Chapter 7 Electrochemistry

Electrolysis

Electric energy Chemical energy

Galvanic cell
 Definition of electrochemistry
• I:
• A science studying the relationship
between chemical energy and electrical
energy and the rules of conversion of
two energies.
• II:
• Electrochemistry is the study of
solutions of electrolytes and of
phenomena occurring at electrodes
immersed in these solutions.
The application of electrochemistry
⒈ Electrolysis
hydrometallurgy of metal；
electrolytic preparation；
electroplating；
electrolytic oxidation.

⒉ Batteries
Primary batteries
Secondary Batteries

⒊ Electro-analysis
polarography，pH，electric
conductivity, etc.
 7.1 Faraday’s law
• Michael Faraday, a British chemist and physicist, studied the decomposition

of solutions of salts, acids and bases by electric current.

• Faraday's law of electrolysis states that the
amount of any substance that is deposited or
dissolved in electrolysis is directly proportional to
the total passed electric charge.
• It can be expressed as

Q  zF 
F is Faraday constant.
F = Le = 96485.309 C·mol-1 = 1 Faraday.
 coulometer

• The silver coulometer and copper

coulometer are commonly used ones.

• If one mole of silver, 107.870 g, is

deposited on the cathode of a silver
coulometer, we will know that the
quantity of electricity passed through
the coulometer is 1 coulomb.
7.2 Transport numbers and mobilities
• The definition of transport number t is that
current carried by ion B divided by the sum of the
current of all the ions in solution, which is also
called the transference number of ion B.
I Q v nc
t    
I   I  Q  Q v  v n
I Q v na
t    
I   I  Q  Q v  v n
nc and na are the amount of substance of positive ions
migrate out from anodic region and that of negative ions
migrate out from cathodic region respectively.
Let 4F be passed through the cell; t+=3t-

Before electrolysis

On electrolysis

After electrolysis
 Mobility
• The transport numbers of ions depend on the
properties of ions and solvents, temperature,
concentration, electric field strength and the like.

• The mobility uB of an ion B is defined as its

velocity in the direction of an electric field E of
unit strength.
u B  vB / E
u u
t  t 
u  u u  u
mobilities of hydrogen and hydroxyl ions
• the mobility of hydrogen and hydroxyl ions in
aqueous solution is abnormally high.

• This is because both the H3O+ ion and hydroxyl

ion are able to transfer a proton to a neighboring
water molecule. This is explained by the fact that
the H+ and OH- ions need not migrate through a
protic solvent, but move through exchange of a
proton between neighboring solvent molecules.

• The unit of mobility is m2·V-1·s-1.

measurement of transport numbers by Hittorf method

The method of
Hittorf is based
on concentration
changes in the
anodic region
and cathodic
region in an
electrolytic cell,
caused by the
passage of
current through
the electrolyte.
measurement of transport number by the moving boundary method

Suppose the boundary moves a distant

x from AA’ to BB’ for the passage of Q
coulombs. All the ions, H+, passed
through the boundary AA’.
The amount of substances transported
is then Q/F, of which t+Q/F are carried
by the positive ion. If the volume
between the boundaries AA’ and BB’ is
V, and the concentration of HCl is c,
then
tQ / F  Vc
FVc
t 
Q
 7.3 Conductance, conductivity and molar conductivity

• 7.3.1 The definition and the measurement

• Conductance G in S

1 As
G G 
R l

• κ in equation is conductivity. In S m-1.

• Molar conductivity (in S m2 mol-1)

m   / c
Measurement of the conductivity

R1 R3

R R4
1 R3
G 
R R1 R4
l
 G  G  K cell
As

l
K cell 
As
 Application of conductivity measurement

• Example The conductivity and molar conductivity

of a saturated aqueous solution of silver chloride
are 3.41×10-4S·m-1 and 138.26×10-4S·m2·mol-1
respectively at 25℃. The conductivity of the water
used to make the solution is 1.60×10-4S·m-1 at
the same temperature. Calculate the solubility of
silver chloride in water at 25℃.
• Solution the conductivity of the silver chloride
solution should be the sum of conductivities of
silver chloride and water.
•  (AgCl)   (solution)   (H 2O)
 (3.41104  1.60 104 )S  m-1
 1.81104 S  m-1
• The solubility of silver chloride solution is then
obtained
•  1.81104 S  m-1
c   0.01309mol  m-3
m 138.26 104 S  m 2  mol-1
 7.3.2 The dependence of molar conductivity on
the concentration

