Corrosion-Manual (2015) Chapter 9

ELECTROCHEMISTRY
AND
CORROSION SCIENCE
SOLUTION MANUAL
NESTOR PEREZ
University of Puerto Rico

Department of Mechanical Engineering
Mayaguez, PR 00680
ii
Contents
1 FORMS OF CORROSION
1.1 QUESTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
1
2 ELECTROCHEMISTRY
2.1 PROBLEMS/QUESTIONS . . . . . . . . . . . . . . . . . . . . .
5
5
3 THERMODYNAMICS OF AN ELECTROCHEMICAL CELL

3.1 PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
9
9
4 NANO ELECTROCHEMISTRY
25
4.1 PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
5 KINETICS OF ACTIVATION POLARIZATION
41
5.1 PROBLEMS/QUESTIONS . . . . . . . . . . . . . . . . . . . . . 41
6 MASS TRANSPORT BY DIFFUSION AND MIGRATION 71
6.1 PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
7 CORROSIVITY AND PASSIVITY
97
7.1 PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
8 DESIGN AGAINST CORROSION
107
8.1 PROBLEMS/QUESTIONS . . . . . . . . . . . . . . . . . . . . . 107
9 ELECTRODEPOSITION
125
9.1 PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
10 HIGH-TEMPERATURE CORROSION
iii
153
iv
CONTENTS
CHAPTERS:
vi
CONTENTS
Chapter 1
FORMS OF CORROSION
1.1
QUESTIONS
1.1 During metallic corrosion there is loss of weight of the metal. Why metals
undergo corrosion in a suitable environment?
Answer: Metals are thermodynamically unstable in their free state and
consequently, they corrode forming a metallic compound due to their reactivity
in the surrounding environment.
1.2 Is copper corrosion an oxidation process?
Answer: Corrosion is an oxidation process in which a pure metal surface
reacts with its environment by loosing electrons, Cu ! Cu2+ +2e , and forming
a green lm on the surface of copper.
1.3 It is known that corrosion on the surface of a metal is due to a direct
reaction of atmospheric gases. Which gas is mainly responsible for the corrosion
of most metallic iron and steel surfaces?
Answer: Oxygen when compared to halogens, oxides of sulphur, oxides of
nitrogen, hydrogen sulphide.
1.4 What are the two mechanisms for oxidation of iron? Write down the
suitable electrochemical reactions.
Answer: (a) In the absence of oxygen, the evolution of hydrogen in acid
solutions (H2 ) is represented by the following electrochemical reactions
F e ! F e2+ + 2e
2H + + 2e ! H2
F e + 2H + ! F e2+ + H2
(anode)
(cathode)
(redox)
(b) Absorption of oxygen (O2 ) in neutral or basic medium.

1
CHAPTER 1. FORMS OF CORROSION
Fe
O2 + H2 O + 2e
F e + O2 + H2 O + 2e
F e2+ + 2OH
!
!
!
!
F e2+ + 2e (anode)
2OH
(cathode)
2+
F e + 2OH
(redox)
F e(OH)2
1.5 Investigate the dierences between dry and wet corrosion Write down
at least three dierences per type of corrosion.
Solution:
Dry Corrosion
1. Corrosion occurs in the absence of moisture
2. Chemicals in the dry environment attack the metal surface
3. It is a slow process
Wet Corrosion
1. Corrosion occurs in presence of moisture
2. It involves formation of electrochemical cells
3. It is a fast process.
1.6 What is bimetallic corrosion?
Answer: It is an electrochemical corrosion due to dissimilar metals being
connected and exposed to an electrolyte, forming a galvanic cell.
1.7 What form of corrosion will cause sand grains, dust particles and an
oxide scale on the surface of metals exposed to a corrosive medium?
Answer: Pitting corrosion.
1.8 Why stress corrosion is not uniform?
Answer: Stress corrosion not uniform because a mechanically stressed
structure is highly strained at certain locations, which become the localized
anodic sites for corrosion to take place there.
1.9 What form of corrosion develops at rivets and bolts?
Answer: Crevice corrosion
1.10 Corrosion is a process of destruction of a metal surface by the surrounding environment. Environmental parameters like temperature, humidity,
gases (CO2 , SO2 , N Ox ) and pH. play an important role in studying corrosion.
What are the two factors that govern the corrosion process?
Answer: Metallic and environmental
1.11 What are the main eects or consequences of corrosion of structures?
Answer: To name a few
1.1. QUESTIONS
Corrosion reduces the thickness of metal parts of a structure and as result,

