2.

1 INTRODUCTION
There can be multiple outputs of a chemical reaction like

Light Electricity Heat

For the purpose of this chapter we’re focusing on electrical output only. And
for the purpose of this chapter it’s also important to note that while electricity

can be one output of a chemical reaction, electricity can also be used to

drive chemical reactions.

(voltaic
cell)
Chemical Reaction Electricity
(electrolysis)
owing through a solution both constitute electrical current. Since redox rea
e the transfer of electrons from one substance to another, these reactions ha
2. 2 REDOX EQUILIBRIA
ial to generate electrical current as we discussed in Section 19.1.
r example, consider the spontaneous redox reaction:

2+ 2+
Zn(s) + Cu (aq) ¡ Zn (aq) + Cu(s)

2+
Zn metal is placed in a Cu solution, the greater tendency of zinc to los
When Zn metal is placed in a Cu 2+ solution,
2+ the greater tendency
esults in Zn being oxidized and Cu being reduced. Electrons are trans of zinc
to lose electrons results
2+ in Zn being oxidized and Cu2+ being reduced.
y from the Zn to the Cu (Figure 19.1▶, on the next page). Although the
Electrons are transferred directly from the Zn to the Cu 2+.
s is more complicated, we can imagine that—on the atomic scale—a zinc
the zinc metal transfers two electrons to a copper ion in solution. The zinc
ecomes a zinc ion dissolved in the solution. The copper ion accepts the tw
nd is deposited on the zinc as solid copper.
ppose we were to separate the zinc atoms and copper ions and force the el
ry

2. 3 REDOX EQUILIBRIA 2+
A Spontaneous Redox Reaction: Zn + Cu

Zinc strip
n.
e Zinc strip

Copper(II)
sulfate solution

Deposited Copper
owing through a solution both constitute electrical current. Since redox rea
e the transfer of electrons from one substance to another, these reactions ha
2. 4 REDOX EQUILIBRIA
ial to generate electrical current as we discussed in Section 19.1.
r example, consider the spontaneous redox reaction:

2+ 2+
Zn(s) + Cu (aq) ¡ Zn (aq) + Cu(s)

2+
Zn metal is placed in a Cu solution, the greater tendency of zinc to los
On the atomic scale—a zinc atom within
2+ the zinc metal transfers
esults in Zn being oxidized and Cu being reduced. Electrons are trans two
electrons to a copper ion
2+ in a solution. Zn atoms being more reactive
y from the Zn to the Cu (Figure 19.1▶, on the next page). Although the
become Zn 2+ (reducing agent) and Cu2+ being less reactive are reduced
s is more complicated, we can imagine that—on the atomic scale—a zinc
to Cu atoms (oxidising agent).

the zinc metal transfers two electrons to a copper ion in solution. The zinc
ecomes a zinc ion dissolved in the solution. The copper ion accepts the tw
nd is deposited on the zinc as solid copper.
ppose we were to separate the zinc atoms and copper ions and force the el
 2. 5 REDOX EQUILIBRIA

Zn atoms
(solid)
2+
Zn ion

2+
Cu ions
in solution Cu atom

−
e
Gains 2e- (oxidising agent)

2+ 2+
Zn(s) + Cu (aq) Zn (aq) + Cu(s)

Loses 2e- (reducing agent)

The Voltaic Cell

2. 6 HALF-CELLS A metal wire dipped
into a salt solution
forms another half
A similar reaction can occur cell
when the two metals are
connected via wires. But it
fails to proceed in such a
setup because Zn needs a
liquid medium to ionise. The
metal must thus be placed in
a solution for the following
reaction to occur .
2. 7 HALF-CELLS
Solid strip of zinc is placed in it’s own salt solution, Zn(NO3)2,(aq) to form a
half-cell.

The metal strips act as electrodes, conductive surfaces through which

electrons can enter or leave the half-cells.

The electrode where oxidation occurs is the anode and the electrode
where reduction occurs is the cathode

Anode is negative. (loses e )

Cathode is positive. (gains e-)

Electrons flow from the anode to the cathode.

2. 8 HALF-CELLS
 Glass wool Cu 2+
ion
plugs allow
2. 9 HALF-CELLS ions to pass
e−− Cu 2+

e
When the rate of ions leaving the metal surface equals the rate at which
Zn(NO3it
they are joining )2(aq) Cu(NO
again, dynamic equilibrium 3)2 (aq)
is established.

− +
NO−3
NO3 K
K
+

Oxidation Reduction
Anode
Anode −
2+ − 2+ − Zn(s) −
Zn(s) Zn ions + 2 e Cu (aq) + 2 e Zn(s) Cu(s)
Saltbridge
Salt bridge
containing
containing
KNO
KNO (aq)
(aq)
aic Cell The tendency of zinc to transfer electrons
−−
to copper results 3 3
2e2e lost
lostby
byeach
each
ugh the wire that lights the bulb. The movement
Zn
Znatom of electrons from
atomoxidized
oxidized Glass
Glass wool
wool
plugs
plugs allow
allow
per cathode creates a positive charge buildup
−−
ee at the zinc half-cell ionstoto
ions pass
pass
dup at the copper half-cell. The flow of ions within the salt bridge
2+
2+
ldup, allowing the reaction to continue. Zn
Zn
Zn(NO
Zn(NO3)32)(aq)
2(aq)
Zn
Zn
Oxidation
Oxidation
2+
2++ 2 e− − 2+2+
Zn(s)
Zn(s) Zn
Zn + 2 e CuCu +
 e half-cells. Each metal strip reaches equilibrium with its ions
hese2. 10 HALF-CELLS
half-reactions: − −
e e
A solid strip of copper is also placed in a Cu(NO3)2 solution forming a
2+ -
Zn(s) ∆ Zn
second half-cell.
(aq) + 2 e
2+ -
Cu(s) ∆ Cu (aq) + 2 e NO3−
K +

Anode − + Cathode
Zn(s) Cu(s)
n of these equilibria is not theSaltsame bridge for both metals. As we have
containing
greater tendency to ionize than
KNO3(aq)the copper, so the zinc half-
2e− lost by each 2e− gained by each
he right. As a result, the zinc
Zn atom oxidized Glass electrode
wool
plugs allow
becomes negatively
Cu 2+
ion reduced

pper electrode.
e− ions to pass Cu 2+

e connected Zn 2+
by a wire running
Zn(NO ) (aq)
32
from the Cu(NO zinc—through
) (aq)32
a light-
Cu e −
Zn
vice—to the copper, electrons Oxidation spontaneously
Reduction flow from the zinc
2+ − 2+ −
Zn(s) Zn + 2 e Cu + 2 e Cu(s)
negatively charged, and therefore, repels electrons) to the cop-
 2. 11 HALF-CELLS
e TO CIRCUITS e − −