Fro strong electrolytes, Kohlrausch observed

that m decreased with concentration according to
the expression

m  m  A c
conductivities and the concentrations of
electrolytes
 7.3.3 Law of the independent migration of ions

Kohlrausch discovered relations between the values

of  m for different electrolytes. For example

 m (KCl)  0.01499 S  m 2  mol-1

 m (LiCl)  0.01150 S  m 2  mol-1
 m (KNO3 )  0.01450 S  m 2  mol-1
 m (LiNO3 )  0.01101S  m 2  mol-1

The difference in for pairs of salts having common ion is

always approximately constant.
 m (KCl)   m (LiCl)   m (KNO3 )   m (LiNO3 )  0.00349 S  m 2  mol -1

 m (KCl)   m (KNO3 )   m (LiCl)   m (LiNO3 )  0.00049 S  m 2  mol -1

This behavior indicates that ions in an extremely dilute

solution migrate independently. There is no interaction
between different ions. Therefore

  

m

m,     
m, 
For example

At 25℃，
 m (NaAc) = 91.0×10-4 S·m2·mol–1，
 m (HCl)=426.2×10-4 S·m2·mol–1，
 m (NaCl)=126.5×10-4 S·m2·mol–1，
What is the molar conductivity of HAc at 25℃?
Solution
 m (NaAc) = m (Na + ) + m (Ac )
 m (HCl) = m (H + ) + m (Cl )
 m (NaCl) = m (Na + ) + m (Cl )
 m (HAc) = m (H + ) + m (Ac )
= m (H + )   m (Cl )   m (Na + )   m (Ac )
  m (Na + )   m (Cl )
= m (HCl)   m (NaAc)   m (NaCl)
=(426.3 +91.0–126.5)×10–4 S·m2·mol–1
=390.7×10–4 S·m2·mol–1
 7.4 Activities of ions and the Debye-
Hückel limiting law
• 7.4.1 Activities of ions
• Consider an electrolyte

C  A    C   A
z z

The total chemical potential of an electrolyte is

         
b   b b   b

a    b / b a   b / b
 C + A   +C   A
z+ z

  $  RT ln a
+    RT ln a+
$
+

    RT ln a
$


    +     (  $    $ )  RT ln(a  a )

 

 
   RT ln(a  a )
$

 
aa a  
For example HCl(aHCl )  H+ (aH+ )  Cl (aCl )

 HCl   HCl
$
 RT ln aHCl

H  H$  RT ln aH
+ + +

Cl  Cl$  RT ln aCl

  

 HCl   H  Cl
 

 (  H$ +  Cl$  )  RT ln(aH+  aCl )

aHCl  aH+  aCl

Define the mean activity of ions as

    1
a def (a a )
   = +  
mean activity coefficient of ions
    1
 def (  )
 
mean molality of ions
def     1  
b (b b )
  aa a    a
b b 
a    $  (  $ )
b b
example
 7.4.2 The ionic strength

The ionic strength, I, is defined by

I 1
2 b z
B
2
B B

In dilute solutions, the activity coefficients of

electrolytes, the solubilities of sparingly soluble
salts, rates of ionic reactions, and other related
properties become functions of ionic strength.
 3.德拜-休克尔极限公式

(1)离子氛（ionic atmosphere）
这是德拜-休克尔理论
中的一个重要概念。他们认
为在溶液中，每一个离子都
被反号离子所包围，由于正、
负离子相互作用，使离子的
分布不均匀。
若中心离子取正离子，周围有较多的负离子，部分电
荷相互抵消，但余下的电荷在距中心离子 r 处形成一
个球形的负离子氛；反之亦然。一个离子既可为中心
离子，又是另一离子氛中的一员。
7.4.3 The Debye-Hückel limiting law
 lg  i   Azi
2
I
lg     Az | z | I
In aqueous solution at 25℃
-1 1/2
A  0.509(mol  kg ) -1

It is only applies to dilute solutions.