loss of mechanical strength occurs, leading failure of the structure.
Eciency of machines is reduced due to corrosion.
Because of corrosion, pipes, boilers and pumps are blocked by the corrosion
compound and therefore, they are dicult to operate eciently.
1.12 The principle constituent of wood is cellulose, which is a polysaccharide. This is a polymer made of sugar molecules joined in long chains. Will
these sugar molecules corrode a galvanized steel nail and weaken a wood beam
in a hypothetical shing vessel?
Answer: Anodic coating is used as a sacricial material during a certain
period of time and cathodic coating is used as a cathodic protection technique.
1.13 What method is used to prevent corrosion of iron by zinc coating?
Answer: Galvanisation
1.14 The principle constituent of wood is cellulose, which is a polysaccharide. This is a polymer made of sugar molecules joined in long chains. Will
these sugar molecules corrode a galvanized steel nail and weaken a wood beam
in a hypothetical shing vessel?
Answer: The galvanized steel nail will corrode and the corrosion product
will soften the wood beam at contact
with the nail. Consequently, the vessel will begin to lose structural stability.
CHAPTER 1. FORMS OF CORROSION
Chapter 2
ELECTROCHEMISTRY
2.1
PROBLEMS/QUESTIONS
2.1 Dene the galvanic electrode potential for the cell shown in Figure 2.4
using the interfacial potentials involved in the electrochemical process.
Solution:
Cu Cu SO4 Half cell + Zn SO4 Zn Half cell
0
0
+ Cu SO4 Zn SO4 + Zn 0
Cu W ire + Cu Cu W ire
+ Cu SO4 Zn SO4 Bridge
= Cu + Cu SO4 Cu SO4 + Zn SO4 Zn SO4 + Zn Zn 0

Cu
0
+Cu 0
Cu
= Cu 0
Cu
0
since Cu = 0
Cu at the copper electrode and copper wire junction. In addi0
0
tion, let Cu and 0
Cu be the potential at the copper wire-zinc electrode and the
potential at copper wire-copper electrode junctions, respectively.
2.2 Described what happens in the galvanic cell shown in Figure 2.4 when
electrons leave the Cu terminal at the Cu-Zn interface.
Explanation: The Cu Zn interface is disturbed causing electrons to ow
out of Zn into Cu terminal and consequently, Zn oxidizes according to the
anodic reaction Zn = Zn+2 + 2e. This reaction occurs at the Zn-ZnSO4(aq:)
interface where Zn+2 cations go into solution loosing electrons. Then, these
electrons react with Cu+2 cations according to the cathodic reaction Cu+2 +2e =
Cu.
5
CHAPTER 2. ELECTROCHEMISTRY
2.3 Explain why an electrode potential dierence occurs in Figure 2.4.

Explanation: The CuSO4 solution is depleted of Cu+2 cations and the
ZnSO4 is enriched in Zn+2 cations. This causes a ow of positive ions (cations)
through the solutions from the Zn electrode to the Cu electrode and a ow of
negative SO4 2 ions (anions) towards the Zn electrode. Hence, the current is
carried through the solution by these ions.
2.4 Why are Cu+2 cations electroplated on the Cu electrode surface in
Figure 2.4?
Answer: During the operation of the galvanic cell both Zn ! Zn+2 + 2e
and Cu+2 +2e ! Cu reactions occur since the electron ow process is 2e (Zn) !
2e (Cu) and Cu+2 is reduced on the Cu electrode surface as a metallic element.
2.5 Calculate the standard potential for the formation of ferric hydroxide
F e(OH)3 (brown rust).
Solution: The possible half-cell reactions and their respective standard potential are
4F e + 12OH ! 4F e (OH)3 + 12e
3O2 + 6H2 O + 12e ! 12 (OH )
4F e + 3O2 + 6H2 O ! 4F e (OH)3
=)
=)
=)
Eao = 0:771 V
Eco = 0:401 V
E o = 1:172 V
The standard potentials were taken from Table 2.3. Thus, E o = Eao + Eco =
1:172 V:
2.6 Explain why care must be exercised in using the galvanic series illustrated in Table 2.2.
Explanation: The electrode anodic and cathodic reactions dissipate energy
and consequently, the electrode potentials and activities may be altered.
2.7 If zinc and copper rods are placed in salt water, a direct chemical
reaction may slightly corrode zinc. Why?
Answer: Because Zn is more active than Cu and therefore, Zn is anodic
to Cu.
2.8 Is the cell potential a surface potential? If so, why?
Answer: Ecorr must be a surface potential because it arises due to simultaneous anodic and cathodic reactions on the metal surface.
2.1. PROBLEMS/QUESTIONS
2.9 If a monopole contains a net charge (Q) due to 10 12 moles of a species

j in a electrically neutral system, then calculate the electric potential (x ), the
electric potential strength (Ex ) and the electric force (Fx ) acting on a particle
within a distance of 9 cm from another charged particle in the x-direction.
Solution:
From eq. (2.4),
Q = zF X = (2)(96; 500 C=mol) 10

Q = 1:93x10
12
mol
C = 0:193 C
But,
1
N: m2
J: m
= 9x109
= 9x109
4o
C2
C2
= 0:09 m
=
r
Inserting these values into eq. (2.8) give the magnitude of the electric potential on a monopole system. Thus,
x
x
x
9 109 J: m= C2 1:93x10 7 C
Q
=
=
r
0:09 m
= 19; 300 J/C = 19; 300 N:m/C
= 19; 300 J/(J=V ) = 19; 300 V = 19:30 kV
which is a high value for the isolated monopole case. The magnitude of the
electric potential strength is expected to have a very high magnitude given by eq.
(2.17). Thus,
Ex
Ex
19; 300 N:m=C

= =
r2
r
0:09 m
= 2:14 105 N=C = 2:14 105 V=m
=
Thus, the electric force acting on the particle becomes