− +
NO3 K
Anode − + Cathode
Zn(s) Cu(s)
Salt bridge
The two half- containing
KNO3(aq)
cells
2 e− lostare put
by each 2 e− gained by each
Zn atom oxidized Glass wool 2+
Cu ion reduced
together. plugs allow
− ions to pass
e Cu2+

Zn2+
Zn(NO3)2(aq) Cu(NO3)2(aq)
−
Zn Cu e
Oxidation Reduction
Zn(s) Zn2+ ions + 2 e− Cu2+(aq) + 2 e− Cu(s)

▲ FIGURE 19.2 A Voltaic Cell The tendency of zinc to transfer electrons to copper results
2. 12 HALF-CELLS TO CIRCUITS − −
e e

Wires are NO3− K+

added, mostly Anode − + Cathode
Zn(s) Cu(s)
of metals that Salt bridge
containing
are less KNO3(aq)
2 e− lost by each 2 e− gaine
reactive orZnof
atom oxidized Glass wool Cu2+ ion r
plugs allow
the samee− ions to pass Cu2+

material as the Zn2+

Zn(NO3)2(aq) Cu(NO3)2(aq)
electrode.Zn
Oxidation Reduction
Zn(s) Zn2+ ions + 2 e− Cu2+(aq) + 2 e− Cu(s)
2. 13 HALF-CELLS TO CIRCUITS
Zinc has a greater tendency to ionise than copper, so the zinc half-
reaction lies further to the right. As a result, the zinc electrode becomes
negatively charged. And acts as the anode.
2. 14 SIGNIFICANCE OF SALT BRIDGE
If the movement of electrons from anode to cathode were the only flow
of charge, the buildup of the opposite charge in the solution would stop
electron flow almost immediately.

To prevent this buildup of opposite charge in the solution, a salt-bridge

is used. Electrons flow out of the salt bridge into the half cell to prevent
positive charge buildup. Electrons can also flow from the half cell
solution into the salt bridge.
 A Voltaic Cell

2. 15 HALF-CELLS TO CIRCUITS
e− e−

Salt bridge is added

to complete the
NO3− K+
circuit. It’s made Anode Cathode
− +
from a salt that Zn(s) Cu(s)
Salt bridge
usually will not react containing
KNO3(aq)
and precipitate and 2 e− lost by each 2 e−
Zn atom oxidized Glass wool Cu2+
will only neutralise plugs allow
e− ions to pass Cu2+
the charge build-up.
KNO3 is mostly Zn2+
Zn(NO3)2(aq) Cu(NO3)2(aq)
used as the ions are Zn
Oxidation Reduction
Zn2+ ions + 2 e− Cu2+(aq) + 2 e−
nonreactive. Zn(s) Cu(s)

▲ FIGURE 19.2 A Voltaic Cell The tendency of zinc to transfer electrons to copper results
in a flow of electrons through the wire that lights the bulb. The movement of electrons from
2. 16 ELECTRODE POTENTIAL
Each half cell has it’s own equilibrium. The more reactive the electrode,
more the equilibrium lies to the ionised side and larger is the buildup of
charge on it, giving rise to greater potential difference between the
electrode and it’s electrolyte.

But as stated previously, it develops an equilibrium, which means the

net potential difference remains zero and hence cannot be detected by
a voltmeter.

2. 17 ELECTRODE POTENTIAL
However, this equilibrium in each half cell is disrupted when the two half
898 Chapter 19 Electrochemistry
cells are connected. There is a net potential difference between the two
half cells, and flow of e occurs from higher to lowerStandard
- potential which
Electrode Potentials
can 19.4
be detected by a voltmeter. Once disrupted, each half cell’s equilibriumAs we have
on the spec
shifts according to the Le Chatelier’s principle.
energy dif
electrode i
electrode
High
the two sta
This potential difference between potential
energy We can
Low
different w
different electrodes forms the basis of potential
in each tan
energy
the reactivity series of various elements. connected
Direction of the tank w
spontaneous electrochem
flow cells are con
2. 18 ELECTRODE POTENTIAL

Absolute potential difference

of a half cell cannot be
measured. Therefore we
measure the potential
difference between two half
cells by connecting the whole
circuit to a voltmeter.
2. 19 ELECTRODE POTENTIAL
Before the potential difference across a circuit can be measured each half cell
has to have standardised conditions as a change in conditions affects the
potential difference.

Each electrode / electrolyte combination (half-cell) has its own half-

reaction which sets up a potential difference (electrode potential).

The value is affected by:

1. temperature

2. pressure of any gases

3. concentration of solutions
2. 20 STANDARD ELECTRODE POTENTIAL
Each standard electrode potential is measured under standard
conditions of :

1. Temperature of 298K

2. Pressure of 1 atm

3. Solution concentration of 1mol/dm3

4. Pure metal electrode

2. 21 STANDARD HYDROGEN ELECTRODE
A voltaic cell combination of Zn/Cu2+ gives a reading of 1.10V. Whereas
Mg/Cu2+ gives a reading of 2.62V. By keeping the Cu2+ half cell in both
combinations, we can compare and deduce that Mg is more reactive

than Zn.

Such a concept is employed in the development of a Standard Hydrogen

Electrode
2. 22 STANDARD HYDROGEN ELECTRODE
To determine the reactivity of various electrodes we compared it against
a Hydrogen half cell as our standard. However, the only source of e- are
metals. H2 being a gas, needs an acid and a metal to complete it’s half
equation.
 2. 23 STANDARD HYDROGEN ELECTRODE
H2(g) is thus passed through
not beplatinum
measuredwirein isolation,
at 1 atm dipped
ard. The standard that is chosen
into 1 mol dm solution of H+
-3 Examiner’s tip
9.14). (aq) ions at 298 K
You will need to recall the
ogen gas at 1 atm pressure features of the standard
ery high surface area in a hydrogen electrode.
−3 H (aq) + e- ⇌ ½ H2(g)
+

dm . Platinum is chosen as it
be oxidised and does not react
The standard electrode Note: the reaction could also have
lf cell potential
is: of this system is been written as:
arbitrarily assigned a value of
zero. + − 1
H (aq) + e 2 H2 (g)
tential (E ) of 0.00 V. E = 0.00 V
2. 24 ZINC STANDARD ELECTRODE POTENTIAL
The standard electrode potential
(EƟ) of Zn could be measured by
connecting a standard Zn half cell
(1moldm−3 Zn2+(aq)/Zn(s)) to the
standard hydrogen electrode.

