21 Electrochemistry

Electricity is such a mystery till

we understand chemistry.
Plain facts and sciences of
electrochemistry continue to 21 Electrochemistry
be important in technologies.

Electricity
Ancient people noticed electricity
1746 B. Franklin demonstrated lightening as electric effect and performed
the kite experiment in 1751. Two people tried to repeat his kite flying
experiment were killed by thunder.
1767 L. Galvani inserted two different metals in frog fluid and constructed
a electric cell
1800 A. Volta substituted frog fluid; made batteries, consisted of several
cells.
1802 G. Romagnosi noticed magnetism related to electricity
Michael Faraday 1791-1867 discovered many theories of electricity and
magnetism
2
21 Electrochemistry

Galvani
Luigi Galvani
(1737-1798):
erroneously
concluded that the
frog's nervous
system generated
an electrical
charge, his work
stimulated much
research into the
electrochemistry.
The depiction of his
laboratory

21 Electrochemistry

Electrochemistry
A. Volta (1745-1827) experimented with different
materials, and made voltaic piles (batteries)
William Nicholson (1753-1815) observed bubbles
forming on the surfaces of metals submerged in
water when they are connected to a voltaic pile
Humphry Davy (1778-1829) observe electrolysis
of water and metal salts. Following that,
Michael Faraday (1791-1860) studied
electrolysis, and discovered the relationship
between charges and chemical stoichiometry
21 Electrochemistry

Electrons
qe = 1.60217733e-19 C
F = 96485 C
me = 0.00054856 amu
= 9.1093897e-31 kg
spin = (two state)
magnetic moment
= 9.284770e24 J/tesla
Voltaic piles (batteries) made the following study possible
W. Crookes (1832-1919) observed cathode rays in low-pressure tubes.
1897: J.J. Thomson determined the charge to mass ratio (e / me) of
cathode rays (electrons).
1916 R. Millikan (1868-1953) measured the amount of charge of e.
21 Electrochemistry

Redox reactions and electrons

Energy drives chemical reactions.
Redox reactions involve the transfer of electrons.
Loss of electron (increase oxidation state) is oxidation, (Leo).
Gain of electron (decrease oxidation state) is reduction, (ger).
Zn Zn2+ + 2 e
leo
Cu2+ + 2 e Cu ger
net:
Zn + Cu2+ Cu + Zn2+ redox
Chemical energy in redox reactions may be convert to electric
energy by applying electrochemistry.
In the meantime, we should learn to balance the redox reaction
equations.
21 Electrochemistry

Galvanic Cell
A galvanic cell consists of two different metals inserted into a solution of
an electrolyte (salt, acid or base), simulated

Representation:
Zn | Zn2+ || Cu2+ | Cu

21 Electrochemistry

Assign oxidation states

3 NH3
2 N2H4
1 NH2OH
0 N2
+1 N2O
+2 NO

0 for any element

1 for H in compounds, but 1 for LiH, NaH, etc
2 for O in compounds, but 1 for H2O2, Na2O2

1 Cl

+1 for alkali metals, +2 for alkaline earth metals

0 Cl2

The oxidation states of other elements are then

assigned to make the algebraic sum of the
oxidation states equal to the net charge on the
molecule or ion.

+3 NO2

+3 ClO2
+4 ClO2
+5 ClO3

+4 NO2
+5 NO3

+1 ClO

+7 ClO4
21 Electrochemistry

Half reaction equations

Oxidation and reduction can be written as
half-reaction equations such as

Steps to balance half reaction

Zn Zn2+ + 2 e

leo

Assign oxidation number

ger

Figure out what is oxidized or

reduced.