Fx
Fx
= QEx = 1:93x10
= 0:04 N
2:14 105 N=C
2.10 A battery (Example 2.2) containing 0:4 moles of M nO2 delivers 1:5 V .
For 4-hour operation, calculate the electric current and the power (in watts).
Solution:
CHAPTER 2. ELECTROCHEMISTRY
From example 2.2, M nO2 + H + + e ! MnOOH and
Q = zF XMnO2 = (1) (96500 A:s=mol) (0:4 mol)
Q = 38; 600 A:s = 38; 600 C = 38:60 kJ=V
Then,
I
P
Q
38; 600 A:s
=
= 2:68 A
t
4 60 60 s
= EI = (1:5 V ) (2:68 A) = 4:02 V:A = 4:02 watts
=
2.11 Write down the reversible hydrogen reaction for a standard electrode
and determine its standard electric potential.
Solution:
H2 = 2H + + 2e
The standard electric potential for the above reaction is taken a zero because
o
it is a standard reference. Thus, EH
+ = 0.
2 =H
2.12 Calculate the E o values for each of the following reactions as written
and determine which one is the cathode and anode.
2F e3+ + Cd ! Cd2+ + 2F e2+
Solution:
From Table 2.2,
Eo
Eo
F e+3
Cd
=
=
=
=
o
EFo e3+ =F e2+ + ECd=Cd
2+ = 0:77 VSHE + 0:403 VSHE
1:173 VSHE
Cathode because it reduces to F e+2
Anode because it oxidizes to Cd2+
Recall that the reactions illustrated in Table 2.2 are for reduction processes.
In this problem cadmium (Cd) oxidizes and therefore, the standard potential
changes its sign from negative to positive. That is,
Cd2+ + 2e
! Cd
o
ECd
2+ =Cd = 0:403VSHE
Cd ! Cd2+ + 2e
o
ECd=Cd
2+ = +0:403VSHE
Chapter 3
THERMODYNAMICS OF
AN ELECTROCHEMICAL
CELL
3.1
PROBLEMS
3.1 Consider the following electrochemical cell Cu+2 ; Cu jH2 ; H + j P t to calculate the maximum activity of copper ions Cu+2 in solution due to oxidation of
a copper strip immersed in sulfuric acid H2 SO4 at 25 C, 101 kP a and pH = 2.
Solution: The possible half-cell reactions and their respective standard potentials (Table 2.2) are
Cu+2 + 2e ! Cu
H2 ! 2H + + 2e
Cu+2 + H2 ! Cu + 2H +
=)
=)
=)
Eco = 0:337 V
Eao = 0 V
E o = 0:337 V
Then,
Go
= zF E = (2) 96; 500

o
= 65
kJ
mol
J
mol:V
(0:337 V )
Therefore, the reactions will occur as written since Go < 0. The maximum activity of Cu+2 cations can be calculated when the potential and current
densities are ECu = EH at icorr = imax . Using the Nernst equation yields
9
10CHAPTER 3. THERMODYNAMICS OF AN ELECTROCHEMICAL CELL
ECu
o
= ECu
EH
o
= EH
RT
[Cu]
ln
zF
[Cu+2 ]
2
EH
RT
[H + ]
ln
= 0:059pH
zF
[H2 ]
= 0:059 (2) = 0:118 V
Letting ECu = EH = 0:118 V yields

RT
[Cu]
ln
= 0:118 V
zF
[Cu+2 ]
zF
o
= (ECu
EH )
RT Cu
o
= ECu
EH
ln
o
(ECu
EH )
[Cu]
[Cu+2 ]
(2)(96500 m oJl . V )
=
(0:337
V
+
0:118
V)
Cu
(8:314 m o lJ. o K )(298 o K)
zF
o
(EH ECu
)
= 35:44
RT Cu
zF
RT
and
ln
[Cu]
[Cu+2 ]
[Cu]
[Cu+2 ]
= 35:44
= 2:46x1015
Thus,
Cu+2
aCu+2
[Cu]
1 mol=l
=
15
15
2:46x10
2:46x10
= Cu+2 = 4:06x10 16 mol=l

=
3.2 Consider a galvanic cell j Zn j0:10M ZnSO4 j j0:10 M N iSO4 j N i j.

Calculate the cell potential using the Nernst equation at T = 25 C.
Solution: The possible half-cell reactions and their respective standard potential (Table 2.2) are
N i+2 + 2e ! N i
Zn ! Zn+2 + 2e
N i+2 + Zn ! Ni + Zn+2
=)
=)
=)
o
ENi
= 0:250 V
o
EZn
= +0:763 V
E = +0:513 V
3.1. PROBLEMS
11
Using the Nernst equation along with N i+2 = Zn+2 = 0:10 mol=l and
[Ni] = [Zn] = 1 mol/l gives
ENi
EZn
E
RT
[N i]
ln
= 0:280 V
zF
[N i+2 ]
+2
Zn
RT
o
= EZn
ln
= 0:793 V
zF
[Zn]
= ENi + EZn = 0:513 V
o
= ENi
3.3 The dissociation constant of silver hydroxide, AgOH, is 1:10x10 4 at

25 C in an aqueous solution. (a) Write down the chemical reaction and (b)
determine the Gibbs free energy change Go .
Solution:
(a) The dissociation chemical reaction is
AgOH
Ke
= Ag+ + OH
[Ag+ ] [OH ]
=
= 1:10x10
[AgOH]
(b) The free energy change is

Go
Go
= RT ln (Ke ) = 8:314
22:58 kJ=mol
J
mol:o K
(298o K) ln 1:1x10 4
Therefore, the reaction will proceed as written since Go < 0.

