to right3 the electrode on the left must be the cell
anode because oxidation is ta0ing place there. %harge in the electrolyte is carried by
ions, both by the positi,e cations and by the negati,e anions. The anions mo,e so as to
complete the circuit )) that is, anions in the electrolyte mo,e from right to left as
electrons in the external circuit mo,e from left to right. %ations, which are carrying
charge in the same direction as are the anions, mo,e in the opposite direction because
their charges are of opposite sign.
Example. The aqueous cell which operates spontaneously using the reaction Mg(s >
Fe
=>
))? Mg
=>
> Fe(s would be written in cell notation as Mg.Mg
=>
..Fe
=>
.Fe. The Fe(II
is being reduced at the cathode so the iron electrode couple is written on the right. The
flow of electrons in the external circuit is from left to right, the flow of anions in the
electrolyte and salt bridge is from right to left, and the flow of cations in the electrolyte
and salt bridge is from left to right.
Electrochemical =otentials
The potential difference across an electrochemical cell is the potential difference (in
,olts measured between two electronic conductors. In the external circuit connected to
an electrochemical cell, the electrons will flow, as they normally do in electronic
conductors, from the most negati,e point to the most positi,e point. This means that the
electrons in the external circuit connected to an electrochemical cell will always flow
from the most negati,e electrode to the least negati,e electrode. !ince the potentials of
electrodes can be either positi,e or negati,e, the electrons in the external circuit can also
be said to flow from the least positi,e electrode to the most positi,e electrode.
:oltmeters or other de,ices used to measure the potential differences across electrical
circuits or electrochemical cells measure potential differences, and so they cannot
measure the actual potential of any electrode. &e,ertheless, it is con,enient to assign
part of the cell potential to one electrode and part to the other. 7hen this is done, that
part of the cell potential assigned to each electrode has a physically real ,alue which
includes a physically real sign. &oth >alue and si'n ha>e physical si'nificance1
Standard Electrode =otentials
!tandard potential differences are the actual cell potential differences measured in
re,ersible cells under standard conditions. !tandard conditions for substances in
electrochemical cells are the same as the standard conditions used elsewhere in
chemistry. They ha,e been, and will be, discussed in se,eral different sections. For solid
or liquid compounds or elements, standard conditions are the pure compound or
element3 for gases they are -(( 0<a pressure3 and for solutes they are the ideal dilute
solution of -.( mol.litre concentration. Inless otherwise specified, standard conditions
also refer to a total pressure of -(( 0<a. !ome other sources of chemical information,
and many older chemistry textboo0s, use an older standard condition for pressure, -.(
atm, and as a consequence their standard potentials may differ slightly (less than (.- :
from those gi,en in the tables of standard potentials used here.
" table of standard electrode potentials is more useful than a table of standard cell
potential differences because it contains much more information in much less space.
Tables of standard electrode potentials can be obtained if any one electrode, operated
under standard conditions, is designated as the standard electrode or standard reference
electrode with which all other electrodes will be compared. This standard reference
electrode can then arbitrarily be assigned an electrode potential of +ero, 8ust as sea le,el
is assigned the ele,ation of +ero.
%hemists ha,e uni,ersally agreed to select the electrode reaction of the simplest
element, hydrogen, as the reaction and electrode against which all others will be
compared. This electrode is called the standard hydro'en electrode, abbre,iated
!.*.E.. The physically measured potential difference across a re,ersible cell made up of
any electrode and a standard hydrogen electrode))a hydrogen electrode which is being
operated under standard conditions of pressure and concentration))is called the
re,ersible potential of that electrode, E. If the electrode other than hydrogen is also
being operated under standard conditions of pressure and concentration, then the
re,ersible potential difference across the cell is the standard electrode potential or
standard potential, E
(
of the electrode other than hydrogen.
Example. The re,ersible potential difference across a cell containing a hydrogen
electrode and an oxygen electrode is -.=1 :, the oxygen electrode being the more
positi,e. 9ne could assign the potential of the hydrogen electrode as (.( :, in which
case the potential of the oxygen electrode must be >-.=1 : (this is the usual
assignment. 9ne could also assign the potential of the oxygen electrode as (.( :, in
which case that of hydrogen must be )-.=1 :, or assign the potential of oxygen as >-.((
:, in which case the potential of hydrogen must be )(.=1 : (these are not the usual
assignments.
The potential difference across a cell in which one of two electrodes is a standard
hydrogen electrode is by definition the electrode potential of the other electrode, since
the potential of the standard hydrogen electrode is +ero. If neither of the two electrodes
is a standard hydrogen electrode, the potential difference across the cell is the difference
of the two electrode potentials including their sign.
Example. " !n(I:.!n(II electrode in a half)cell ha,ing a potential of )(.-( : is
connected to the half)cell of a Fe
1>
.Fe
=>
electrode ha,ing a potential of >(.D( :. The
potential difference across the cell is (.B( :, the iron electrode being the more positi,e.
Example. " %d
=>
.%d electrode in a half)cell ha,ing a potential of )(.1D : is connected to
the half)cell of a !n
=>
.!n electrode ha,ing a potential of )(.-/ :. The potential
difference across the cell is (.== :, the tin electrode being the more positi,e.
In many practical potential measurements, the standard hydrogen electrode cannot be
used because hydrogen reacts with other substances in the cell or because other
substances in the cell react with the catalytic platinum electrode surface upon which the
*
>
.*
=
potential is established. %hemists then employ alternati,e electrodes whose
potentials are precisely 0nown with respect to the standard hydrogen electrode. Two of
the electrodes most commonly used for this purpose are the "g%l."g electrode,
.."g%l(s,%l
)
."g(c at E
(
4 >(.===- :, and the saturated calomel electrode (!%E. The
chloride concentration in the "g%l."g electrode is the standard concentration, -.(
molar. The saturated calomel electrode is based on the *g
=
%l
=
(s.*g(l couple.
*owe,er, the saturated calomel electrode is not ..*g
=
%l
=
(c,%l
)
(aq, -.( molar.*g(l
but ..*g
=
%l
=
(c,J%l(aq,sat..*g(l. The solution is saturated not only with *g
=
%l
=
but
also with J%l, and the saturation concentration of the highly soluble J%l is well abo,e
-.( molar. "s a consequence the potential of the !%E reference electrode, >(.=@-= :,
differs significantly from the standard reduction potential of the *g
=
%l
=
(c.*g(l couple,
>(.='B( :.
The effect of changing the reference electrode is to change the +ero of a potential scale
while lea,ing the relati,e positions of all of the potentials unchanged, as shown in the
Figure below.
Example. " cell containing a !n
@>
.!n
=>
electrode and a saturated calomel reference
electrode has a measured potential difference of (.-(DD :, the saturated calomel
electrode being positi,e. The potential of the !n
@>
.!n
=>
electrode on the standard
hydrogen reference scale is calculated as follows.
The tin electrode is (.-(DD : negati,e of saturated calomel, which in turn is (.=@-= :
positi,e with respect to standard hydrogen. !tandard hydrogen is therefore (.=@-= :
negati,e of saturated calomel. The potential difference between standard hydrogen and
tin is (.=@-= ) (.-(DD 4 (.-11/ :, hydrogen being the more negati,e. The potential of
the tin electrode is thus >(.-11/ : on the standard hydrogen reference scale. !ince the
tin electrode does not in this example ha,e standard concentrations of one molar, its
,alue differs from the standard potential of the !n
@>
.!n
=>
couple, >(.-/1E :.