Topic 5.

3
REDOX EQUILIBRIA
Oxidation and Reduction
Electrochemical ell! and "uel ell!
The Electrochemical #erie!
#pontaneou! Reaction!
OXIDATION AND REDUCTION
Redox reactions were studied extensively at AS-level. The key points are summarized
here:
The gain and loss of electrons can e shown y means of half-equations.
Oxidation is the loss of electrons. !hen a species loses electrons it is said to e
oxidised.
"g #e
$%
#e
&%
% e
Reduction is the gain of electrons. !hen a species gains electrons it is said to e
reduced.
"g 'n()
-
% *+
%
% ,e 'n
$%
% )+$(
"lectrons can in fact never e created or destroyed- they can only e transferred
from one species to another. Reactions which involve the transfer of electrons are
known as redox reactions.
Overall redox equations can e created ! co"ining the half-equations for
the oxidation process and reduction processes. after multiplying all the
coefficients of the species in one of the half-e/uations y a factor which ensures
that the numer of electrons gained is e/ual to the numer of electrons lost.
"g #e
$%
#e
&%
% e oxidation
'n()
-
% *+
%
% ,e 'n
$%
% )+$( reduction
'ultiplying all coefficients in the oxidation reaction y ,:
,#e
$%
,#e
&%
% ,e
means that , electrons are gained and five are lost
overall e/uation:
'n()
-
% *+
%
% ,#e
$%
'n
$%
% )+$( % ,#e
&%
A species which can accept electrons from another species is an oxidising agent.
(xidising agents are reduced during redox reactions.
"g 'n()
-
is the oxidizing agent in the aove reaction.
A species which can donate electrons to another species is a reducing agent.
Reducing agents are oxidised during redox reactions.
"g #e
$%
is the reducing agent in the aove reaction.
The oxidation nu"er of an ato" is the charge that would exist on the atom if
the onding were completely ionic.
In si"#le ions$ the oxidation nu"er of the ato" is the charge on the ion:
0a
%
. 1
%
. +
%
all have an oxidation numer of %2.
(
$-
. S
$-
all have an oxidation numer of -$.
In "olecules or co"#ounds$ the su" of the oxidation nu"ers on the ato"s
is %ero:
"g S(&- oxidation numer of S 3 %4. oxidation numer of ( 3 -$.
%4 % &5-$6 3 7
In co"#lex ions$ the su" of the oxidation nu"ers on the ato"s is equal to
the overall charge on the ion.
"g 'n()
-
- oxidation numer of 'n 3 %8. oxidation numer of ( 3 -$.
%8 % )5-$6 3 -2
"g 9r$(8
$-
- oxidation numer of 9r 3 %4. oxidation numer of ( 3 -$.
$5%46 % 85-$6 3 -$
"g :($
%
- oxidation numer of : 3 %,. oxidation numer of ( 3 -$.
%, % $5-$6 3 %2
In ele"ents in their standard states$ the oxidation nu"er of each ato" is
%ero:
;n 9l$. S. 0a and ($ all atoms have an oxidation numer of zero.
'any atoms. including most d-lock atoms. exist in different oxidation numers.
;n complex ions or molecules. the oxidation numer of these atoms can e
calculated y assuming that the oxidation numer of the other atom in the species
is fixed.
(xidation numers are useful for writing half-e/uations:
The nu"er of electrons gained or lost can e deduced from the formula:
0o of electrons gained<lost 3
change in oxidation numer x numer of atoms changing oxidation numer
The ox!gen ato"s are alanced y placing an appropriate numer of water
molecules on one side.
The h!drogen ato"s are alanced y placing an appropriate numer of + ions
on one side.
Dis#ro#ortionation is the simultaneous oxidation and reduction of the same
species.
There are many d-lock species which readily undergo oth oxidation and
reduction. and which can therefore ehave as oth oxidising agents and reducing
agents. 9u
%
. 'n
&%
and 'n()
$-
are all examples:
"g 9u
%
9u
$%
% e oxidation
9u
%
% e 9u reduction
"g 'n
&%
% $+$( 'n($ % )+
%
% e oxidation
'n
&%
% e 'n
$%
reduction
"g 'n()
$-
'n()
-
% e oxidation
'n()
$-
% $+
%
% $e 'n($ % $+$( reduction
Species such as these are capale of undergoing oxidation and reduction
simultaneously. =isproportionation reactions are special examples of redox
reactions.