 7.5 Electrochemical cells
• There are two basic types of electrochemical cell.
• A galvanic cell and an electrolytic cell

Zn Zn 2+ +2e
Cu 2+ +2e Cu
Zn+Cu 2+ Zn 2+ +Cu
• This electrochemical cell is represented by the
schematic diagram or cell symbol

Zn | Zn (a1 )┊
┊Cu (a2 ) | Cu
2+ 2+

the vertical lines indicate boundaries between different

phases. For boundary between two liquid phases a
dashed line ┋ is used to denote. A double dashed line ┋ ┋
used to stand for a salt bridge.
The standard convention is to put the negative pole of
the battery on the left hand side and the positive pole on
the right hand side.
example

Zn|ZnSO4(b)┊CuSO4(b)|Cu
example

Pt | H2 (p) | HCl(b) | AgCl(s) |Ag

7.6 Types of electrodes
• 7.6.1 Metal electrodes
2 2
Zn | Zn: Zn + 2e Zn
• Some time an amalgam instead of a pure metal
is used to form a metal electrode.

• 7.6.2 Gas electrodes 2H   2e H2

• In an alkaline solution,
-
2H 2 O + 2e H 2 (g) + 2OH
Schematic diagram of hydrogen electrode
• The oxygen electrode has the same structure as
hydrogen electrode. The electrode reaction is
+
O2 (g) + 4H + 4e 2H 2O

• In an alkaline solution, it is

-
O2 (g) + 2H 2O + 4e 4OH
7.6.3 Oxidation-reduction electrodes
• For example
3+ 2+
Fe + e Fe
• It is denoted as
3+ 2+
Fe , Fe | Pt
• Quinhydrone electrode is one of several oxidation-
reduction electrodes
+
C6 H 4 O2 +2H +2e C6 H 4 (OH) 2
7.6.4 Metal-insoluble-salt electrodes
• Metal-insoluble-salt electrodes are denoted as M |
MX | X-. For example,
•

AgCl(s)+e Ag(s)+Cl-
calomel electrode
-
Hg 2 Cl2 (s) + 2e 2 Hg + 2Cl
7.6.5 Metal-insoluble-oxide electrodes
• Metal-insoluble-oxide electrodes consist of a
metal covered with one of its insoluble oxide
which is in contact with an electrolyte solution.

Sb 2 O3 (s) + 3H 2 O + 6e 2Sb + 6OH -

7.6.6 Ion selective electrodes (ISEs)
• The important ion selective electrode is Glass
membrane electrode. glass acts as a weak acid

- +
Glass-H Glass + H
The hydrogen ion activity of the
internal solution is held constant.
When a solution of different pH from
the inside comes in contact with the
outside of the glass membrane, the
glass is either deprotonated or
protonated relative to the inside of
the glass.
7.7 Designs of galvanic cells
• Example Design a galvanic cell by using
following two reactions:
1
2 Cl2 (g) + Ag  AgCl(s)
H + OH  H 2O
+ -

• Solution
Anode reaction: Ag + Cl- (a)  AgCl(s) + e
Cathod reaction: 1
2 Cl2 (g) + e  Cl- (a)

Ag|AgCl(s)|Cl- (a)|Cl(g)|Pt
Solution
anode 1
2 H 2 (g, p) + OH -  H 2 O + e
cathode H + + e  12 H 2 (g, p)

Pt|H 2 (g, p)|OH ┊

┊H |H 2 (g, p)|Pt
- +

If oxygen electrode is considered, the reactions for two electrodes are

anode OH -  14 O 2 (g, p) + 1
2 H 2O + e
cathode 1
4 O 2 (g, p)  H + + e  12 H 2O

Pt|O 2 (g, p)|OH ┊

┊H |O 2 (g, p)|Pt
- +
Example
• Devise galvanic cells with the following diffusion
processes.