The Zn half equation goes

backward, and H2 half equation
goes forward.
- H+(aq) + e- ⇌ ½ H2(g)
 half-cell (the anode) from the measured cell potential (E°c ell ):
Electrons travel from the anode (where oxidation occurs) to the cathode (where re
tion occurs), so we define E°cell as the difference in voltage between the cathode (final s
E°cell = E°cathode - E°
2. 25 ZINC
0.76 V = 0.00 V - E°anode
STANDARD
anode
E°
and the anode (initial state):
E°cell = E°final - E°initial
(E Ɵ)

E°anode = -0.76 V = E°cathode - E°anode

The sign with the voltage value in
electrode
Suggestsis negative.
that 0.76VThe negative
is The measuredpotential indicates
cell potential that
for this cell
such a cell setup always tells the
is +0.76 V. The anode (in this case, Zn>Z
is at a more negative voltage (higher potential energy) than the cathode (in this case
ctrode
thehas greater
potential potential energy
difference than
direction of it does
reaction atthethe
for SHE.
element
SHE). Therefore, electrons spontaneously flow from the anode to the cathode. We
e theproduced
electrode potential is, the greater
when a diagram thewhosethe potential
reactivity
potential energy weandenergy
are finding
the of an
out.
voltage as follows:
standard
se negative zinc repels
charge electrode
electrons). –
is placed with a standard 2 e– Anode: Zn(s) 2+
Zn (aq) +2 e–
hydrogen electrode. The – 0.76 V
Potential
negative sign means that Energy spontaneous
Voltage
Zn acts as the negative Cathode: 2 H+(aq) + 2 e– H2(g)
electrode and it’s 0.00 V
equilibrium moves
backwards. +

Referring back to our water tank analogy, the zinc half-cell is like the water tank with
 In the hydrogen
In the standard standard hydrogen
electrode,electrode,
hydrogenhydrogen gas pressure
gas at 1 atm at 1 atm press
is bubbledis around
bubbleda around
platinum a platinum
electrodeelectrode of very
of very high higharea
surface surface
in a area
2. 26 COPPER STANDARD ELECTRODE POTENTIAL +
solution
solution of H ions of of +
ions of concentration
H concentration −3
1 mol dm1 mol −3
dm . Platinum
. Platinum is chosenisascho
it
is an inertis metal,
an inert
hasmetal, has very
very little little tendency
tendency to be and
to be oxidised oxidised
does and
not does
react
The standard electrode with acid.with
Theacid. The occurring
reaction reaction occurring in cell
in this half this is:
half cell is:
potential (EƟ) of copper could +
2H (aq) +2H +−
2e (aq) H
+ 22e −
(g) H2(g)
be measured by connecting a
and this isand this is assigned
assigned a standarda electrode
standard electrode
potential potential (E V.
(E ) of 0.00 ) of 0.00 V.
standard copper half cell
(1moldm−3 Cu2+(aq)/Cu(s)) to
the standard hydrogen The electrode
The standard standard electrode
potential potential (E ) ofcould
(E ) of copper copper
be could be measur
measured by
2+ −3 2+
electrode
connectingconnecting
a standarda copper
standardhalf
copper half
cell (1 molcell −3
dm(1 mol Cu (aq)/Cu(
Cudm(aq)/Cu(s)) to the
standard hydrogen
standard hydrogen electrodeelectrode (Figure
(Figure 9.15, 9.15,).overleaf ).
overleaf
ReactionsReactions
that go onthat
in go
theon
halfincells
the half
are: cells are:
The H2 half equation goes + +− − 2+ 2+− −
H2(g) H 2H2(g)(aq) +
2H2e (aq) + 2e Cu (aq)Cu + 2e (aq) +Cu(s)
2e Cu(s
backward while the Cu equation
2+ 2+
goes forward. The hydrogen
The hydrogen is and
is oxidised oxidised and the
the Cu ionsCu ions are reduced.
are reduced.
The cell potential
The cell potential wheniscopper
when copper is to
attached attached to the hydrogen
the standard standard hyd
electrodeelectrode
is 0.34 V isand
0.34
weVcan
andwrite:
we can write:
2+ 2+− −
Cu (aq) + 2e Cu(s) E =
 electron).
E°cell = E°cathode - E°anode
For example, suppose we connect the standard hydrogen electrode to a Cu electrod
immersed in a 1 M Cu2+ solution. The measured cell potential for this cell is -0.34 V
2.V27
-0.34 COPPER
= 0.00 V - E°anodeSTANDARD E°
The anode (defined as Cu>Cu2+ ) is at a more positive voltage (lower potential energy
than the cathode (the SHE). Therefore, electrons will not spontaneously flow from th
anode to the cathode. We can diagram the potential energy and the voltage of this cel
(EƟ) = +0.34 V
E°anode as follows:

+ –
electrode
Suggests is 0.34V is The
positive.
that the positive potential indicates that
Cathode: 2 H+(aq) + 2 e– H2(g)
ectrode hasdifference
potential lower potential
producedenergy than it does at the SHE. 0.00 V
Potential
de potential, the lower
when a standard copper the potential energy
Energy
of an electron
nonspontaneous
Voltage
tiveelectrode
charge isattracts electrons).
placed with a 2e – Anode: Cu(s) Cu 2+(aq) + 2 e–

+0.34 V
electrode potentials
standard are written for reduction half-reactions.
hydrogen electrode.
The positive sign means that Cu
de potentials for the two half-reactions just discussed as: +
acts as the positive electrode
- The copper half-cell is like the water tank with the lower water level, and electrons do no
) + and
2 e it’s¡ Cu(s)moves
equilibrium E° = +0.34 V
spontaneously flow from the copper electrode to the standard hydrogen electrode.
forward. We can again determine the electrode potential for the Cu>Cu2+ half-cell (th
-
) + 2 e ¡ Zn(s) anode)V
E° = -0.76 from the measured cell potential:

E°cell = E°cathode - E°anode

+
electrode is positive relative to the SHE (and therefore,
-0.34 V = 0.00 V - E°anode
 half-cell. This because the Cu /Cu half-cell is better at half-equation, the more oxidised
3+ 2+
losing electrons than the Fe /Fe half-cell. the more reduced form is on the