E&ECTROC'E(ICA& CE&&)
*+ Electrode #otentials
9onsider a zinc rod immersed in a solution containing >n
$%
ions 5eg >nS()6:
zinc electrode
Zn
2+
ions in solution
The >n atoms on the rod can deposit two electrons on the rod and move into solution as
>n
$%
ions:
>n5s6 33 >n
$%
5a/6 % $e
This process would result in an accumulation of negative charge on the zinc rod.
Alternatively. the >n
$%
ions in solution could accept two electrons from the rod and move
onto the rod to ecome >n atoms:
>n
$%
5a/6 % $e 33 >n5s6
This process would result in an accumulation of positive charge on the zinc rod.
;n oth cases. a potential difference is set up etween the rod and the solution. This is
known as an electrode #otential.
A similar electrode potential is set up if a copper rod is immersed in a solution containing
copper ions 5eg 9uS()6. due to the following processes:
9u
$%
5a/6 % $e 33 9u5s6 - reduction 5rod ecomes positive6
9u5s6 33 9u
$%
5a/6 % $e - oxidation 5rod ecomes negative6
0ote that a chemical reaction is not taking place - there is simply a potential difference
etween the rod and the solution. The potential difference will depend on the nature of
the ions in solution. the concentration of the ions in solution. the type of electrode used
and the temperature.
,+ Creating an e"f
;f two different electrodes are connected. the potential difference etween the two
electrodes will cause a current to flow etween them. Thus an electro"otive force -e"f.
is estalished and the system can generate electrical energy.
The circuit must e completed y allowing ions to flow from one solution to the other.
This is achieved y means of a salt ridge - often a piece of filter paper saturated with a
solution of an inert electrolyte such as 10(&5a/6.
The e.m.f can e measured using a volt"eter. :oltmeters have a high resistance so that
they do not divert much current from the main circuit.
The comination of two electrodes in this way is known as an electroche"ical cell. and
can e used to generate electricity. The two components which make up the cell are
known as half-cells.
A typical electrochemical cell can e made y comining a zinc electrode in a solution of
zinc sulphate with a copper electrode in a solution of copper sulphate.
V
Cu Zn
Zn
2+
Cu
2+
+ve
-ve
The #ositive electrode is the one /hich "ost favours reduction. ;n this case it is the
copper electrode which is positive.
The negative electrode is the one /hich "ost favours oxidation. ;n this case it is the
zinc electrode which is negative.
Thus electrons flow from the zinc electrode to the copper electrode.
Reduction thus takes place at the copper electrode: 9u
$%
5a/6 % $e 9u5s6
(xidation thus takes place at the zinc electrode: >n5s6 >n
$%
5a/6 % $e
The overall cell reaction is as follows: >n5s6 % 9u
$%
5a/6 >n
$%
5a/6 % 9u5s6
The sulphate ions flow through the salt ridge from the 9u
$%
5a/6 solution to the >n
$%
5a/6
solution. to complete the circuit and compensate for the reduced 9u
$%
concentration and
increased >n
$%
concentration. The cell reaction including spectator ions can thus e
written as follows: 9uS()5a/6 % >n5s6 9u5s6 % >nS()5a/6.
The external connection must e made of a metallic wire in order to allow electrons to
flow. The salt ridge must e made of an a/ueous electrolyte to allow ions to flow.
?y allowing two chemical reagents to e connected electrically. ut not chemically. a
reaction can only take place if the electrons flow externally. The chemical energy is thus
converted into electrical energy.
0+ Designing electroche"ical cells
+alf-cells do not necessarily have to consist of a metal immersed in a solution of its ions.
Any half-reaction can e used to create a half-cell.
;f the half-reaction does not contain a metal in its elemental state. an inert electrode must
e used. @latinum is generally used in this case. as it is an extremely inert metal.
;f a gas is involved. it must e uled through the solution in such a way that it is in
contact with the electrode.
A few examples are shown elow:
a6 #e
&%
5a/6 % e 33 #e
$%
5a/6
A platinum electrode is used. immersed in a solution containing oth #e
$%
and #e
&%
ions:
Pt
mixture of
Fe
2+
and Fe
3+
6 9r$(8
$-
5a/6 % 2)+
%
5a/6 % 4e 33 $9r
&%
5a/6 % 8+$(5l6
A platinum electrode is used. immersed in a solution containing 9r$(8
$-
. +
%
and
9r
&%
ions:
Pt
mixture of
Cr
2
O
7
2-
, H
+
and Cr
3+
c6 9l$5g6 % $e 33 $9l
-
5a/6
A platinum electrode is used. immersed in a solution containing 9l
-
ions. 9hlorine
gas is uled through the solution. in contact with the electrode:
Pt
Cl
2
Cl
-
d6 $+
%
5a/6 % $e 33 +$5g6
A platinum electrode is used. immersed in a solution containing +
%
ions.