H2 (g, p1 )  H2 (g, p2 ) (p1  p2 )

Ag + (a1 )  Ag + (a2 ) (a1  a2 )
• Solution
• (1) Reactions at two electrodes are
anode H2 (g, p1 )  2H+ (a) + 2e
cathode 2H+ (a) + 2e  H2 (g, p2 )
Pt|H 2 (g, p1 )|H + (a)|H 2 (g, p2 )|Pt
• (2) Solution

Anode Ag  Ag (a2 ) + e
+

Cathode Ag (a1 ) + e  Ag
+

Cell Ag|Ag + (a2 )┊

┊Ag + (a1 )Ag
example
1
H 2 (g)+ O 2 (g)  H 2O(l) Is the following design correct？
2
anode　　　H 2 (g)  2H + +2e
1
cat hod　　O 2 (g)+H 2O(l)+2e  2OH -
2
desi gn　　Pt｜H 2 (g)｜H＋ ┆ OH - ｜O 2 (g) | Pt
1
cel l r xn　 H 2 (g)+ O2 (g)+H 2 O(l)  2H + +2OH -
2
This design is not correct, because two ions, hydrogen
ion and hydroxyl ion, are in different solutions.
The correct design is
anode　　　H 2 (g)＋2OH -  2H 2O+2e
1
cat hod　　O 2 (g)+H 2 O(l)+2e  2OH -
2
cel l 　　Pt｜H 2 (g)｜OH - ｜O 2 (g) | Pt
1
cel l r xn　 H 2 (g)+ O 2 (g)  H 2 O(l)
2
or
anod　　　H 2 (g)  2H＋ +2e
1
cat hod　　O 2 (g)+2H＋ +2e  H 2 O
2
desi gn　　Pt｜H 2 (g)｜H＋ ｜O 2 (g) | Pt
1
cel l r xn　 H 2 (g)+ O 2 (g)  H 2 O(l)
2
7.8 Electrode potentials
• 7.8.1 The EMF in a galvanic cell
• If the cell is connected to a measurement circuit,
an inevitable potential difference called contact
potential between two electrodes, copper and
zinc in the Daniell cell, exists as a part of total
EMF of the cell.
• Cu|Zn|ZnSO4(a1)|CuSO4(a2)|Cu
E  [ (Cu)   (Cu 2+ )]  [ (Cu 2+ )   (Zn 2+ )]  [ (Zn 2+ )   (Zn)]  [ (Zn)  (Cu)]

E  1  2  3  4

• 1   (Cu 2+ )   (Cu) is the potential between
solution of copper sulfate and electrode of copper;
• 2   (Zn )   (Zn)
2+
is the potential between
solution of zinc sulfate and electrode of zinc;
•  3   (Cu 2+
)   (Zn 2+
) is the potential between
two solutions of copper sulfate and zinc sulfate, it
is called the liquid junction potential;
• 4   (Zn)   (Cu) is the contact potential
between two metals of zinc and copper.
7.8.2 Potential difference between electrode and solution

n+
M + ne M
7.8.3 Potential difference between two solutions

For a simple case of I-I type of electrolyte,

RT a ,1
El  (t  t ) ln
F a ,2
7.8.4 Potential of standard hydrogen electrode

• The ultimate reference is the normal hydrogen

electrode (NHE), or the standard hydrogen
electrode (SHE), the potential of which is defined
as zero at all temperatures.

E (H + /H 2 )  0V

• The standard hydrogen electrode consists of a

platinum electrode in contact with a solution of H+
at unit activity and saturated with H2 gas with the
standard pressure of 100 kPa.
7.8.5 Standard electrode potentials

Pt|H 2 (p )|H + (a =1)┊

┊electrode tested

E (cell)  E (tested electrode)  E (H + /H 2 )

=E (tested electrode)  0
=E (tested electrode)

Pt|H 2 (p )|H (a =1)┊

+
┊Zn (a =1)|Zn(s)
2+

E (Zn /Zn)  0.763V

2+
7.9 Electrochemical thermodynamics
• 7.9.1 Gibbs function and reversible EMF
• EMF: Electromotive force