3.4 Calculate (a) the concentration of AgOH and Ag + in g=l at 25 C and
(b) the pH if [OH ] = 4:03x10 3 mol=l and Ke = 1:10x10 4 .
Solution:
(a) AgOH = Ag+ + OH and Ke = 1:10x10 4 . Let [Ag + ] = [OH ] for
charge balance so that
2
Ke
[AgOH] =
But,
[Ag + ] [OH ]
[OH ]
=
[AgOH]
[AgOH]
2
2
4:03 10 3
[OH ]
=
= 0:15 mol=l
Ke
1:10 10 4
CAgOH
= [AgOH] Aw;AgOH
g
CAgOH = (0:15 mol=l) 107:87
= 18:73 g=l
l
+
Ag
= OH = 4:03x10 3 mol=l
mol
g
CAg+ = Ag+ Aw;Ag = 4:03x10 3
107:87
= 0:43 g=l
l
l
mol
g
COH = OH Aw;OH = 4:03x10 3
17
= 6:85x10
l
mol
g=l
(b) The dissociation of water ant its rate constant are

H2 O
Kw
= H + + OH
[H + ] [OH ]
=
= 10
[H2 O]
14
where [H2 O] = 1 mol=l and
H+
pH
Kw
10 14
=
= 2:48x10 12 mol=l
[OH ]
4:03x10 3 mol=l
= log H + = log 2:48x10 12 = 11:61

=
3.5 For an electrochemical copper reduction reaction at 25 C and 101 kP a,

calculate (a) the Gibbs free energy change Go as the driving force, (b) the
equilibrium constant Ke and (c) the copper ion concentration Cu+2 in g=l.
Solution:
(a) The reduction reaction and its standard potential are

Cu+2 + 2e = Cu
E o = 0:337 V
Go
= zF E o = (2) 96; 500
Go
= 65; 041
J
mol
J
mol:V
(0:337 V )
(b) The equilibrium constant is

ln Ke
Ke
J
65; 041 mol
Go
=
=
= 26:25
RT
8:314 mol:J o K (298 o K)
= 2:52x1011
3.1. PROBLEMS
13
(c) The concentration of copper cations is

[Cu]
[Cu+2 ]
+2
[Cu]
1 mol=l
Cu
=
=
= 3:97x10 12 mol=l
Ke
2:52x1011
CCu+2 = Cu+2 Aw;Cu = 3:97x10 12 mol=l (63:55 g=mol)

Ke
= 2:52x10
CCu+2
10
g=l
3.6 Use the electrochemical cell j Cd 0:05 M Cd+2 0:25 M Cu+2 Cu j to

calculate a) the temperature for an electric potential of 0:762 VSHE , and b) S,
G; H, and Q.
Solution:
a) The reactions and the required temperature are
Cu+2 + 2e = Cu
Cd = Cd+2 + 2e
Cu+2 + Cd = Cu + Cd+2
E
Ke
T
T
T
=)
=)
=)
o
ECu
= 0:337 V
o
ECd
= 0:403 V
E o = +0:740 V
RT
= Eo
ln (Ke )
zF +2
[Cu] Cd
[1] [0:05]
=
=
= 0:2
+2
[Cd] [Cu ]
[1] [0:25]
zF (E E o )
=
R ln (Ke )
J
(2) 96; 500 mol:V
(0:762 V 0:740 V )
=
J
8:314 mol:o K ln (0:2)
= 317:32o K = 44:32o C
b) Using eqs. (2.32) and (2.35) at constant pressure yields
E
@E
@T
S
S
= Eo
RT
ln (Ke )
zF
R
ln (Ke )
zF
@E
= zF
= R ln (Ke )
@T
J
J
= 8:314
ln (0:2) = 13:38
mol:o K
mol:o K
=
From eq. (2.26),
G = zF E = (2) 96; 500

G = 147 kJ=mol
J
mol:V
(0:762 V )
From eq. (2.34),
= G + T S
= 147; 000 J=mol + (317:32o K) 13:38
H
H
J
mol:o K
= 151:25 J=mol
From eq. (236),
Q = T S = (317:32o K) 13:38
J
mol:o K
Q = 4:25 kJ=mol
3.7 Pure copper and pure cobalt electrodes are separately immersed in
solutions of their respective divalent ions, making up a galvanic cell that yields
a cell potential of 0:65 VSHE . Calculate a) the cobalt activity if the activity of
copper ions is 0:85 mol=l at 25 C and b) the change in entropy S o and Gibbs
free energy Go .
Solutions:
a) The reactions and the required cobalt activity are
Cu+2 + 2e = Cu
Co = Co+2 + 2e
Cu+2 + Co = Cu + Co+2
=)
=)
=)
o
ECu
= 0:337 V
o
ECo
= 0:227 V
E o = +0:614 V
Using eq. (2.32) yields