+ydrogen gas is uled through the solution. in contact with the electrode:
Pt
H
2
H
+
;n addition to making electricity. half-cells provide important information on the relative
aility of a half-reaction to undergo oxidation or reduction. The "ore #ositive the
electrode$ the greater the tendenc! to undergo reduction$ and the "ore negative the
electrode$ the greater the tendenc! to undergo oxidation.
1+ )tandard conditions
The electrode potential depends on the conditions used. including temperature. pressure
and concentration of reactants.
;t is therefore necessary to specify the conditions used when measuring electrode
potentials. These conditions are normally set at a temperature of $A* 1. a pressure of 2
atm and with all species in solution having a concentration of 2.7 moldm
-&
. "lectrode
potentials measured under these conditions are known as standard electrode #otentials.
They are denoted y the symol "
o
.
;t is possile to predict how the electrode potential will vary if non-standard conditions
are used y using Be 9hatelierCs @rinciple.
;f the oxidizing agent has a concentration greater than 2.7 moldm
-&
. it is more likely to
favour reduction and the electrode potential will e more positive than the standard
electrode potential. ;f it has a concentration of less than 2.7 moldm
-&
. it is more likely to
favour oxidation and the electrode potential will e more negative than the standard
electrode potential. #or reducing agents. the reverse is true.
"g: #e
$%
5a/6 % $e 33 #e5s6
Standard electrode potential 3 -7.)) :
;f D#e
$%
E 3 7.2 moldm
-&
the electrode potential 3 -7.,7 :
The concentration is lower than standard so reduction is less likely to take place.
and hence the electrode potential is more negative than expected.
;f the temperature is higher than $A* 1. then the system will move in the endothermic
direction and the electrode potential will change accordingly.
;f the pressure is greater than 2 atm. then the system will move to decrease the pressure
and the electrode potential will change accordingly.
In general$ a change /hich favours the reduction direction /ill "a2e the electrode
#otential "ore #ositive$ and a change /hich favours the oxidation direction /ill
"a2e the electrode #otential "ore negative.
3+ Reference electrodes
The emf of electrochemical cells is easy to measure. ut the individual electrode
#otentials the"selves cannot actuall! e "easured at all4 it is onl! #ossile to
"easure the #otential difference et/een t/o electrodes. "ven if another electrode
were inserted into the solution. it would set up its own electrode potential and it would
only e possile to measure the difference etween the two electrodes.
It is therefore onl! #ossile to assign a value to a half-cell if one half-cell is
aritraril! allocated a value and all other electrodes are "easured relative to it+ An
electrode used for this #ur#ose is 2no/n as a reference electrode. The electrode
conventionally used for this purpose is the standard hydrogen electrode.
Pt
H
2
H
+
The gas pressure is fixed at 2 atm. the temperature is $,
o
9 and the +
%
ions have a
concentration of 2.7 moldm
-&
.
This electrode is aritrarily assigned a value of 7.77:.
Fsing this electrode. it is possile to assign an electrode potential to all other half-cells.
:oltmeters measure potential on the right-hand side of the cell and sustract it from the
potential on the left-hand side of the cell:
E"f 5 ER') - E&')
;f the standard hydrogen electrode is placed on the left-hand side of the voltmeter.
therefore. the E&') will e zero and the emf of the cell will e the electrode potential on
the right-hand electrode:
"g if the standard >n
$%
5a/6 % $e 33 >n5s6 electrode is connected to the standard hydrogen
electrode and the standard hydrogen electrode is placed on the left. the emf of the cell is
-7.84:.
The >n
$%
5a/6 % $e 33 >n5s6 half-cell thus has an electrode potential of -7.84:.
"g if the 9u
$%
5a/6 % $e 33 9u5s6 electrode is connected to the standard hydrogen
electrode and the standard hydrogen electrode is placed on the left. the emf of the cell is
%7.&):.
The 9u
$%
5a/6 % $e 33 9u5s6 half-cell thus has an electrode potential of %7.&):.
The standard electrode potential of a half-reaction can e defined as follows:
GThe standard electrode #otential of a half-reaction is the e"f of a cell /here the
left-hand electrode is the standard h!drogen electrode and the right-hand electrode
is the standard electrode in questionG.