 W  ( zFd ) E
r
'

• For a cell reaction at constant temperature and

pressure,  r G  Wr'

d  r G   zFEd
 r G 
r Gm      zFE
  T , p
7.9.2 Entropy and enthalpy of cell reaction

  r Gm   E 
    r Sm  r Sm  zF  
 T  p  T  p

• at constant temperature,
 r H m   r Gm  T  r Sm
 E 
 r H m   zFE  zFT  
 T  p
In a reversible galvanic cell Qr  T  r S
 E 
Qr ,m  zFT  
 T  p
For a reversible galvanic cell at constant pressure

 E 
   0, Qr  0
 T  p

 E 
   0, Qr  0
 T  p

 E 
   0, Qr  0
 T  p

The reversible heat in a galvanic cell is different from the

heat of chemical reaction
 Example
• The EMF and temperature coefficient are
1.01832V and -5.00×10-5V·K-1 respectively for
the Weston standard cell at 25℃. Calculate the
• rGm , r Sm , r H m , and Qr.
• Solution The cell reaction is
Cd(amalgam) Cd 2+ +2e
Cd 2+ +SO424  83 H 2 O(l) CdSO 4  83 H 2O(s)
Anode
Cd(amalgam)+SO424  83 H 2 O(l) CdSO 4  83 H 2O(s)+2e

Cathode Hg 2SO4 (s) + 2e 2Hg(l) + SO42

Cell Cd(amalgam)+SO424  83 H 2O(l) CdSO 4  83 H 2O(s)+2e

 r Gm   zFE  2  96485 1.01832  196505J  mol-1

 E  5
 r Sm  zF    2  96485  ( 5.00  10 )  9.65J  K -1

 T p

 r H m   r Gm  T  r Sm  196505  298.5  (9.65)  199359J  mol-1

Qr  T  r Sm  298.15  (9.65)  2877.1J  mol-1

 Weston standard cell

3
Cd(汞齐) | CdSO4  H 2 O(s) | CdSO4 (饱和溶液) | Hg 2SO 4 (s) | Hg
8
7.9.3 The Nernst equation
• For a chemical reaction or an electrochemical cell
reaction, the isotherm equation is
 r Gm   r Gm  RT ln   f B / p 
B

 r Gm   r Gm  RT ln  aBB
B
 r Gm   zFE
RT
EE  ln  aBB
zF B
• 25℃, and convert natural logarithm into common
logarithm, equation can be expressed as
0.05916V
EE  lg  aBB
z B
• When cell reaction reaches the equilibrium state,
E=0, then
RT
E  ln K
zF
• The Nernst equation applies not only to the
electrochemical cells but also to the electrodes.
RT
ln  aB(electrode)
 B(electrode)
E (electrode)  E (electrode) 
zF B(electrode)
• For instance, Cl2(g) + 2e = 2Cl-
- 2
RT [ a (Cl )]
E (Cl2 |Cl- )  E (Cl2 |Cl- )  ln
2F p(Cl- ) / p
 example Cu2++2e-→Cu

RT a(Cu)
E (Cu |Cu)  E (Cu |Cu) 
2+ $ 2+
ln
2 F a(Cu 2+ )

example O2(g) + 4H+ + 4e–  2H2O

2
RT { a (H O)}
E (O2 |H 2O, H + )  E $ (O2 |H 2O, H + )  ln + 4
2
$
4 F {a(H )} p(O2 ) / p
 Calculation of EMF

Zn(s)|Zn 2 (aZn2 ) ￤Cu 2 (aCu2 )|Cu(s)

 Zn 2 (aZn2 )  2e
() Zn(s) 
() Cu 2 (aCu2 )  2e 
 Cu(s)
2 2
Total: Zn(s)  Cu (aCu2 ) 
 Cu(s)  Zn (aZn2 )
method 1:
E  E右  E左
RT 1 RT 1
 [E $ 2
(Cu |Cu)  ln ]  [ E (Zn |Zn) 
$ 2
ln ]
2 F aCu 2  2 F aZn 2 
Method 2:
total: Zn(s)  Cu 2 (aCu2 ) 
 Cu(s)  Zn 2 (aZn2 )