2. 28 THE ELECTROCHEMICAL SERIES

strongest weakest
By arranging the elements and their
oxidising agent reducing agent
corresponding ions (or any two oxidation
states of any species) in the order of their Cl2(aq) + 2e– 2Cl – (aq) E = +1.36 V
standard electrode potentials, a series, referred Ag+(aq) + e– Ag(s) E = +0.80 V
to as the electrochemical series, can be increasing oxidising 2+ – increasing reducing
power of ions/molecules Cu (aq) + 2e Cu(s) E = +0.34 V power of element on the
obtained.
1
on the left (increasing +
H (aq) + e –
E = +0.00 V right (increasing tendency
2 H2(g)
tendency to gain electrons) to lose electrons)
The series gives the relative tendencies of the Zn2+(aq) + 2e– Zn(s) E = –0.76 V
elements to form the hydrated ions. It’s a useful Mg2+(aq) + 2e– Mg(s) E = –2.38 V
guide to the behaviour of oxidising and
reducing agents. It is an electrochemical series.
weakest strongest
oxidising agent reducing agent
Since most chemical reactions depend on this
tendency, the table can be looked upon as the
280 19 Electrode potentials
reactivity series of the elements.
 2. 29 THE ELECTROCHEMICAL SERIES

The electrochemical series is an arrangement of the elements and their

corresponding ions (or any two oxidation states of any species) in the
order of their standard electrode potentials. It gives the relative
tendencies of the elements to form hydrated ions. It’s a useful guide to
the behaviour of oxidising and reducing agents.

Since most chemical reactions depend on this tendency, the table can
be looked upon as the reactivity series of the elements.
 2. 30 THE ELECTROCHEMICAL SERIES
strongest weakest
oxidising agent reducing agent

– –
Cl2(aq) + 2e 2Cl (aq) E = +1.36 V
+ –
Ag (aq) + e Ag(s) E = +0.80 V
increasing oxidising 2+ – increasing reducing
power of ions/molecules Cu (aq) + 2e Cu(s) E = +0.34 V power of element on the
on the left (increasing + – 1 right (increasing tendency
H (aq) + e 2 H2(g) E = +0.00 V
tendency to gain electrons) to lose electrons)
2+ –
Zn (aq) + 2e Zn(s) E = –0.76 V
2+ –
Mg (aq) + 2e Mg(s) E = –2.38 V Figure 1
Standard
weakest strongest potential
oxidising agent reducing agent oxidising
reducing

280 19 Electrode potentials

2. 31 REACTIVITY SERIES

Note that H2 hasEƟ

value of 0.00V as it is
the standard electrode.
Elements more reactive
than it have a negative
value. Elements less
reactive than it have a
positive value.
2. 32 ELECTRODE POTENTIAL AND REDOX REACTION
By convention, the electrode potential refers to the reduction reaction.

The more negative (or less positive) the electrode potential, the more difficult it is to
reduce the ions on the left. The backward reaction is favoured.

Cu2+(aq) + 2e ⇌ Cu(s) E° = + 0.34 V

The more positive (or less negative) the electrode potential, the easier it is to reduce
the ions on the left. The forward reaction is favoured here.

Zn2+(aq) + 2e ⇌ Zn(s) E° = - 0.76 V

2. 33 ELECTRODES
There are three kinds of electrodes. But because electron transfer can
only occur through metals, all three kinds have a metal that facilitates
electron exchange.

Metal Electrodes Gaseous Redox Electrodes Aqueous Redox Electrodes

metals in contact with solutions gases in contact with solutions of ions in two
of their ions
solutions of their ions
different oxidation states

(electrode is the metal itself) (platinum electrode) (platinum electrode)

2. 34 GASEOUS REDOX ELECTRODES
In an electrode system containing gaseous elements, the gas is
bubbled through 1 mol dm-3 solution of its ions at 1 atm pressure and
25oC around platinum electrodes.

In such instances the standard electrode potential is more correctly

referred to as standard redox potential.

Standard redox potential of a half-cell is the potential difference of that

half-cell relative to a standard hydrogen electrode under standard
conditions.

 the 2 Cl2/Cl half-cell.

2. 35 GASEOUS REDOX ELECTRODES

+ 1.36 V –

voltmeter Reaction Cl2(g) + 2e¯ ⇌ 2Cl¯(aq)

Cl2(g), Electrode Pt
1 atmosphere H2(g),
1 atmosphere
salt bridge Solution 1M sodium chloride

Gas Chorine at 1 atm

platinum
Potential + 1.36V
298 K
– –3 + –3
platinum Cl , 1.00 mol dm H , 1.00 mol dm A potential difference of 1.36V exists
Pt houses free electrons for voltaic cell reactions between Cl2 and H2. The Cl2 half reaction
Figure 19.9 Measuring the standard electrode potential of a
− to occur between Cl2 and H2 shifts forward. While H2 shifts backwards.
Cl /Cl half-cell.
2
 2. 36 AQUEOUS REDOX ELECTRODES

If the oxidant and reductant are both ions, a solutions used where both
oxidant and reductant are 1 mol dm-3 in concentration and electrical
contact is made by platinum rod.

Standard redox potential of a cell that has an aqueous electrode is the

potential difference of that half-cell relative to a standard hydrogen
electrode under standard conditions.
 voltmeter
2. 37 AQUEOUS REDOX ELECTRODES
H (g),
8 What is t
2
1 atmosphere left-hand
platinum
salt bridge
Reaction Fe3+(aq) + e¯ ⇌ 9 Why
Fe2+(aq)
is p
metals in
Electrode Pt
not invol
platinum
Solution Fe3+(aq) (1M) and Fe2+(aq) (1M)
298 K 10 Show, wi
Potential + 0.77 V
3+
Fe , 1.00 mol dm–3 + –3
H , 1.00 mol dm would m
2+ –3
Fe , 1.00 mol dm shown by
2+
Figure 19.11 Measuring the standard electrode potential of the VO +
3+ 2+
Fe /Fe half-cell.
 It is also possible to measure the standard electrode potentials of electrode
In the standard hydrogen electrode,
systems in which both the oxidised and reduced forms are ions in solution, hydrogen gas at 1 atm pressure
2. 38 AQUEOUS REDOX ELECTRODES
such as ions of the same is element
the electrode in the system
bubbledinaround
is
differentaoxidation
platinum + (Figure
platinum
15.12).
electrode
states. In theseof very high surface area in a
cases,
−3 Electrons
solution of H ions of concentration 1 mol dm . Platinum is chosen as it
move from the
H2 half cell to this half
is an inert metal, has very little V tendency to be oxidised and does not react
cell via platinum for
with
H2(g) at acid. The reaction
high occurring in this
resistance voltmeter half cell is: redox reactions to occur
298 K and
+
1 atm pressure 2H (aq) + 2e −
H2(g) between Fe 2+ and Fe3+

and this is assigned a standard electrode potential (E ) of 0.00 V.