RT
ln (Ke )
zF
zF (E E o )
ln (Ke ) =
RT
J
(2) 96; 500 mol:V
(0:65 V 0:614 V )
ln (Ke ) =
= 2:8044
J
8:314 mol:o K (298o K)
Ke = 0:0605
E
= Eo
3.1. PROBLEMS
15
Thus,
[Cu] Co+2
Ke =
[Cu+2 ] [Co]
+2
K Cu+2 [Co]
(0:0605) [0:85 mol=l] [1 mol=l]
Co
=
=
[Cu]
[1 mol=l]
+2
aCo+2 = Co
= 0:0515 mol=l
b) Using eqs. (2.32) and (2.35) at constant pressure yields
E
@E
@T
S
S
= Eo
RT
ln (Ke )
zF
R
ln (Ke )
zF
@E
= zF
= R ln (Ke )
@T
J
J
= 8:314
ln (0:0605) = 23:32
o
mol: K
mol:o K
=
From eq. (2.26),
G = zF E = (2) 96; 500
J
mol:V
G = 125:45 kJ=mol
(0:65 V )
3.8 Show that the activities are M1+2 = M2+2 in a galvanic cell, provided
that the potentials is E = E o .
Solution:
The reactions and the required activities are
M1 = M1+2 + 2e
M2+2 + 2e = M2
M1 + M2+2 = M1+2 + M2
=)
=)
=)
o
EM
1
o
EM
2
o + Eo
E o = EM
M2
1
RT
ln (Ke )
zF
dE
R ln (Ke )
=
=0
dT
zF+2
M
ln (Ke ) = ln 1+2 = 0
M2
+2
+2
ln M1 ln M2
= 0
+2
ln M1
= ln M2+2
+2
M1
= M2+2
E
= Eo
3.9 Show that S = R ln Ke in a galvanic cell at constant pressure.

Solution:
Using eqs. (2.32) and (2.35) at constant pressure yields
E
@E
@T
= Eo
RT
ln (Ke )
zF
R
ln (Ke )
zF
@E
S = zF
= R ln (Ke )
@T
+2
3.10 Derive an expression for ln Cu
= f(T ) for the given cells below.
Assume that the current ceases to ow and that the cells are not replenished
with fresh solutions. Plot the expressions for a temperature range of 0 C
T 60 C, and draw some suitable conclusions to explain the electrochemical
behavior based on the resultant trend.
=
e-
e-
Cu
Zn
Cu
Pb
a(Zn+2) = 1 mol/l
CuSO4 (aq)
a(H+) = 1 mol/l
Solution:
a) The reactions and the required copper activity are
3.1. PROBLEMS
17
Cu+2 + 2e = Cu
Zn = Zn+2 + 2e
Cu+2 + Zn = Cu + Zn+2
Ke
ln (Ke ) =
1
=
[Cu+2 ]
ln Cu+2 =
ln
o
ECu
= 0:337 V
o
EZn
= 0:763 V
E o = +1:10 V
=)
=)
=)
[Cu] Zn+2
[1] [1]
1
=
=
+2
+2
[Cu ] [Zn]
[Cu ] [1]
[Cu+2 ]
RT
Eo
ln (Ke ) = 0
zF
o
zF E
=
RT
o
zF E
RT
J
(1:10 V )
zF E o (2) 96; 500 mol:V
J
RT
8:314 mol:o K T
2:55x104
ln Cu+2 =
=y
T
(Solid curve)
b) Similarly, the Pb-Cu Cell gives
H2 = 2H + + 2e
Cu+2 + 2e = Cu
Cu+2 + H2 = Cu + 2H +
Ke
ln (Ke ) =
1
=
[Cu+2 ]
ln Cu+2 =
ln
ln Cu+2 =
=)
=)
=)
o
ECu
=0V
o
EH
= 0:337 V
E o = +0:337 V
[Cu] P b+2
[1] [1]
1
=
=
[Cu+2 ] [P b]
[Cu+2 ] [1]
[Cu+2 ]
RT
Eo
ln (Ke ) = 0
zF
zF E o
RT
zF E o
RT
J
(0:337 V )
zF E o (2) 96; 500 mol:V
J
RT
8:314 mol:o K T
7823: 1
=y
(Dash curve)
T
The required plots are y = ln Cu+2 = f (T )

0
-25
-50
-75
-100
275
287.5
300
312.5
325
337.5
The plot below shows the trend of the derived expressions at a larger range.
y -500
-1000
-1500
-2000
0
50
100
150
200
250
300
350
Besides the dierences in activity behavior, either trend means that the activity, solution conductivity and ionic diusivity increase with increasing temperature. In addition, the reduction of copper ions is faster at higher temperature.
EXTRA:
EX1. From Levine [2].
The entropy change (dS), the electrical energy change (dE), and the change
of charge (dq) for a - coupling are, respectively
3.1. PROBLEMS
dS
T dS
T dS
dE
dq
19
=
=
=
=
=
dS + dS
dU + P dV [( d )M + ( d )e ]
dU + P dV ( d )M z+
dU + dU + dq + dq
dq + dq = ze F (d )e + zF (d )M z+
where = Chemical potential

U = Internal energy
S = Entropy
q = Electron charge
= Electric potential
(3.1a)
(3.1b)
(3.1c)
(3.1d)
(3.1e)
P = Pressure
E = Total energy
V = Volume
T = Temperature
= Number of moles
F = Faradays constant
Figure 3.1 Galvanic cell and its phase components.