Cu2+ + 2 e Cu
net: Zn + Cu2+ Cu + Zn2+

redox

Demonstrate how to balance these

Fe2+ Fe3+ + __ e

Add electrons according to

oxidation number change

C2O42- 2 CO2 + __ e

Balance charge with H+ (acid) or

OH (base)

MnO4 + __ e Mn2+

Balance atoms with H2O

Cr2O72 + __ e + __ H+ 2 Cr3+ + __ H2O

21 Electrochemistry

More half-reaction equations

2 I I2 + __ e
ClO2 + __ OH ClO3- + __ e + H2O (in basic solution)
2 S2O32 S4O62- + __ e
HS(=S)O3 S + __ e- + HSO4
__ H3O+ + __ e H2(g) + __ H2O
H2O2 + __ e 2 H2O
ClO2 + __ e ClO2
+
NO3 + __ e NH
214 Electrochemistry

10

Electrochemical Series
An electrochemical series is a list of metals in order of decreasing
strength as reductant, or increasing strength as oxidant.
An example of an activity series of metals based on the Standard
Potentials given would be:
K > Ba > Ca > Na > Mg > Al > Mn > Zn > Fe > Ni > Sn > Pb > Cu > Ag
In this series the most active metal is potassium (K) and the least active
metal is silver (Ag)
Reactions and cells are illustrated in 21-1 of Text (PHH).

21 Electrochemistry

11

Constructing half cells

A half cell consists of an oxidizing and its oxidized species
Zn | Zn2+
Cu | Cu2+
Pt | H2 | H+
Pt |Fe2+ , Fe3+
Cl | Cl2 | Pt

(Pt as conductor)

Explain the cell convention

and reactions of cells.
21 Electrochemistry

Student cell set from School

Master Science $30
12

Galvanic cells
Using corns for a galvanic cells is illustrated by an Internet site:
(schoolnet.ca/general/electric-club/e/page9.html)
This picture illustrates a way
to make a pact of battery
using coins of different metals.
Apply the principles you
have learned regarding
electrochemical series and
electrolytes to make such a
pile will be an interesting
exercise.
21 Electrochemistry

13

Cell convention
Oxidation takes place always at the anode
Zn (s) Zn2+ (aq) + __ e Zn(s) | Zn2+(aq)
Fe2+ (aq) Fe3+ (aq) + e

Pt | Fe2+ , Fe3+

H2 (g) 2 H+ (aq) + __ e

Pt | H2(g) | H+(aq)

Reduction takes place at the cathode

Cu2+ (aq) + __ e Cu (s) Cu2+ | Cu(s)
Cl2 (g) + __ e Cl (aq)

Cl2(g) | Cl (aq) | Pt

Fe3+ (aq) + __ e Fe2+ (aq) Fe3+(aq), Fe2+(aq)| Pt

2 H+ (aq) + __ e H2 (g)

H+(aq) | H2(g)| Pt

Concentration (1.1 M) and pressure (0.9 atm) are also

included
in cell notations.
14
21 Electrochemistry

Electric energy and work

Electric energy or electric work = charge * potential difference
W=q*V

(1 J = 1 Coulomb Volt, C V)

compare W = m g h

The Faraday constant F is the charge for one mole of electrons,

F = 96485 C;
F / NA = 96485 C / 6.022e23 = 1.602177e-19 C, charge per e
The maximum chemical energy of the cell that can be converted to
electric work is the Gibbs free energy change, G
G = n F E (n F = q is the charge)
electromotive force (emf, or V)
number of electrons in the reaction equation
n F is the charge q
See slides in
16 Equilibria

21 Electrochemistry

15

Standard cell emfs and electrode potentials

The standard cell emf is the emf of a voltaic cell operating under
standard conditions (1 M, 1 atm, 25oC etc). E.g.
Zn (s) | Zn2+ (aq, 1 M) || Cu2+ (aq, 1 M) | Cu (s)

Eo = 1.10 V

Mg (s) | Mg2+ (aq, 1 M) || Cu2+ (aq, 1 M) | Cu (s)

Eo = 2.90 V

The absolute potential of the electrode cannot be determined. Only

relative potential can be measured. The standard reduction potential is
measured against a SHE, for which Eo = 0.0000 V
Zn (s) | Zn2+ (aq, 1 M) || H+ (aq, 1 M) | H2 (1 atm)(g)
Zn = Zn2+ + 2 e

(oxidation, displace H+ possible)

Zn2+ + 2 e Zn
21 Electrochemistry

(reduction)