salt bridge

solution of Fe3+(aq) and

2+ –3
Fe (aq) both at 1mol dm
platinum electrode The standard electrode potential (E ) of copper could be measured by
shiny platinum electrode
−3 2+
coated with finely connecting a standard copper half cell (1 mol dm Cu (aq)/Cu(s)) to the
acid solution
divided platinum black +
containing H (aq)
standard hydrogen electrode (Figure
(1mol dm )–3 9.15, overleaf ).
Reactions that go on in the half cells are:
The cell diagram for the cell in Figure 15.12
+
is: − 2+
Figure 15.12!
−
H 2(g) 2H (aq) + 2e Fe Cu
3+(aq) +(aq)
e¯
The+ 2e
⇌
diagram Fe
ofCu(s)
a (aq)
2+cell for measuring the
Pt[H2(g)]2H+(aq) Fe3+(aq), Fe2+(aq)Pt E = +0.77 V standard electrode potential of the redox
2+
The hydrogen is oxidised and Thisthe
reaction ions are
Cu moves reduced.
reaction
forward Fe3+ −
as suggested by the(aq)
(aq) + e Fe2+
.
+0.77V
Test yourself
The cell potential when copper is attached to the standard hydrogen
 + 1.52 V –
2. 39 AQUEOUS REDOX ELECTRODES+ 1.52 V –
voltmeter
voltmeter
H2(g),
H1MnO
(g),
platinum Reaction atmosphere
2
4¯ + 8H+(aq) + 5e¯ ⇌ Mn2+(aq) + 4H O(l)
2
salt bridge 1 atmosphere
platinum salt bridge
Electrode Pt

Solution platinum
MnO 4¯(aq) (1M) & Mn2+(aq) (1M) & H+(aq)
platinum
298 K
MnO4–, 1.00 mol dm–3 298 K H+Potential
, 1.00 mol dm+–3
1.52 V
MnO 2+
– , 1.00 mol dm –3
–3 H+, 1.00 mol dm–3
Mn 2+, 1.00 mol dm –3
4
Mn , 1.00 mol
H +, 1.00 mol dm–3
+ dm
H , 1.00 mol dm –3

−
Figure 19.12 Measuring the standard electrode potential of the MnO / −4
Figure
2+ 19.12
Mn 2+half-cell. Measuring the standard electrode potential of the MnO / 4
Mn half-cell.
Figure 19.12 shows the set-up of aiscell
theused to measure
standard hydrogen theelectrode (Figure 9.14).
− 2+
standard electrode potential of the MnO
In the4 /Mn
standardhalf-cell.
hydrogen electrode, hydrogen gas at 1 atm pressur
2. 40 AQUEOUS REDOX ELECTRODES
is bubbled around
+
a platinum electrode of very high surface area in
−3
solution of H ions of concentration 1 mol dm . Platinum is chose
+ 1.52 V – is an inert metal, has very little tendency to be oxidised and does no
voltmeter with acid. The reaction occurring in this half cell is:
+ −
2H (aq) +H2e
2(g),
H2(g)
1 atmosphere
platinum salt bridge and this is assigned a standard electrode potential (E ) of 0.00 V.

The standard electrode potential (E ) of copper could be measured

−3 2+
standard copper half cell (1 mol dm Cu (aq)/Cu(s))
connecting a platinum
standard hydrogen Electron
electrodetransfer
(Figure 9.15, overleaf
between the two ).
half cells
298 K
– –3 H
Reactions
+, 1.00 mol dm
that
–3 go on in the half cells
occurs are:
via Pt
MnO4, 1.00 mol dm
Mn2+, 1.00 mol dm–3 H2(g) +
2H (aq) + 2e − 2+
Cu (aq) + 2e −
Cu(s)
+
H, 1.00 mol dm–3

MnO4¯ + 8H+(aq) + 5e¯ ⇌ Mn2+The + 4H2O(l)is oxidised and the Cu2+ ions are reduced.
(aq) hydrogen
This reaction moves forward as suggested by cell
The +1,52V
potential when
− copper is attached to the standard hydro
2. 41 METAL ELECTRODE
high-resistance
In such a cell the metal itself serves as voltmeter
the electrode. The rod made from pure V

metal and is dipped in a solution of its + –

own salt at a concentration of 1 mol

copper zinc rod
rod

dm-3
salt bridge

It has a standard electrode potential

relative to a standard hydrogen electrode
under standard conditions.
298 K
2+ –3 2+ –3
Cu , 1.00 mol dm Zn , 1.00 mol dm

Figure 19.5 One type of electrochemical cell is made by connecting a

2. 42 MEASURING EMF high-resistance
voltmeter
One type of electrochemical cell V
is made by connecting a Cu2+/Cu + –
half-cell to a Zn /Zn half-cell.

2+
copper zinc rod
rod
The voltage generated by this cell
is +1.10 V. salt bridge

298 K
2+ –3 2+ –3
Cu , 1.00 mol dm Zn , 1.00 mol dm
2. 43 MEASURING EMF
One reaction will proceed in the forward direction and one in the
backward direction.

The half reaction with a more positive E value is easier to reduce from
it’s ionic state compared to the one that has a less positive value. So
Cu2+ ions will accept electrons from the Zn2+/Zn half-cell and zinc will
lose electrons to the Cu /Cu half-cell.
2+

Cu2+(aq) + 2e¯ ⇌ Cu(s) E° = + 0.34V

Zn2+(aq) + 2e¯ ⇌ Zn(s) E° = - 0.76V

 clockwise pattern (reactant, product, reactant, product
starting from the top left as shown in Figure 19.18 for
2e −
2. 44 MEASURING EMF 2+
cell made from the two half-cells Cu /Cu and Zn /Zn2+

e twoHence
half-equations to show
the copper equation goes forward and the zinc equation goes
action in the electrochemical cell E /V
backward:

2+
→ Zn (aq) + Cu(s) +0.34 2+
Cu + 2e –
Cu
better (product)
Zinc is more reactive,
ng place in the electrochemical cell. it dissolves to give ions

oxidant
n thatZn(s)
takes place
➝ −3if a piece of zinc
Zn (aq) + 2e¯
2+ (reactant) /oxidising agent
2+
into a 1.00 mol dm solution of Cu Zn2+
+ 2e–
Zn
–0.76
to be feasible if it is likely to occur. product better
inc metal and copper ions is feasible. reductant
Electrons are picked
on is feasible, the reverse reaction up by copper ions
(reactant)
/reducing agent
nd zincCu ions) is not
2+(aq) feasible.
+ 2e¯ ➝ Cu(s) If a piece
−3 Figure 19.18 A reaction occurs in a direction so that the stronger
ced directly into a 1.00 mol dm oxidising agent reacts with the stronger reducing agent.
2. 45 MEASURING EMF
To calculate the overall cell potential:

Step 1: Reverse the more negative half-equation.