For an isolated - thermodynamic system, the following constraints can be
used to develop the equilibrium conditions and the Gibbs free energy change
(G) [2]
(d )M z+
dV
dV
dE
dq
=
=
=
=
=
(d )M
dV
0
0
0
(3.2a)
(3.2b)
(3.2c)
(3.2d)
(3.2e)

Hence, combining eq. (3.1e) and (3.2e) and the resultant expression with
eq. (3.2a) yields
(d )e
(d )e
= + (d )e
= z (d )M
since ze = 1
since z 1
(3.3a)
(3.3b)
Adding (d )e and (d )M z+ moles to the phase and the phase, respectively, the change in electron charges becomes [2]
dq
dq
= F (d )e
= +zF (d )M z+
(3.4a)
(3.4b)
Substituting eqs. (3.2a) and (3.3a) into (3.1e) and (3.1e) into (3.1d) yields
dU + dU + zF ( ) (d )M = 0
(3.5a)
dU = [dU + zF ( ) (d )M ]
(3.5b)
Substituting eqs. (3.2a) through (3.5b) into (3.2b) and (3.2c) and the resultant expressions into (3.2a), and subsequently, collecting terms yields the
entropy change of the - system
dS
1
1
P
P
dU
+
dV
(3.6)
T T
T
T
( )M
z ( )e ( )M z+
(zF ) ( )
+
+
+
(d )M
T
T
T
T
At equilibrium, dS = 0 and the following is deduced from eq. (3.6) [2]

1) For thermal equilibrium,
1
1
= 0 since T = T
T T
2) For mechanical equilibrium,

P
P
= 0 since P = P
T
T
(3.7)
(3.8)
3) For electrochemical equilibrium, T = T and
( )M [z ( )e ( )M z+ ] + zF ( ) = 0
(3.9a)
( )M [z ( )e ( )M z+ ] = zF ( )
(3.9b)
3.1. PROBLEMS
21
and
G
G
= ( )M [z ( )e ( )M z+ ]
= zF ( )
(3.9c)
(3.9d)
Thus, ( )M [z ( )e ( )M z+ ] is the anity for M = (M z+ ) + (ze )

and G is the Gibbs free energy change for the - subsystem.
In addition, the potential dierence ( ) between two phases in a halfcell at equilibrium cannot be measured. Instead, two electrodes are connected
as shown in Figure 3.1 to measure the electric potential dierence between the
electrodes. This can be done by connecting, say, - system to the previous -
system using a salt bridge or porous membrane. Thus,
the electrical
potential
dierence between the and electrodes is E = . Recall that the

salt bridge is a glass tube lled with an electrolyte that allows charge transfer
between the cell electrolytes without disturbing the equilibrium state.
Additionally, the anodic and cathodic reactions, the Gibbs free energy changes
and the electron balance expressions for the electrochemical system schematically shown in Figure 3.1 are given next.
Case 1: The electron balance in the reactions is (z1 e ) = (z2 e ) = ze
and = . Case 2: If (z1 e ) 6= (z2 e ) and = , then z = x (z1 e ) =
y (z2 e ) , where x and y are integer numbers. Hence, the reactions are
M1
z+
M2
+ z2 e
M1 + M2z+
z+
M1
+ z1 e
= M2
= M1z+ + M2
G = zF E (3.10)
G = zF E
(3.11)
G = zF E
(3.12)

where E = , E = , E = , e = ( )e and
G = G + G . In general, the standard and non-standard Gibbs free
energy change expressions are, respectively
Go = zF E o (standard)
G = zF E (non-standard)
(3.13)
(3.14)
EX2. From thermodynamics,

The rst law for a closed system is
dQ dW = dU
(1)
dW = dWP + dWe = P dV + zF dE
(2)
where dV is the dierential volume of the electrolyte and the total dierential
work due to pressure (P) and electrical potential (E) is

Combining eqs. (1) and (2) yields
dQ = dU + dW
dQ = dU + P dV + zF dE
(3)
(4)
From the second law of thermodynamics,

dQ = T dS
(5)
Then, eq. (4) becomes

T dS
T dS
= dU + P dV + zF dE
= dH + zF dE
(6)
(7)
where dH is the dierential enthalpy.