Eo = 0.76 V
Eo = 0.76 V
Eo = 0.76 V
16

Gibbs Free Energy in a Cell

How much energy is available for the cell
Zn | Zn2+ || Ag+ | Ag
operating at standard condition when one mole of Zn is consumed ?
Solution
Zn = Zn2+ + 2 e
2 Ag+ + 2e = 2 Ag
Zn + 2 Ag+ = Zn2+ + 2 Ag

Eo
0.762 V
0.799 V (from table)
Eo = 1.561 V

Go = n F E = 2 * 96485 C * 1.561 V
= 301226 J (1J = 1 C V)
= 301.2 kJ
How much silver is consumed?
21 Electrochemistry
How much energy is available
if 6.5 g of Zn is consumed?

17

Table of standard reduction potential

Reaction E o (V)
Li+ + e = Li (s)
Na+ + e = Na (s)
Mg2+ + 2 e = Mg (s)
Zn2+ + 2 e = Zn (s)
(reference) 2 H+ + 2 e = H2 (g)
(reference) H2 (g) = 2 H+ + 2 e
Cu2+ + 2 e = Cu (s)
Cu+ + e = Cu (s)
I2 (s) + 2e = 2 I (aq)
Br2 (l) + 2 e = 2 Br (aq)
Cl2 (g) + 2 e = 2 Cl (aq)
F2 (g) + 2 e = 2 F (aq)

3.04
2.71
2.38
0.76
0.000
0.000
0.34
0.52
0.54
1.07
1.36
2.87

21 Electrochemistry

Standard cell potentials

E o

Cell
Li | Li+ || Cu2+ | Cu

____

Mg | Mg2+ || I2 | I | Pt

____

Zn | Zn2+ || Br2 | Br | Pt ____

Cu | Cu2+ || Zn2+ | Zn

____

Which is not spontaneous?

See 21-2

18

Table of standard reduction potential

Reaction E o (V)
F2 (g) + 2 e = 2 F (aq) 2.87
Cl2 (g) + 2 e = 2 Cl (aq) 1.36
Br2 (l) + 2 e = 2 Br (aq) 1.07
I2 (s) + 2e = 2 I (aq) 0.54
Cu+ + e = Cu (s) 0.52
Cu2+ + 2 e = Cu (s) 0.34
(reference) H2 (g) = 2 H+ + 2 e
0.000
(reference) 2 H+ + 2 e = H2 (g) 0.000
Zn2+ + 2 e = Zn (s) 0.76
Mg2+ + 2 e = Mg (s) 2.38
Na+ + e = Na (s) 2.71
Li+ + e = Li (s)
3.04
21 Electrochemistry

The listing order in the table

may be different in different
text books. However, the
principles and methods of
application remain the same.
This is the order given on the
Exam Data Sheet, that is
different from the text.

19

Strength of oxidation
The ability of a chemical to oxidize is its ability to take electrons from
other species,
Oxidizing agent + n e Reduced species
Strength of oxidation of an oxidizing agent is measured by its reduction
potential.
Similarly, strength of reduction of a reducing agent is measured by its
oxidation potential.
Oxidized species Reducing agent + n e
Be able to order the species according to oxidizing strength.
_____
21 Electrochemistry

20

Reaction direction and emf

What is the emf for the reaction,
Zn2+ (aq) + 2Fe2+ (aq) = Zn (s) + 2Fe3+ (aq)?
Solution:
Know what data to look for

Zn2+ + 2 e Zn Eo = 0.76 V
Fe3+ + e Fe2+ Eo = + 0.77 V +
2 Fe2+ 2 Fe3+ + 2 e Eo = 0.77 V
Zn2+ (aq) + 2 Fe2+ (aq) Zn (s) + 2Fe3+ (aq) Eo = 1.53 V
non-spontaneous Pt | Zn2+ | Zn || Fe2+ | Fe3+ | Pt impractical
The reverse reaction is spontaneous,
Zn (s) + 2Fe3+ (aq) Zn2+ (aq) + 2Fe2+ (aq)
Zn | Zn2+ || Fe3+ | Fe2+ | Pt
21 Electrochemistry