The e/uation emf 3 "R+S - "B+S can e applied to electrochemical cells in two ways:
a6 If the R') and &') electrode are s#ecified$ and the e"f of the cell "easured
accordingl!$ then if the E
o
of one electrode is 2no/n then the other can e
deduced.
"g ;f the standard copper electrode 5%7.&):6 is placed on the left. and the standard silver
electrode is placed on the right. the emf of the cell is %7.)4:. 9alculate the standard
electrode potential at the silver electrode.
"mf 3 "R+S - "B+S
%7.)4 3 " - 5%7.&):6
" 3 7.)4 % 7.&) 3 %7.*7:
6 If oth )E67s are 2no/n$ the e"f of the cell for"ed can e calculated if the
right-hand electrode and left-hand electrode are s#ecified.
"g ;f R+S 3 silver electrode 5%7.*7:6 and B+S is copper electrode 5%7.&):6. then emf 3
%7.*7 - 7.&) 3 %7.)4:
;n fact. the hydrogen electrode is rarely used in practice for a numer of reasons:
- the electrode reaction is slow
- the electrodes are not easily portale
- it is difficult to maintain a constant pressure
(nce one standard electrode potential has een measured relative to the standard
hydrogen electrode. it is not necessary to use the standard hydrogen electrode again. Any
electrode whose electrode potential is known could e used to measure standard electrode
potentials. Such electrodes are known as secondar! standard electrodes. A useful
example is the calomel electrode.
8+ Conventional Re#resentation of Cells
As it is cumersome and time-consuming to draw out every electrochemical cell in full. a
system of notation is used which descries the cell in full. ut does not re/uire it to e
drawn.
+alf-cells are written as follows:
- the electrode is placed on one side of a vertical line.
- the species in solution. whether solid. li/uid. a/ueous or gaseous. are placed together
on the other side of the vertical line.
- if there is more than one species in solution. and the species are on different sides of
the half-e/uation. the different species are separated y a comma.
"g >n
$%
5a/6 % $e 33 >n5s6
Zn Zn
2+
"g #e
&%
5a/6 % e 33 #e
$%
5a/6
Pt Fe
2+
Fe
3+
,
"g 9l$5g6 % $e 33 $9l
-
5a/6
Pt Cl
2
, Cl
-
!hen two half-cells are connected to form a full electrochemical cell. the cell is written
as follows:
- the more positive electrode is always placed on the right
- the two half-cells are placed on either side of two vertical roken lines 5which
represent the salt ridge
- the electrodes are placed on the far left and far right. and the other species are placed
adHacent to the vertical roken lines in the centre
- on the left 5oxidation6. the lower oxidation state species is written first. and the higher
oxidation state species is written second.
- on the right 5reduction6 the higher oxidation state species is written first. and the
lower oxidation state species is written second.
"g 9ell reaction 3 >n5s6 % $+
%
5a/6 >n
$%
5a/6 % +$5g6
Zn Zn
2+
Pt H
+
, H
2
"g 9ell Reaction 3 9u
$%
5a/6 % +$5g6 9u5s6 % $+
%
5a/6
Pt H
2
, H
+
Cu
2+
Cu
"g 9ell reaction 3 Ag
%
5a/6 % #e
$%
5a/6 Ag5s6 % #e
&%
5a/6
Pt Fe
2+
, Fe
3+
!
+
!
This method of representing electrochemical cells is known as the conventional
representation of a cell. and it is widely used.
(ne advantage of this notation is that it is easy to see the reduction and oxidation
processes taking place.
(n the B+S 5oxidation6: electrode reduced species oxidised species
(n the R+S 5reduction6: oxidised species reduced species electrode
9+ Rechargeale and non-rechargeale cells
"lectrochemical cells are the asis for all atteries. ?atteries contain two separate half-
cells. The solutions are connected y a salt ridge or semi-permeale memrane which
allows ions to flow through without allowing complete mixing of the solutions. The
electrodes are connected to the terminals of the attery. and when the attery is connected
to an electrical device a current can flow.
;f the reactions taking place in the half-cells are reversile. the attery is rechargeale. ?y
connecting the attery to another power supply with a larger emf. electrons and ions are
forced around the circuit in the opposite direction. This reverses the spontaneous
chemical reaction and hence recharges the attery.
;f the reactions taking place in the half-cells are irreversile the attery is non-
rechargeale.
:+ ;uel Cells
A fuel cell is a cell in which a chemical reaction etween a fuel and oxygen is used to
create a voltage. The fuel and oxygen flow into the cell continuously and the products
flow out of the cell. Therefore the cell does not need to e recharged.