By denition, the dierential Gibbs free energy is
dG = dH T dS
(8)
dG = zF dE
(9)
Go = zF E o (standard)
G = zF E (non-standard)
(10)
(11)
Combining eqs. (7) and (8) gives
Integrating
EX3 3.3 Use the data given in Table 3.1 to determine the half-cells and the
redox standard potentials for the galvanic cell shown in Figure 3.1 if = Zn
and = Cu. Compare the results with the data given in Table 2.2.
Solution:
The redox reaction is
Zn + Cu2+ = Zn2+ + Cu
From eq. (3.16) and Table 3.1,
o
ECu
2+ =Cu
o
ECu
2+ =Cu
(o )Cu (o )Cu2+
zF
(1)(0) (1)(+64:98 kJ=mol)

=
= +0:337 V
(2)(96:50 kJ=mol V )
=
3.1. PROBLEMS
o
EZn=Zn
2+
o
EZn=Zn
2+
23
(o )Zn2+ (o )Zn
zF
(1)(147:21 kJ=mol) (1)(0)

=
= +0:763 V
(2)(96:50 kJ=mol V )
=
These results are exactly the same given in Table 2.2. Thus, the standard
cell potential is
o
o
E o = ECu
2+ =Cu + EZn=Zn2+ = +1:10 V
Chapter 4
NANO
ELECTROCHEMISTRY
4.1
PROBLEMS
4.1 In an electrochemical cell, the bulk electrolyte has uniform and constant
ion densities, but the electrical-double layer is an inhomogeneous uid. Why?
Answer: The ion densities in the electrical-double layer vary in space in
the vicinity of the electrode surface due to the charged particle forming the inhomogeneous structure.
4.2 The interface region between two bulk phases may contain a complex
distribution of electric charge. Name at least two causes for this phenomenon.
Answer: (a) The charge transfer between phases and (b) unequal adsorption
of positive and negative ions.
4.3 Explain how it is possible for a scanning tunneling microscope (STM)
to image atoms on the surface of a sample. Recall that one of the metals is the
sample and the other is the probe.
Answer: Move the tip up and down in the z-direction to obtain a constant
current across the contour of the substrate (sample) surface. Then, record the
position of the tip as it scans the substrate surface along the x and y directions.
The tip will trace out a contour of constant probability for nding an atom on
the surface. The constant tunneling current for this process can be approximated
by
It = Io exp (z)
25
26
CHAPTER 4. NANO ELECTROCHEMISTRY
where Io and is a constant. Nonetheless, when the tip is scanned over the
surface, the tip height (z) is determined by the local geometric and electronic
structure of the surface and thus it produces a surface map in real space.
4.4 For a nite depth energy well, the wave function (x) within the barrier
of width w, the tunneling current It through the barrier and the decay length
are related as shown below:
(x) = o exp (k2 x)
It
k2
/ jo j exp (k2 x)
2 p
2 p
=
2m (Uo E) =
2m
h
h
If the work function and the barrier width are = 4:32 eV and w = 0:151
nm in a ST M experiment, then determine It for a barrier of width 2w. Explain.
Solution:
k2
k2
k2
5:1268 nm 1 :eV
=
5:1268 nm 1 :eV
=
= 10:656 nm
1=2
1=2
(Uo E)
1=2
1=2 = 5:1268 nm 1 :eV
1=2
(4:32 eV )1=2
Then,
It;w
It;2w
It;w
It;2w
It;w
It;2w
jo j exp (k2 w)
jo j2 exp (2k2 w)
= exp (k2 w) = exp 10:656 nm 1 (0:20 nm)

= 5 or It;w = 5It;2w or It;2w = 0:2It;w
Denote the signicant change in It;2w as w ! 2w. Therefore, the ST M cell

is very sensitive to changes in the barrier size.
4.5 Determine (a) the Fermi energy and (b) the velocity of the electron for
a copper (Cu) substrate and a tungsten (W ) tip in a ultra high vacuum ST M
cell at temperature T .
Solution:
(a) The Fermi energy: For gold, Cu ! Cu2+ + 2e , with two free electron
per reaction. The electron density, eq. (4.11), is
4.1. PROBLEMS
e;Cu
e;Cu
e;Cu
27
= [ne NA =Aw ]Cu
8:94 103 Kg=m3

6:02 1023 atom
= (2)
63:55 Kg=Kmol
10 3 Kmol
= 1:6937 1029 1=m3
and
2=3
h2
3
e
2me 8
2=3
6:63 10 34 J:s
3
28
3
UF;Cu =
7:6514
10
1=m
2 9:11 10 31 Kg
8
2 2
J .s
UF;Cu = 1:0541 10 18
= 1:0541 10 18 J
Kg:m2
1:0541 10 18 J
UF;Cu =
= 6:59 eV
1:60 10 19 J=eV
The units: J 2 .s2 = Kg:m2 = J 2 = (N:m) = J. Similarly, for tungsten,

W ! W 4+ + 4e , with 4 free electrons, eqs. (4.7) and (4.6) give
UF;Cu
e;W
e;W
UF;W
UF;W
= [ne NA =Aw ]W
19:3 103
6:02 1023
= (4)
= 2:5278 1029 1=m 3
183:85
10 3
2
2=3
6:63 10 34 J:s
3 1:694 1029 1
=
= 2:3383 10
2 9:11 10 31 Kg
8
m3
2:3383 10 18 J
=
= 14:61 eV
1:60 10 19 J=eV
18
Obviously, UF;W > UF;Cu due to the dierences in the amount of free electrons and the electron densities between gold and tungsten metals.
(b) The velocity of electrons: Using eq. (4.12) yields
ve
ve;Cu
ve;Cu
r
s
2UF
me
s
2 (1:0541 10 18 J)
N:m
6
=
= 1:52 10
9:11 10 31 Kg
Kg
s
Kg:m m
= 1:52 106
= 1:52 106 m=s
s2 Kg
28

and for tungsten
s
(2) (2:3383 10 18 J)
9:11 10 31 Kg
ve;W
ve;W
= 2:27 106 m=s = 2; 270 Km=s
Therefore, an electron travels very fast in the vacuum gap. Lets determine
the atom density using eq. (4.9)
8:94 103 Kg=m3