Eo = + 1.53 V
21

Free energy and emf

What is the free-energy change for the cell,
Zn | Zn2+ (aq) 1 M || Ag+ (aq) 1 M | Ag?
Solution: Reduction potential required,
Zn Zn2+ + 2e
Eo = 0.76
Ag+ + e Ag

2 Ag+ + 2e 2Ag
Cell reaction

Eo = 0.80

Eo = 0.80

2 Ag+ + Zn 2Ag + Zn2+

Eo = 1.56 V

Go = n F Eo = 2 * 96485 * 1.56
= 3.01e5 J or 302 kJ
Condition for spontaneous
reaction is G or + E.
Negative indicate energy is released.
The free energy for the cell is 301 kJ per mole of Zn, what is the emf?
21 Electrochemistry

22

General cell emf

G o is the standard energy change. G is for non-standard conditions.
Text uses Ecell instead of E

G = n F E

Similarly, E o is the standard emf whereas E is general emf.

G = G o + R T ln Q

E = Eo R T / n F ln Q

reaction quotient

When a system is at equilibrium (Q = K), G = 0. Therefore,

G = G o + R T ln K = 0 E = Eo R T / n F ln K = 0 equilibrium constant
G o = R T ln K

E o =

RT

or G o = ln(10) R T log K

E o =

2.303 R T

/ n F ln K

21 Electrochemistry

/ n F log K

At 298 K

0.0592
E o = log K
n

23

The Nernst equation

For a general reaction,
aA+bB=cC+dD
RT
[C]c [D]d
E = E o ln
nF
[A]a [B]b
This Nernst equation correlates cell emf with [ ] or reactivities
of reactants and products as well as T
Units for [ ]:
mol L-1 for aqueous solution,
atm (for gas),
and constant for solid and liquid.
21 Electrochemistry

See 21-4

24

Evaluating E

RT
[C]c [D]d
E = E o ln
nF
[A]a [B]b

At 300 K, evaluate the cell emf for

Zn | Zn2+ (0.100 M) || H+ (0.200 M) | H2 (1.111 atm) | Pt
Solution:
Look up:

Zn Zn2+ (aq) + 2e,

2 H+ (aq) + 2 e H2 (g),

(R = 8.314 J mol-1 K-1, F = 96485 C mol-1)

The reaction is
Zn(s) + 2 H+ (aq) Zn2+ (aq) + H2(g)
8.314 J mol-1 K-1 * 300 K

E o = 0.76 V
E o = 0.00 V
E o = 0.76 V

(0.100) (1.111)

E = 0.76 ln
2 * 96485 C mol-1

= 0.76 0.0129 * (1.02)

= 0.76 0.013 = 0.75
V
21 Electrochemistry

(0.200)2

See example 19.12

25

Concentration cell
Problem: At 298 K, evaluate the emf of the cell
Cu | Cu2+ (0.10 M) | | Cu2+ (1.0 M) | Cu
Cu(s) Cu2+(0.1 M) + 2e;

Cu2+ (1.0 M) + 2e Cu(s)

Solution:
The standard emf (Eo = 0.00)for
Cu | Cu2+ || Cu2+ | Cu
The reaction is actually Cu (s) + Cu2+ (1.0 M) = Cu2+ (0.1 M) + Cu (s)
R T [Cu2+]
R T 0.10
E = 0.00 - ln = ln
2F
[Cu2+]
2F
1.00
8.3145 * 298 1.0
When 2 [ ]s are
= + ln = 0.0295 V
equal, E = 0
2*96485
0.1
The voltage is purely due to concentration difference. Solutions in the two
compartment try to become21
equal.
26
Electrochemistry
See p. 841

Equilibrium Constant K and Eocell

Calculate the solubility product of AgCl from data of standard cell
Solution: Look up desirable data
Ag+Cl (s) + e Ag0(s) + Cl E = 0.2223 V
Ag+ (aq) + e Ag (s) E = 0.799 V
Ag (s) Ag+ (aq) + e E = 0.799 V
Get the desirable eqn
AgCl (s) Ag+ (aq) + Cl (aq) E = 0.577 V
Ksp = [Ag+][Cl ]
Show that for this cell
Ag | Ag+, 1 M || Cl, 1 M | AgCl | Ag
log Ksp = 0.577 / 0.0592 = 9.75
Eo = 0.577 V
9.75
Ksp = 10
= 1.8e10
but for this cell