The most widely used fuel cell is the h!drogen-ox!gen fuel cell:
A fuel cell. like a regular electrochemical cell. consists of two half-cells connected y a
semi-permeale memrane. An a/ueous solution of sodium hydroxide is used as the
electrolyte.
(xygen is pumped into one of the half-cells:
($5g6 % +$(5l6 % )e
-
3 )(+
-
5a/6 "
7
3 %7.)7 :
+ydrogen is pumped into the other half-cell:
+$(5l6 % $e
-
33 +$5g6 % $(+
-
5a/6 "
7
3 -7.*& :
The oxygen half-cell is more positive and therefore undergoes reduction. The hydrogen
half-cell is more negative and undergoes oxidation:
($5g6 % +$(5l6 % )e
-
)(+
-
5a/6 reduction
+$5g6 % $(+
-
5a/6 +$(5l6 % $e
-
oxidation
($5g6 % $+$5g6 $+$(5l6 overall cell reaction. emf 3 2.$& :
+ydroxide ions are generated in the oxygen half-cell and travel through the memrane
into the hydrogen half-cell. where they are used up.
!ater is the product of the reaction and it is allowed to run off.
-
+
H
2
in
O
2
in
H
2
O out
OH
-
There are a numer of advantages of fuel cells as a way of producing energy:
- The hydrogen-oxygen fuel cell produces water as the only product. ;t therefore
does not produce any of the greenhouse or polluting gases associated with
comustion engines. The process of generating hydrogen for use in fuel cells does
produce a small /uantity of caron dioxide. ut much less than would e
generated y a comustion engine.
- #uel cells are more efficient than comustion engines. Typically fuel cells are
approximately ,7I efficient ut comustion engines are approximately $7I
efficient.
+owever there are also a numer of limitations of fuel cells as a way of producing
energy:
- +ydrogen is a flammale gas with a low oiling point. ;t is therefore oth difficult
and dangerous to store and transport. ;t can e stored as a li/uid under pressure or
as a solid adsored to the surface of a solid. ut oth of these techni/ues are
expensive.
- As a result. otaining hydrogen as a fuel is difficult and this means that people
will not uy hydrogen-powered vehicles.
- #uel cells use toxic chemicals in their manufacture
- #uel cells have a limited lifetime
T'E E&ECTROC'E(ICA& )ERIE)
;f all of the standard electrode potentials are arranged in order. usually starting with the
most negative. a series is set up which clearly shows the relative tendency of all the half-
reactions to undergo oxidation and reduction. This series is known as the electrochemical
series. and a reduced form of this series is shown as follows:
+AB#-"JFAT;(0 "
o
<:
Bi
%
5a/6 % e 33 Bi5s6 -&.7&
1
%
5a/6 % e 33 15s6 -$.A$
9a
$%
5a/6 % $e 33 9a5s6 -$.*8
0a
%
5a/6 % e 33 0a5s6 -$.82
'g
$%
5a/6 % $e 33 'g5s6 -$.&8
?e
$%
5a/6 % $e 33 ?e5s6 -2.*,
Al
&%
5a/6 % &e 33 Al5s6 -2.44
'n
$%
5a/6 % $e 33 'n5s6 -2.2A
:
$%
5a/6 % $e 33 :5s6 -2.2*
>n
$%
5a/6 % $e 33 >n5s6 -7.84
9r
&%
5a/6 % &e 33 9r5s6 -7.8)
#e
$%
5a/6 % $e 33 #e5s6 -7.))