RT a 2
EE 
$
ln Zn
2F aCu2
E E
$ $ 2
(Cu |Cu) E $
(Zn 2  |Zn)

Two methods, one result.

example
• Write the reactions of the following cell and
calculate the EMF at 25℃ when b(HCl)=0.1mol
kg-1.
Pt|H2 (g, 100kPa)|HCl(b)|AgCl(s)|Ag
• Solution
• H + (b) + e
1
Anode: 2 H 2 (g, 100kPa)

• Cathode: AgCl(s) + e Ag + Cl- (b)

• Total: 1
2 H 2 (g, 100kPa) + AgCl(s) Ag  H + (b) + Cl- (b)

RT a(Ag)a(H + )a(Cl- )
EE  ln
F [ p(H 2 ) / p ]1/2 a(AgCl)
 E  E [AgCl(s)|Ag]  E [H |H 2 (g)] +

a(H )a(Cl )  a   (b / b )
 - 2

2

2

2 RT b 2 RT
E  E [AgCl(s)|Ag]  ln  ln  
F b F
From table 7.4.1, the activity coefficient can be
obtained. therefore

E  0.2221  0.05916lg(0.796  0.1)2  0.3521V

From this equation we can conclude that activity coefficient
can be obtained in terms of the determination of EMF of the
cell at different concentrations of HCl.
7.9.4 Determination of E values
• Take the following cell as an example
Pt|H2 (g, 100kPa)|HCl(b)|AgCl(s)|Ag
1
2
H(
2
g) + AgCl ( s)  Ag + HCl ( aq)
RT a  Ag  a  HCl 
EE  ln
 a  H 2   a  AgCl 
1/ 2
F

a(HCl)  a2  (   b / b ) 2
2
RT  b  2 2 RT b 2 RT
EE  ln     E  ln  ln  
F b  F b F

2 RT b 2 RT
E ln E  ln  
F b F
• For small enough values of b, γ± will be given by
the Debye-Hückel formula. For HC1, the ionic
strength is equal to the molality b if no other
electrolytes are present. Therefore,
ln     Az | z | I   A ' b
1/2

2 RT b 2 RT
E ln E  A ' b1/2
F b F

• the left-hand side of this equation is plotted as a

function of b1/2, the extrapolation to b = 0 gives
the value of E from the intercept.
7.9.5 Pourbaix diagrams
• Marcel Pourbaix (1904-1998)
• Marcel Pourbaix was born in Russia, where his father, a
Belgian engineer, was working at the time.
• The significance of Marcel Pourbaix’s great achievement
was pointed out by Ulick R. Evans, widely recognized as
the “father of corrosion science,” in his foreword to
Pourbaix’s Thermodynamics of Dilute Aqueous Solutions:
“During the last decade (the 1940s) Dr. Marcel Pourbaix
of Brussels has developed a graphical method, based on
generalized thermodynamical equations, for the solution of
many different kinds of scientific problems, involving
numerous types of heterogeneous or homogeneous
reactions and equilibria... Some of these problems have
long been treated from the aspect of thermodynamics...
The application of thermodynamics to typical corrosion
reactions is a much newer development.”
For Mr. Zhang Zhongcheng

As a memory of his stay at Cebelcor in 1984/1985.

With all best wishes from
Marcel Pourbaix
April 26, 1985
Prof Pourbaix, his wife, and Zhang Zhongcheng, in 1985
Prof Pourbaix with his colleagues at Cebelcor in 1984
The E-pH diagram of copper-water system
7.10 Decomposition voltage
7.10 Decomposition voltage

氯气 氢气
• Decomposition voltage is a cell voltage at which
the electrolysis current begins to increase
appreciably.

• evolution potentials
7.11 Polarization
• 7.11.1 Electrode polarization
• The deviation of voltage from the value at
equilibrium upon the passage of current is called
polarization.
• For an electrode, the deviation of electrode
potential from its equilibrium state is called the
electrode polarization.
• overpotential, denoted as η and expressed in volts.