Step 2: Change the sign of the equation that you reversed.

Step 3: Add the two electrode potentials and the half-equations to construct
the overall equation.


Zn(s) ➝ Zn2+(aq) + 2e¯ - (-0.76) V

Cu2+(aq) + 2e¯ ➝ Cu(s) + 0.34 V
OVERALL: Zn(s) + Cu2+(aq) ➝ Zn2+(aq) + Cu(s) +1.10 V
 Consider again the cell made from Mg/Mg2+ and Zn/Zn2+ half cells
(Figure 9.18). In the right-hand half cell, the magnesium is oxidised and

2. 46 CALCULATING EMF
therefore electrons are lost. This means that the magnesium electrode is
the negative one, as electrons are produced there. The electrons move
through the external circuit from the Mg to the Zn electrode, where they
combine with Zn2+ ions in the reduction reaction. The Zn electrode is
the positive electrode as the electrons are used up there.
Consider again the cell made from Mg/Mg2+ and Zn/Zn2+ half
cells.

Mg2+(aq) + 2e¯ ⇌ Mg(s) E° = — 2.38 V

Zn2+(aq) + 2e¯ ⇌ Zn(s) E° = — 0.76 V

In the right-hand half cell, the magnesium is oxidised and

therefore electrons are lost.This means that the magnesium
electrode is the negative one, as electrons are produced there.

The electrons move through the external circuit from the Mg to

the Zn electrode, where they combine with Zn2+ ions in the
reduction reaction. The Zn electrode is the positive electrode as The electrode at which oxidation occurs is the anode; therefore
the Mg electrode is the anode. The electrode at which reduction
the electrons are used up there. occurs is the cathode; therefore the Zn electrode is the cathode.

Another way to determine which is the negative and positive electrode

is to just look at the original electrode potentials:

Mg2+(aq) + 2e− Mg(s) E = −2.36 V

2. 47 CALCULATING EMF
Always balance the electrons in both half-equations before
constructing the overall equation.

E° is not related to the quantity of the material.

Thus for the reaction Ag+ + e ➝ Ag

The E° is +0.80V irrespective of whether it is for one mole or two moles. 


That is,

Ag+ + e ➝ Ag E°= +0.80 V

Electrode potential
remains the same
2Ag+ + 2e ➝ 2Ag E°= +0.80 V
2. 48 STEP-BY-STEP CALCULATION
What happens if an Sn(s) / Sn2+(aq) and a Cu(s) / Cu2+(aq) cell are connected?

Write out the equations:

Cu2+(aq) + 2e¯ ⇌ Cu(s) E° = +0.34 V

Sn2+(aq) + 2e¯ ⇌ Sn(s) E° = -0.14 V

Step 1: Reverse the equation with the more negative electrode potential.

Sn(s) ➝ Sn2+(aq) + 2e¯

Step 2: Change the sign of the reversed equation’s potential.
E = -(-0.14) V = + 0.14 V
2. 49 STEP-BY-STEP CALCULATION
Step 3: Add potentials and combine equations.

The overall reaction is:

Cu2+(aq) + Sn(s) ➝ Sn2+(aq) + Cu(s)

The cell voltage is: (+0.34) + (+0.14) = + 0.48V

2. 50 REACTIVITY SERIES & ELECTRODE POTENTIALS
We saw earlier in this chapter that a more reactive metal will displace a less
reactive metal from solution. For example, zinc is more reactive than copper and
displaces copper ions from solution:

Zn(s) + Cu2+(aq) ➞ Zn2+(aq) + Cu(s) E cell = +1.10 V

In terms of standard electrode potentials, the more reactive a metal the more
negative its standard electrode potential.

The more negative standard electrode potential indicates that the reduction
reaction of the metal ion is very unfavourable and therefore that the oxidation of
the metal is very favourable.

Mg2+(aq) + 2e¯ ⇌ Mg(s) E° = — 2.38 V

Zn2+(aq) + 2e¯ ⇌ Zn(s) E° = — 0.76 V
2.51 STRENGTH OF OXIDISING & REDUCING AGENTS
The values of the standard electrode potentials provide a direct measure of the
relative oxidising and reducing powers of the different species.

System with more negative E° System with more positive E°

The backward reaction takes place The forward reaction takes place more
more readily. readily

More powerful reducing agent More powerful oxidizing agent

2. 52 PREDICTION OF POSSIBLE REACTIONS
E° values of redox systems can be used to predict whether a given
reaction can take place or not. For a given reaction to occur the
reductant must have a more negative value and the oxidising agent
relatively a more positive value.

A reaction would be spontaneous and energetically feasible if the

overall potential of the redox pair is positive.

If the value is negative, it indicates that only the backward reaction is

energetically favoured.

If the overall potential is less 0.10 V the reaction may not occur.
2. 53 PREDICTION OF POSSIBLE REACTIONS
Will Sn(s) and Cu2+(aq) react?

Step 1: Find the relevant half-equations from the data booklet

Step 2: Circle the species involved.

Cu2+(aq) + 2e ⇌ Cu(s) E° = +0.34V

Sn2+(aq) + 2e ⇌ Sn(s) E° = - 0.14V

Step 3: Rearrange the two half equations to reflect the starting species, i.e.
Sn(s) and Cu2+(aq)
The elections must be
equal and on the opposite
Cu2+(aq) + 2e ➝ Cu(s) E° = +0.34V
sides in the two equations
Sn(s) ➝ Sn2+(aq) + 2e E° = + 0.14V to cancel each other out
2. 54 PREDICTION OF POSSIBLE REACTIONS
Step 4: Combine the two half equations:
One equation
should be
Sn(s) + Cu2+(aq) ➝ Sn2+(aq) + Cu(s)
undergoing
oxidation and the
other reduction
Step 5: Add the two E values of the rearranged equations

(+0.34V) + (+ 0.14V) = +0.48V

• If the value is positive, the reaction will occur.

• If the forward reaction is feasible, the reverse reaction between


Sn2+(aq) + Cu(s) is not feasible.
2. 55 PREDICTION OF POSSIBLE REACTIONS
E° indicates the feasibility of the reaction only from the energetic
standpoint.

Energetically favoured reactions need not always take place, as the

reaction may not be kinetically feasible, i.e. the energy of activation could
be too high and the rate of reaction may be too slow to be observed.

Reactions that are predicted to be not feasible may be made to take

place by altering the conditions. E° values refer to standard conditions.

Hence when conditions are altered electrode potential would change and
the reaction may become feasible.
2. 56 EFFECT OF CONCENTRATION ON E°
The value of the electrode potential depends on the position of the following equation.