$+$(5l6 % $e 33 +$5g6 % $(+
-
5a/6 -7.)$
@S()5s6 % $e 33 @5s6 % S()
$-
5a/6 -7.&4
9o
$%
5a/6 % $e 33 9o5s6 -7.$*
:
&%
5a/6 % e 33 :
$%
5a/6 -7.$4
0i
$%
5a/6 % $e 33 0i5s6 -7.$,
Sn
$%
5a/6 % $e 33 Sn5s6 -7.2)
9r()
$-
5a/6 % )+$(5l6 % &e 33 9r5(+6&5s6 % ,(+
-
5a/6 -7.2&
@
$%
5a/6 % $e 33 @5s6 -7.2&
9($5g6 % $+
%
5a/6 % $e 33 9(5g6 % +$(5l6 -7.27
$+
%
5a/6 % $e 33 +$5g6 7.77
S)(4
$-
5a/6 % $e 33 $S$(&
$-
5a/6 %7.7A
9u
$%
5a/6 % e 33 9u
%
5a/6 %7.2,
)+
%
5a/6 % S()
$-
5a/6 % $e 33 +$S(&5a/6 % $+$(5l6 %7.28
9u
$%
5a/6 % $e 33 9u5s6 %7.&)
:(
$%
5a/6 % $+
%
5a/6 % e 33 :
&%
5a/6 % +$(5l6 %7.&)
9u
%
5a/6 % e 33 9u5s6 %7.,$
;$5a/6 % $e 33 $;
-
5a/6 %7.,)
$+
%
5a/6 % ($5g6 % $e 33 +$($5a/6 %7.4*
#e
&%
5a/6 % e 33 #e
$%
5a/6 %7.88
Ag
%
5a/6 % e 33 Ag5s6 %7.*7
$+
%
5a/6 % 0(&
-
5a/6 % e 33 0($5g6 % +$(5l6 %7.*2
:($
%
5a/6 % $+
%
5a/6 % e 33 :(
$%
5a/6 % +$(5l6 %2.7$
?r$5a/6 % $e 33 $?r
-
5a/6 %2.7A
$;(&
-
5a/6 % 2$+
%
5a/6 % 27e 33 ;$5a/6 % 4+$(5l6 %2.2A
($5g6 % )+
%
5a/6 % )e 33 $+$(5l6 %2.$&
'n($5s6 % )+
%
5a/6 % $e 33 'n
$%
5a/6 % $+$(5l6 %2.$&
9r$(8
$-
5a/6 % 2)+
%
5a/6 % 4e 33 $9r
&%
5a/6 % 8+$(5l6 %2.&&
9l$5g6 % $e 33 $9l
-
5a/6 %2.&4
@($5s6 % )+
%
5a/6 % $e 33 @
$%
5a/6 % $+$(5l6 %2.)4
'n()
-
5a/6 % *+
%
5a/6 % ,e 33 'n
$%
5a/6 % )+$(5l6 %2.,2
@($5s6 % )+
%
5a/6 % S()
$-
5a/6 33 @S()5s6 % $+$(5l6 %2.4A
'n()
-
5a/6 % )+
%
5a/6 % &e 33 'n($5s6 % $+$(5l6 %2.87
+$($5a/6 % $+
%
5a/6 % $e 33 $+$(5l6 %2.88
Ag
$%
5a/6 % e 33 Ag
%
5a/6 %2.A*
#$5g6 % $e 33 $#
-
5a/6 %$.*8
0ote that all half-e/uations are written as reduction processes. This is in
accodance with the ;F@A9 convention for writing half-e/uations for electrode
reactions.
The electrochemical series has a numer of useful features:
All the species on the left-hand side of the series are can accept electrons and e
reduced to a lower oxidation state. They are therefore all oxidising agents. All the
species on the right-hand side of the series can give up electrons and e oxidised
to a higher oxidation state. and are thus reducing agents.
The higher a half-e/uation is located in the electrochemical series. the more
negative the standard electrode potential and the greater the tendency to undergo
oxidation. The reducing agents at the top of the series are thus very strong. and the
oxidising agents very weak. The lower down a half-e/uation is located in the
electrochemical series. the more positive the standard electrode potential and the
greater the tendency to undergo reduction. The oxidising agents at the ottom of
the series are thus very strong. and the reducing agents very weak.
;t can therefore e deduced that:
i6 oxidising agents increase in strength on descending the electrochemical series
ii6 reducing agents decrease in strength on descending the electrochemical series
;f two half-cells are connected. the half-cell higher up the electrochemical series
5ie more negative6 will undergo oxidation and the half-cell lower down the
electrochemical series 5ie more positive6 will undergo reduction.
'any of these electrode potentials cannot e measured experimentally. since one
of the species involved reacts with water. ;n such cases the standard electrode
potentials are calculated. often using a complex ?orn-+aer cycle.
)6ONTANEOU) REACTION)
;f two half-cells are connected electrically and a current allowed to flow. the more
positive electrode will undergo reduction and the more negative electrode will undergo
oxidation. The oxidising agent at the more positive electrode is reduced. and thus oxidises
the reducing agent at the more negative electrode.
"g ;f the zinc electrode and the copper electrode are connected. the following reaction
takes place:
>n5s6 % 9u
$%
5a/6 >n
$%
5a/6 % 9u5s6
;t can e assumed that if a reaction occurs electrochemically. it will also occur
chemically. Thus if zinc metal is added to a solution of copper 5;;6 sulphate. the aove
reaction will occur.