At 298 K

0.0592
E o = log K
n

Ag | AgCl |Cl, 1 M || Ag+, 1 M | Ag

Eo = +0.577 V
21 Electrochemistry

See p. 837

27

Evaluate free-energy change

Evaluate G o for the reaction
Zn (s) + 2 Ag+ (aq) = Zn2+(aq) + 2 Ag (s)
Solution:
Required to look up:
Eo V
Ag+ + e = Ag
Zn2+ + 2 e = Zn

2 Ag+ + 2 e 2Ag
Zn Zn2+ + 2 e
Zn (s) + 2 Ag+ (aq) Zn2+(aq) + 2 Ag (s)

See slides 17 and 22

Write the cell for this rxn

0.80
0.76

0.80 +
+ 0.76
1.56 (= E o)

G o = n F
E o
= 2 * 96485 C * 1.56 V
= 301000 J
= 301 kJ
21 Electrochemistry

28

Summary of thermodynamics
Chemical energy
Ho, So

Stoichiometry

G = H T S
o

n
Reaction quotient &
equilibrium constant
G = G o + R T ln Q
G o = R T ln K
21 Electrochemistry

Electric energy
Go = n F Eo

Reaction quotient &

equilibrium constant
E = E o R T/ n F ln Q
E o = R T/ n F ln K
29

insight from cold denaturation and

a two-state water structure
By Tsai CJ, Maizel JV Jr, Nussinov R.

The exposure of non-polar surface reduces the entropy and

enthalpy of the system, at low and at high temperatures. At low
temperatures the favorable reduction in enthalpy overcomes the
unfavorable reduction in entropy, leading to cold denaturation. At high
temperatures, folding/unfolding is a two-step process: in the first, the
entropy gain leads to hydrophobic collapse, in the second, the
reduction in enthalpy due to protein-protein interactions leads to the
native state. The different entropy and enthalpy contributions to the
Gibbs energy change at each step at high, and at low, temperatures
can be conveniently explained by a two-state model of the water
structure.
21 Electrochemistry

30
Biochem Mol Biol. 2002;37(2):55-69

pH and emf
Consider the cell,
Zn | Zn2+ (1.00 M) || H+ (x M) | H2 (1.00 atm) | Pt
From table data,
Zn2+ + 2e = Zn

Eo = 0.76

2 H+ + 2 e = H2
Eo = 0.00
Zn = Zn2+ + 2e
Eo = 0.76
Zn + 2H+ = Zn2+ + H2
Eo = 0.76
RT
[Zn2+] PH2
E = Eo ln
2F
[H+]2
= Eo + 0.0592 log [H+]

At 298 K (pH meters)

0.76 E
pH =
0.0592

= 0.76 0.0592 pH
21 Electrochemistry

31

pH electrodes
pH Range:
0-14
Temp. Range:
0-100 C
Internal Ref:
ROSS
Junction:
Ceramic
Dimensions:
120 mm x 12 mm
Slope:
92 - 102%
Temp. Accuracy:
0.5 C
Catalog Number: 8202BN
(BNC Connector, 1 meter cable)

21 Electrochemistry

32

Ion selective electrode

More research has gone into pH
measurements. Nernst started it.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Concentration;
Temperature;
Electrode surface conditions;
Number of charges of ions (8);
Stirring (6);
Suspension (7);
Zwitterionic nature, net charge density;
Anything changing ionic adsorption;
Isoelectric nature of surface material;
The Nernst equation deals only with concentration and temperature
21 Electrochemistry

33

Battery technology
By use: automobile, flash light, radio, computer,
camera, watch, emergency equipment, artificial
heart machine, pace makers, hearing aids,
calculators, (portable energy)
By type: alkaline, dry, wet, storage, rechargeable,
etc