Mn+(aq) + ne ⇌ M(s)

We can apply Le Chatelier’s principle to redox equilibria. If we increase the

concentration of the species on the left of the equation, the position of equilibrium
will shift to the right. So the value of E becomes more positive / less negative.
Concentration of ions is increased Solution is diluted

Equilibrium will be pushed forwards Equilibrium will be pushed backwards

Electron density on the rod will decrease Electron density on the rod will increase

E° will become more positive (or less negative) E° will become more negative.
2. 57 EFFECT OF CONCENTRATION ON E°
A2+ + e ⇌ A+

If A2+ is increased, Equilibrium shifts right. Eo increases, implies more +ve/less –ve

If A+ is decreased, Equilibrium shifts right. Eo increases, implies more +ve/less –ve

If A2+ is decreased, Equilibrium shifts left. Eo decreases, implies less +ve/more –ve

If A+ is increased, Equilibrium shifts left. Eo decreases, implies less +ve/more –ve

2. 58 NERST EQUATION
This change in the value of Eo cell due to change from standard to non-standard
conditions can be calculated using the Nernst equation.

For a half-cell against a standard hydrogen electrode at room temperature, this

equation can be written as:
E = Eo + (0.059) log [oxidised species]
1

z [reduced species]
where z is the number of electrons added to the oxidised species to form the reduced species.

A ten-fold change in concentration only affects the Eo value by 0.059 V for a single electron
transfer and 0.030V for the transfer of two electrons. These are very small changes and this is
the reason why Eo values are such a good guide to the feasibility of the reaction, even under
non-standard conditions.
2. 59 NERST EQUATION
For a metal/metal ion electrode, e.g. Cu2+ + 2e– ➞ Cu, the reduced form is the metal.
The concentration of the metal does not change.

So the ratio [oxidised form]/[reduced form] can be written [oxidised form], e.g. [Cu2+(aq)].

[Reduced species]=1 E = Eo + (0.059) log [oxidised species]

1

if it’s a metal z
What is E for a copper electrode dipping into a solution of 0.00010 moldm–3 Cu2+(aq) ions?

= +0.34 + 0.059/2 log 1.0 × 10−4

= +0.34 + 0.059/2 × (−4)

= +0.34 − 0.118 = +0.22 V

2. 60 ELECTROLYSIS
While electrochemical cells used energy from chemical reactions
generate current, electrolysis breaks down a chemical substance (in
molten state or solution) by the passage of electricity through it.
ELECTROCHEMICAL CELL ELECTROLYTIC CELL

It converts chemical energy into electrical It converts electrical energy into chemical
energy. energy

It is based upon the redox reactions which The redox reactions are non-spontaneous
are spontaneous. and take place only when energy is
supplied.

Positive Eo Negative Eo (Forced electrolysis)

2. 61 ELECTROLYSIS- MOLTEN ELECTROLYTES
When pure molten ionic compounds containing two simple ions are electrolysed:

a metal is formed at the cathode AND a non-metal is formed at the anode

COMPOUND CATHODE PRODUCT ANODE PRODUCT

aluminium oxide aluminium oxygen

magnesium bromide magnesium bromine

sodium chloride sodium chlorine

zinc iodide zinc iodine

2. 62 ELECTROLYSIS- AQUEOUS SOLUTIONS
Aqueous solutions, unlike molten electrolytes, contain more than one anion and
more than one cation. The multiple ions arise from the auto-ionisation of water:

H2O ⇌ H+ + OH−

The ions that are discharged during electrolysis of aqueous solutions depends on:

• the relative electrode potential of the ions

• the concentration of the ions

If inert electrodes are used, there is usually only one product obtained at each
electrode. The positive electrode is called the anode; the negative one the
cathode.
 2. 63 EASE OF DISCHARGE
E /V
+ –
+0.80 Ag (aq) + e Ag(s)
2+ –
+0.34 Cu (aq) + 2e Cu(s)
+ – 1
0.00 H (aq) + e 2 H2(g)
increasing ease
2+ –
–0.13 Pb (aq) + 2e Pb(s) of discharge of
2+
–0.76 Zn (aq) + 2e –
Zn(s) cation at cathode
2+ –
–2.38 Mg (aq)+ 2e Mg(s)
+ –
–2.71 Na (aq) + e Na(s)

Figure 19.25 The ease of discharge of ions at a cathode in electrolysis is

related to the electrode potential of the ions.
2. 64 ELECTROLYSIS- AQUEOUS SOLUTIONS
If a metal has a positive E° value, then you get the metal. Metals like this
include copper and silver.

If a metal has a fairly negative E° value, then you get hydrogen. Metals
like this include magnesium and sodium.

The cation which is most easily reduced is discharged at the

cathode.

The anion which is most easily oxidised is discharged at the


anode.
2. 65 ELECTROLYSIS OF AgF
CATHODE(REDUCTION):

Ag+ + e→Ag 0.80V OR 2H+ +2e→H2 0.00V

As Ag+ is more positive, Ag will be deposited.

ANODE(OXIDATION):

F2 + 2e→ 2F— +2.87V OR O2+ 4H+ +4e→2H2O +1.23V

Now reverse the two equations (this will change their signs)

2F—→F2 + 2e —2.87V OR 2H2O→ O2 + 4H+ +4e —1.23 V

Since the second E0 is more positive, O2 gas will be seen.

2. 66 ELECTROLYSIS OF FeSO4
CATHODE(REDUCTION):

Fe2+ + 2e→ Fe —0.44V OR 2H+ +2e→H2 0.00V

As the second equation is more positive, H2 gas is evolved.

ANODE(OXIDATION):

S2O82— + 2e→ SO42— +2.01V OR O2+ 4H+ +4e→2H2O +1.23V

Now reverse the two equations (this will change their signs)

SO42— → S2O82— + 2e —2.01V OR 2H2O→ O2 + 4H+ +4e —1.23V

Since the second E0 is more positive, O2 gas will be seen.

2. 67 USING E TO DETERMINE PRODUCTS
COMPOUND ANODE CATHODE

MgBr2 (aq)
2. 68 CONCENTRATION AND PRODUCT PREDICTION
An ion, Z, higher in the discharge series may be discharged in preference to
one below it if Z is present at a relatively higher concentration than normal.

For this to be possible, the E values of the competing ions are usually less
than 0.30 V different from each other.

For example, if you have a concentrated solution of sodium chloride, you

will get mainly chlorine at the anode.

With more and more dilute solutions, you will get less chlorine and more
oxygen.

Very dilute solutions will give mainly oxygen.