;f copper metal is added to a solution of zinc 5;;6 sulphate. however. no reaction will
occur. ;f any reaction did occur. it would have to e
9u5s6 % >n
$%
5a/6 9u
$%
5a/6 % >n5s6
This reaction is not the one which takes place if the two half-cells are connected. and
therefore cannot e expected to take place in other circumstances.
2. (xidising agents and reducing agents
Since the more positive electrodes are at the ottom of the electrochemical series. the
oxidising agents in these systems will oxidise any reducing agent which lies aove it in
the electrochemical series.
"g +
%
5a/6 will oxidise @5s6 to @
$%
5a/6. and any other metal aove it. ut will not oxidise
9u5s6 to 9u
$%
5a/6 or any metal elow it.
@5s6 % $+
%
5a/6 @
$%
5a/6 % +$5g6
Acids such as nitric acid. however. which contains the more powerful oxidising agent
0(&
-
5a/6. will oxidise any reducing agent with a standard electrode potential more
negative than %7.*2:. eg 9u5s6
9u5s6 % )+
%
5a/6 % $0(&
-
5a/6 9u
$%
5a/6 % $0($5g6 % $+$(5l6
Reducing agents will reduce any oxidising agent which lies elow it in the
electrochemical series.
"g #e
$%
5a/6 will reduce :($
%
5a/6 to :(
$%
5a/6. ut not :(
$%
5a/6 to :
&%
5a/6 or :
&%
5a/6 to
:
$%
5a/6
:($
%
5a/6 % $+
%
5a/6 % #e
$%
5a/6 :(
$%
5a/6 % +$(5l6 % #e
&%
5a/6
$. 9ell potential
A more systematic method of predicting whether or not a reaction will occur is to
construct two half-e/uations. one reduction and one oxidation. for the reaction trying to
take place.
Since reduction occurs at the more positive electrode. consider the reduction process to
e the right-hand electrode and the oxidation process to e the left-hand electrode.
The cell #otential for the reaction is given ! ER') - E&')$ or EReduction - EOxidation.
If the cell #otential is #ositive$ the reaction /ill occur.
If the cell #otential is negative$ the reaction /ill not occur.
This method can e used to predict whether or not any given redox reaction will take
place.
a6 =isplacement reactions
"g. @redict whether or not zinc metal will displace iron from a solution of #eS()5a/6.
The reaction under consideration is >n5s6 % #e
$%
5a/6 33 >n
$%
5a/6 % #e5s6
Reduction: #e
$%
5a/6 % $e 33 #e5s6 5"
o
3 -7.)):6
(xidation: >n5s6 33 >n
$%
5a/6 % $e 5"
o
3 -7.84:6
"9"BB 3 -7.)) -5-7.846 3 %7.&$:
So the reaction will occur.
"g @redict whether or not zinc metal will desplace manganese from a solution of
'nS()5a/6
The reaction under consideration is >n5s6 % 'n
$%
5a/6 >n
$%
5a/6 % 'n5s6
Reduction: 'n
$%
5a/6 % $e 33 'n5s6 5"
o
3 -2.2A:6
(xidation: >n5s6 33 >n
$%
5a/6 % $e 5"
o
3 -7.84:6
"9"BB 3 -2.2A -57.846 3 -7.)&:
So the reaction will not occur.
"g @redict whether or not romine will displace iodine from a solution of 1;5a/6
The reaction under consideration is ?r$5a/6 % $;
-
5a/6 33 $?r
-
5a/6 % ;$5a/6
Reduction: ?r$5a/6 % $e 33 $?r
-
5a/6 5"
o
3 %2.7A:6
(xidation: $;
-
5a/6 33 ;$5a/6 % $e 5"
o
3 %7.,):6
"9"BB 3 2.7A - 7.,) 3 %7.,,:
So the reaction will occur.
"g @redict whether or not romine will displace chlorine from a solution of 0a9l5a/6
The reaction under consideration is ?r$5a/6 % $9l
-
5a/6 33 $?r
-
5a/6 % 9l$5a/6
Reduction: ?r$5a/6 % $e 33 $?r
-
5a/6 5"
o
3 %2.7A:6
(xidation: $9l
-
5a/6 33 9l$5a/6 % $e 5"
o
3 %2.&4:6
"9"BB 3 2.7A - 2.&4 3 -7.$8:
So the reaction will not occur.