 (cathode)  E (cathode, equilibrium)  E (cathode)

 (anode)  E (anode)  E (anode, equilibrium)
Various overpotentials
• Concentration overpotential
• Activation overpotential (electrochemical
overpotential)
• Ohmic polarization
7.11.2 Determination of polarization curves
Polarization curves

  a  b lg J (Tafel equation)
 7.11.3 Polarizations of electrolytic and galvanic cells

anode
cathode

E
E

(anode)
(cathode)

J J
(a) electrolytic cell (b) Galvanic cell
7.12 Reactions in electrolytic cells
• At anode, the reaction which has the lowest
polarized potential E(anode) takes place.

• At cathode, the reaction which has the highest

polarized potential E(cathode) takes place.

E (anode)  E (anode, equilibrium)   (anode)

E (cathode)  E (cathode, equilibrium)   (cathode)

Example
• A zinc cathode is used to electrolyze an aqueous
solution of ZnSO4 (a±=1). What will give off at
cathode under atmospheric pressure, hydrogen or
zinc? The overpotential of hydrogen on zinc is
0.7V.
• Solution The overpotential of zinc on the cathode
is negligible. a(Zn )  1 E (Zn |Zn)  0.7630V
2+ 2+

0.05916V 1
E (Zn |Zn)  E (Zn |Zn) 
2+ 2+
lg
2 a(Zn 2+ )
 0.7630V
• The evolution potential of hydrogen at equilibrium on
cathode is
0.05916V p(H2 ) / p
E[H+ |H2 (g)]  E [H+ |H2 (g)]  lg
2 a(H2 )2
• Suppose the pressure of hydrogen is 101.325kPa, the
aqueous solution is neutral, a(H+)=10-7. Then,
0.05916V 101.325 /100
E[H + |H 2 (g)]  0  lg -7 2
 0.4140V
2 (10 )
• Consider the overpotential of hydrogen on zinc, the
polarized potential of hydrogen evolution is
E[H + |H 2 (g)]  0.4140  0.7  1.114V
• This value is lower than the deposition potential of zinc.
Therefore, it is zinc that forms on the cathode.
7.13 Corrosion
• Ulick R. Evans, the British scientist who is
considered the "Father of Corrosion Science", has
given the definition of corrosion:

• "Corrosion is largely an electrochemical

phenomenon, may be defined as destruction by
electrochemical or chemical agencies".
Fig 7.13.2 Schematic representation of current flow in a simple corrosion cell
Fig 7.13.3 The galvanic corrosion of zinc plate caused by Fe impurity
Corrosion

19.7
 Dental Filling Discomfort

2+
Hg2 /Ag2Hg3 0.85 V
2+
Sn /Ag3Sn -0.05 V
Fig 7.13.1 Simplified E-pH diagram of Fe-H2O system
Measures preventing metals from corrosion
• Cathodic protection
• There are two ways to carry out a cathode
protection.
• One is the attachment of an active metal to a
system to protect the system from corrosion.
• For example, galvanized iron.

• Another way to carry out cathode protection is the

application of an external voltage or current to set
the voltage of the material at a sufficiently
negative potential such that the rate of corrosion is
very low.
Cathodic Protection of an Iron Storage Tank

19.7
• Anode protection
 Batteries

Dry cell

Leclanché cell

Anode: Zn (s) Zn2+ (aq) + 2e-

Cathode: 2NH+4 (aq) + 2MnO2 (s) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l)

Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)
 Batteries

Mercury Battery

Anode: Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) + 2e-

Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH- (aq)

Zn(Hg) + HgO (s) ZnO (s) + Hg (l)

 Batteries

Lead storage
battery

Anode: Pb (s) + SO2-4 (aq) PbSO4 (s) + 2e-

Cathode: PbO2 (s) + 4H+ (aq) + SO2-

4 (aq) + 2e
- PbSO4 (s) + 2H2O (l)

Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2-

4
(aq) 2PbSO4 (s) + 2H2O (l)
 Batteries

A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning

Anode: 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-

Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq)

2H2 (g) + O2 (g) 2H2O (l)