Aluminum for battery

By chemistry: alkaline, carbon zinc, dry, cell, lithium, manufacture
lithium ion, lithium polymer, NiCd, etc.
By material: anode material, cathode material,
electrode, etc.
21 Electrochemistry

See 21-5

34

Lead Storage Battery for Autos

Anode Negative plate
Pb + SO42- PbSO4 +
2eSeparator
Cathode
Positive plate
A 12-V battery
consists of 6
such cells

PbO2 + 4H+ + SO42- + 2e PbSO4 + 2 H2O

H2SO4

Net reaction: Pb + PbO2 + 2 H2SO4 = 2 PbSO4 + H2O

21 Electrochemistry

35

Figure 18.6: Schematic of one cell of the lead battery.

21 Electrochemistry

Copyright by Houghton Mifflin Company. All rights reserved.

3610

A mercury battery.

21 Electrochemistry

37

Corrosion:
Unwanted Voltaic Cells
Fe(s) Fe2+ (aq) + 2e
O2 + H2O (l) + 4e 4 OH (aq)
2 Fe(s) + O2 + H2O
2 Fe2+ (aq) + 4 OH (aq)
What are effective corrosion
prevention methods?
Coating
Use sacrifice electrode
21 Electrochemistry

See 21-6

38

Cathodic protection of an
underground pipe.

21 Electrochemistry

39

Ion displacement reactions (corrosion)

Reaction E o (V)
What metal will react
with certain ions?

Li+ + e = Li (s)
Na+ + e = Na (s)
Mg2+ + 2 e = Mg (s)
Zn2+ + 2 e = Zn (s)
Zn + 2 Ag+ Zn2+ + 2 Ag
(reference) 2 H+ + 2 e = H2 (g)
Zn + 2 Cu2+ Zn2+ + Cu
(reference) H2 (g) = 2 H+ + 2 e
Zn2+ + 2 Ag Zn + 2 Ag+
2+

Cu
+
2
e
= Cu (s)
2+
2+
Zn + Cu Zn + 2 Cu
Cu+ + e = Cu (s)
I2 (s) + 2e = 2 I (aq)
Ag+ (aq) + e- = Ag (s)
Br2 (l) + 2 e = 2 Br (aq)
Cl2 (g) + 2 e = 2 Cl (aq)
See 21-1
21 Electrochemistry F (g) + 2 e = 2 F (aq)
2

3.04
2.71
2.38
0.76
0.000
0.000
0.34
0.52
0.54
0.80
1.07
1.36
40
2.87

Electrolysis of molten salts

Eo=-1.36 V; 2 Cl Cl2 + 2e Battery
e
oxidation

2 Cl Cl2 + 2e
2 Na+ + 2 e 2 Na
Net
2 NaCl 2 Na + Cl2

Eo=-2.71V;
2Na+ + 2e 2Na
e
C
A
T
H
O
D
E

A
N
O
D
E

805o C

reduction

Molten salts consists of Na+ and Cl ions

Charges required to produce 1 mole Cl2 and 2 moles Na = 2F

Energy required = 2 F E;
21 Electrochemistry

(E > 4.07 V)
See 21-7

41

Electrometallurgy of Sodium

21 Electrochemistry

42

Electrolysis of NaCl solution

2 Cl = Cl2 + 2e
Battery
Cl2 + H2O = HCl + O2
e
oxidation
A
N
O
D
E

2Na+ + 2e = 2Na
2Na + 2H+ = H2 + 2Na+
C
A
T
H
O
D
E

reduction

Salt solution consists of Na+ and Cl ions

21 Electrochemistry

43

Refining Copper by Electrolsis

Copper can be purified by electrolysis. Raw copper is oxidized
Cu = Cu2+ + 2e
and purer copper deposited on to the cathode from a solution
containing CuSO4
Cu2+ + 2e = Cu
If a current of 2 amperes pass through the cell, how long will it take to
deposit 5.00 g of copper on the cathode? (1 ampere = 1 C s 1)
Solution
5.00
2*96485 C 1 s
------ mol ----------- ------ = work out your answer
65.5
1 mol 2 C 21 Electrochemistry
_______

New
44

Aluminum (Al), the third most abundant elements on Earth crust as bauxite or alumina Al2O3,
remain unknown to man until 1827, because it is very reactive. By then, Wohler obtained some
Al metal by reducing Al2O3 with potassium vapore.
In 1886, two young men electrolyzed molten cryolite Na3AlF6 (melting point 1000 C), but did
not get aluminum.