 2. 69 ELECTROPLATING
med,Anode
and coats the electrode:
is the pure Copper rod and
the article to be plated is the
cathode.

ving copper ions in solution: +

Electrolyte is the soluble solution of

copper copper cathode
Cu 2+ ions e.g copper(II) nitrate
ert. The anode dissolves, giving anode grows larger
de, to form copper. So copper dissolves
copper(II)
The colour of the solution does sulfate solution
blue colour does not fade

ses of electrolysis: for refining (or

ng.
 At the cathode Again, copper is formed, and coats the electrode:
Cu2 ! (aq) ! 2e " Cu (s)
2. 70 ELECTROLYSIS FOR PURIFICATION
At the anode The anode dissolves, giving copper ions in solution: +

Cu (s) Cu2 ! (aq) ! 2e "

copper copper cathode
The impure copper is cast into a block to form the positive anode.
So this time, the electrodes are not inert. The anode dissolves, giving anode grows larger
copper ions. These move to the cathode, to form copper. So coppercopper(II)
dissolves
The cathode is made of previously purified copper.

moves from the anode to the cathode. The colour of the solution does
sulfate solution
not fade. blue colour does not fade

The mass of copper dissolving at the anode exactly equals the mass of
The idea in B leads to two important uses of electrolysis: for refining (or
copper
purifying) deposited
copper, on the cathode. The concentration of the copper(II)
and for electroplating.

sulphate
Refining copper remains constant.

Any impurities present in the impure copper anode fall to the bottom
anode
(impure copper)
cathode
(pure copper)
+ – + – + –

sludge
containing
precious
metals

The anode is made of impure The copper in the anode dissolves. A layer of pure copper builds up
copper. The cathode is pure copper. But the impurities do not dissolve. on the cathode. When the anode is
2. 71 QUANTATIVE ELECTROLYSIS
The mass of a substance produced at an electrode during electrolysis is
proportional to:

1. the time over which a constant electric current passes

2. the strength of the electric current.

3. the charge on the ion

From physics, the charge, Q (in C) is related to the current, I (in A), and
the time, t (in s), as follows:

Q = It
2. 72 THE FARADAY CONSTANT
One mole of electrons carries a charge of −96500C. This is the same charge as the
charge on one electron, 1.603 × 10−19C, multiplied by the Avogadro constant, 6 ×
1023 mol−1

1e- has a charge of 1.6 x 10–19 C


1mol of e- has a charge of 1.6 x 10–19 C x 6 x 1023 = 96500 C

therefore 1mol of e— carries 96500 C

F = Le
This quantity is called the Faraday constant, F, and has a value of 96500 C
mol−1.
2. 73 EXAMPLE OF QUANTITAIVE ELECTROLYSIS
Q. If 10A of current is passed for 20 minutes, calculate the mass of Cu deposited.

Step 3
Step 1 Step 2 Step 4
Cu2+ + 2e ➞
Q = I x t
 1 mol of e : 96500 C
 n = mass/Mr

Cu

= 10 x (20 x x mol of e : 12000 C

60)
 e : Cu
 0.062 = m/63.5

nmol of e = 0.124 mol

= 12000 C 2 : 1
 m = 3.93g
0.124 : ?

nCu = 0.062 mol

2. 74 DETERMINATION OF AVAGADRO CONSTANT
d.c. power supply
We can use an electrolytic method to find a value for
+ – the Avogadro constant by calculating the charge
associated with 1 mole of electrons . F = Le

A ammeter variable L = charge on 1 mole of electrons / charge on 1

resistor
electron

+ – F = charge on 1 mole of electrons (Faraday’s Constant)

copper copper Avagadro’s Constant = 6.02 x1023

anode cathode
The charge on the electron is approximately 1.60×10−19
C.

aqueous
copper(II) sulfate The apparatus for this procedure is shown on the left.
2. 75 DETERMINATION OF AVAGADRO CONSTANT
1. Weigh the pure copper anode and pure copper cathode separately,

2. Arrange the apparatus as shown on the previous slide. The variable

resistor is used to keep the current constant,

3. Pass a constant electric current for a measured time interval,

4. Remove the cathode and anode and wash and dry them with
distilled water and then with propanone,

5. Reweigh the cathode and anode.


2. 76 CALCULATION
A sample calculation is shown below, using a current of 2.0 A for 34 min.

• mass of anode at start of the experiment = 56.53 g

• mass of anode at end of experiment = 55.19 g

• mass of copper removed from anode = 1.34 g

Step 1 Step 2 Step 3 Step 4 Step 5

Q=Ixt 1 mol of e : F C
 Cu2+ + 2e ➞ n = mass/Mr F = Le

x mol of e : 4080 C Cu
= 2.0×34×60 4080/2F = 96672 = (L)1.6 x 10–19
=4080 C nmol of e = 4080/F mol e : Cu

1.34/63.5 L = 6.04 x 1023
2 : 1

F = 96672 C
4080/F : ?
2. 77 CELLS AND BATTERIES
A wide variety of electrochemical cells have been developed for specific
functions. When selecting a cell for a particular job, the following must
be considered:

whether or not the cell can be recharged

the size and mass of cells

the voltage delivered by the cell

the nature of the electrolyte

cost of the cell

 A hydrogen–oxygen fuel cell with an acidic electrolyte is shown
in Figure 19.24.
cells can only be
2. 78 HYDROGEN-OXYGEN FUEL CELL • Fuel cells do not
temperature fall
porous negative electron flow
porous positive
electrode coated electrode coated
V
with platinum with platinum
Check-up
hydrogen H + oxygen 24 A car’s fue
• 1 kg of pe
water when it b
proton exchange
• Only 40%
membrane electrolyte (acid) petrol bu
6
• 1 × 10 J o
Figure 19.24 A hydrogen–oxygen fuel cell. car 1 km.
 2. 79 LEAD-ACID ACCUMULATOR
The half-equations in a lead–acid car battery are:

in series to provide 12PbO (s)

V. The battery
2 +is 4H + (aq)
recharged by +
the 2e− ⇌ Pb2+(aq) + 2H2O(l) E = +1.47 V
car’s alternator while the car engine is running. Lead–acid
batteries are very heavy but are cheap to manufacture.
Pb2+(aq) + 2e− ⇌ Pb(s) E = −0.13 V
positive
gas vents +
terminal
g negative
terminal – When the battery is recharged both the half-
insulating
reactions are reversed. So the overall reaction
case
during charging is:

2Pb2+(aq) + 2H2O(l) → Pb(s) + PbO2(s) + 4H+(aq)

lead oxide
sulfuric lead
acid

Figure 19.21 The storage cell used in a car.