6 =isproportionation
Standard electrode potentials can e used to predict whether or not a species will
disproportionate.
"g @redict whether or not Ag
%
ions will disproportionate in a/ueous solution.
Ag
%
might e expected to disproportionate according to the following half-
reactions:
Ag
%
5a/6 % e 33 Ag5s6 reduction. "
o
3 % 7.*7:
Ag
%
5a/6 33 Ag
$%
5a/6 % e oxidation. "
o
3 % 2.A*:
"9"BB 3 7.*7 - 2.A* 3 -2.2*:
Therefore Ag
%
will not disproportionate
"g @redict whether or not +$($ will disproportionate in a/ueous solution.
+$($ might e expected to disproportionate according to the following half-
reactions:
+$($5a/6 % $+
%
5a/6 % $e 33 $+$(5l6 reduction. "
o
3 %2.88:
+$($5a/6 33 $+
%
5a/6 % ($5g6 % $e oxidation. "
o
3 %7.4*:
"9"BB 3 2.88 - 7.4* 3 %2.7A:
Therefore +$($5a/6 will disproportionate:
$+$($5a/6 % $+
%
5a/6 $+
%
5a/6 % ($5g6 % $+$(5l6
$+$($5a/6 $+$(5l6 % ($5g6
0+ Non-standard conditions
Though cell potential is often a correct prediction of whether or not a given reaction will
take place. it does strictly apply only to standard conditions. ;f the solutions used are
either very concentrated or very dilute. then the electrode potentials will not e the
standard electrode potentials and the sign of the cell potential may e different from that
predicted under standard conditions. Thus many reactions which are not expected to
occur do in fact take place if the solutions are hot or concentrated. and many reactions
which are expected to occur do not take place if the solutions are too dilute.
"g The reaction etween manganese dioxide and hydrochloric acid.
'n($5s6 % )+
%
5a/6 % $9l
-
5a/6 'n
$%
5a/6 % 9l$5g6 % $+$(5l6
Reduction: 'n($5s6 % )+
$%
5a/6 % $e 33 'n
$%
5a/6 % $+$(5l6 "
o
3 %2.$&:
(xidation: $9l
-
5a/6 9l$5g6 % $e "
o
3 %2.&4:
"9"BB 3 "r - "o 3 -7.2&:
This reaction does not occur under standard conditions. +owever if hot
concentrated +9l is used. the high 9l
-
concentration favours oxidation. the
electrode potential ecomes less positive and "9"BB thus ecomes positive and the
reaction occurs.
"g The reaction etween potassium dichromate 5:;6 and hydrochloric acid.
9r$(8
$-
5a/6 % 2)+
%
5a/6 % 49l
-
5a/6 $9r
&%
5a/6 % &9l$5g6 % 8+$(5l6
Reduction: 9r$(8
$-
5a/6 % 2)+
%
5a/6 % 4e 33 $9r
&%
5a/6 % 8+$(5l6 "
o
3 %2.&&:
(xidation: $9l
-
5a/6 33 9l$5g6 % $e "
o
3 %2.&4:
"9"BB 3 "r - "o 3 -7.7&:
This reaction does not occur under standard conditions. +owever if solid
potassium dichromate is dissolved in hydrochloric acid. the high 9r$(8
$-

concentration favours reduction and makes the electrode potential more positive.
Thus "9"BB ecomes positive and the reaction occurs.
1+ <inetic stailit!
9ell potentials can e used effectively to predict whether or not a given reaction will take
place. ut they give no indication as to how fast a reaction will proceed. ;n many cases
"9"BB is positive ut no apparent reaction occurs. This is ecause the reactants are
kinetically stale- the reaction has a high activation energy so is very slow at room
temperature. There are many examples of this in inorganic chemistry:
"g 'g5s6 % $+$(5l6 'g
$%
5a/6 % $(+
-
5a/6 % +$5g6
" 3 -7.)$:. " 3 -$.&*: so "9"BB 3 "r - "o 3 %2.A4:
So a reaction is expected ut no reaction takes place.
This is ecause the activation energy is too high 5magnesium will react with steam
and slowly with hot water6.
Thus if a reaction is ex#ected to ta2e #lace ut is found not to$ there are t/o #ossile
reasons=
- the solutions are too dilute -ie conditions are non-standard.
- the reaction is ver! slo/ -ie reactants are 2ineticall! stale.
If a reaction is not ex#ected to ta2e #lace ut does ta2e #lace$ then it is ecause the
conditions are non-standard -ie the solutions are concentrated.+