Production of aluminum
Hall and Heroult tried to mix about 5% alumina in their molten cryolite, and
obtained Al metal. This is the Hall process.
AlF63 + 3 e Al + 6 F . . . Cathode
2 Al2OF62 + C(s) + 12 F + 4 AlF63 + CO2 + 4 e . . . Anode
2 Al2O3 + 3 C 4 Al + 3 CO2 . . . Overall cell reaction
Charge required for each mole Al = 3 F
Energy required = 3 F E
21 Electrochemistry

45

Electrometallurgy of Aluminum

21 Electrochemistry

46

Electrolysis of acid solution

H2O = O2 + 2e + 2 H+
oxidation

Battery
e

A
N
O
D
E

2H+ + 2e = H2
C
A
T
H
O
D
E

reduction

Solutions containing H+ and SO42 ions

Charges required to produce 1 mole H2 and moles O2 = 2F
Energy required = 2 F E
21 Electrochemistry

47

Electrolysis of H2SO4 solution

Pure water is not a good electric conductor. In the presence of
electrolytes, water can be decomposed by electrolysis.
On the other hand, electrolysis of electrolyte solutions may reduce H +
and oxidize O2 in H2O.
In an H2SO4 solution,
cathode reductions are
2 H2O (l) + 2 e = H2 (g) + 2 OH
(same as 2H+ + 2e = H2)
Anode oxidation:
2 H2O (l) = 4 e + O2 (g) + 4 H+
2 SO42 = [SO3OOSO3]2 + 2 e
21 Electrochemistry

E o = 1.23 V (observed)
E o = 2.01 V (not observed)
48

Electrolysis of H2SO4 solution

E o = 1.23 V
E o = 2.01 V

2 H2O (l) = 4 e + O2 (g) + 4 H+

2 SO42 = [SO3OOSO3]2 + 2 e

Battery
e

oxidation
A
N
O
D
E

2H+ + 2e = H2

reduction

C
A
T
H
O
D
E

Solution consists of H+ and SO42 ions

21 Electrochemistry

49

Electroplating of metals
Galvanizing

Zn2+ + 2 e Zn

onto metal surface

Copper purification

Cu2+ + 2 e Cu

onto pure Cu electrode

Silver plating

Ag+ + e Ag

onto metal surface

Over a half century of extensive and

innovative research has made us one of the
nation's leading experts in plating on
magnesium

Since 1971, Cal-Aurum has provided electroplating

services to the electronic component industry with
the highest standards of quality, performance, and
competitive pricing.
Miller specializes in plating metals such as
magnesium, aluminum, zinc, copper, powdered
metals, steel and various other substrates.
21 Electrochemistry

50

Summary
The 20th century belongs to electrons. They continue affecting our lives the 21st century.
Chemistry studies the drama played by electrons, and electrochemistry is the finale.
Energy directs and produces the show, but you set the magic stage for a great
performance.

Leo and Ger tell electrons to get in and out of your stage, and you must
skillfully provide paths to balance the flow.
Cells are the stages for the performance, you must construct,
represent, figure out the potentials, and control the show.
Chemical reaction, equilibrium, (acid, base, heterogeneous, and
complex formation) and electrochemistry guide us using simple rules.
Apply rules you have learned in Chem1235 to understand what is
happening around you and may your live be full of happiness.
21 Electrochemistry

51

Skills for Electrochemistry (review)

Make up a Daniel cell using Pb and Ag as the
electrodes. Draw a diagram for it.

Use short notation to represent the cell for the

spontaneous reaction
Write half reaction equations for both cathode and
anode and explain the reactions

Write balanced redox equations

Calculate emf for a nonstandard cell and its energy

Calculate equilibrium constant K from Eo

21 Electrochemistry

52