NA
6:02 1023 atoms
=
Aw
63:55 Kg=Kmol
10 3 Kmol
na;Cu
na;Cu
= 8:4687 1028 atoms=m3
19:30 103 Kg=m3

NA
6:02 1023 atoms
=
=
Aw
183:85 Kg=Kmol
10 3 Kmol
na;W
na;W
= 6:3196 1028 atoms=m3
Verify the number of free electrons being used. Thus,
ne;Cu
ne;W
=
=
e
na
e
na
Cu
W
=
=
1:6937 1029 1=m3

=2
1:8302 1029 atoms=m3
2:5278 1029
=4
6:3196 1028
According to the above calculations, the amount of energy (oset) being given
to the electrons during tunneling is
S
T
= EF;Cu
EF;W
= 6:59 eV 14:61 eV = 8:02 eV
This is the energy that causes the electrons to acquire a specic velocity in
the tunneling gap (electrical conduction region).
4.6 For the reaction O + e R in an electrochemical cell, the cyclic
voltammetry method provided the formal potential (standard potential) o =
133 mV against a reference electrode. If the activity ratio is [O] = [R] = 0:2,
then calculate (a) the applied potential at 25o C and (b) the required energy
for the reaction to proceed to the right as written.
Solutions:
(a) Using the Nernst equation yields
4.1. PROBLEMS
29
RT
[R]
ln
zF
[O]
RT
[O]
(8:314 J=mol:K) (298 K)
= o +
ln
= 0:133 V +
ln (0:2)
zF
[R]
(1) (96; 500 J=mol:V )
= 0:09168 V = 91:68 mV
= o
(b) The reaction energy:

U
U
= qe = 1:602 10
= 0:092 eV
19
J=V (0:09168 V ) = 1:4687 10
20
4.7 Show that PT = exp (2k2 x), eq. (4.48), using the following equations
= A exp (i)
p
2m [U E]
P2
=
}2
}2
d
dx2
where P is the moment, x = w and } = h=2. Hint: extract the resultant

real and imaginary parts for solving this problem.
Solution:
Derivatives:
d
dx
d2
dx2
d2
dx2
= A exp (i)
dA
d
=
+ iA
exp (i)
dx
dx
"
2 #
d2 A
d2
dA d
d
=
+ iA 2 + 2i
A
exp (i)
dx2
dx
dx dx
dx
"
2 #
d2 A
d2
dA d
d
=
+ iA 2 + 2i
A
dx2
dx
dx dx
dx
A
(a)
(b)
Equate d2 =dx2 terms:

P2
2
}
AP 2
2
}
=
=
"
"
d2 A
d2
dA d
+ iA 2 + 2i
A
2
dx
dx
dx dx
d2 A
d2
dA d
+
iA
+ 2i
A
dx2
dx2
dx dx
d
dx
d
dx
2 #
2 #
A
(c)
30

Imaginary parts:of eq. (c) and multiply by A and eliminate i:
d2
dA d
+ 2i
dx2
dx dx
2
d
dA d
0 = A2 2 + 2A
dx
dx dx
0 = iA
(d)
Eq. (d) becomes
d2
A2 2 =dx = 0
dx
(e)
Integrating eq. (e) yields the wave amplitude A as

d
dx
A2
= C1
p
C1
C
A = p
=p
d=dx
d=dx
Real Parts of eq. (c):
AP 2
}2
P2
2
}
d2 A
A
dx2
1 d2 A
A dx2
and
1 d2 A
=
A dx2
If
then
d
dx
1 d2 A
< <
A dx2
1 d2 A
! 0
A dx2
d
dx
d
dx
d
dx
d
dx
d
dx
(f)
P2
}2
P2
}2
P
}Z
1
P dx
}
P2
}2
(g)
4.1. PROBLEMS
31
and
p
C
C
}C
p 1 =p
=p
d=dx
d=dx
P
D
p
P
A =
A =
Thus,
But,
= A exp (i)
Z
D
i
= p exp
P dx
}
P
p
2m (E U)
p
P = i 2m (U E)
p 2
and eq. (h) along with i2 =
1 = 1 and xed U = Uo
P
p
P
D
2Z
p
D
i
p exp
2m (U E)dx
}
P
" Z p
#
2m (U E)
D
p exp
dx
}
P
Z
D
2 p
p exp
2m [U (x) E] dx
h
P
Z
D
p exp k2 dx
P
Z x
D
D
p exp
k2 dx = p exp (k2 x)
P
P
0
= exp (k2 x)
where
k2 =
Then,
2 p
2m [U (x) E]
h
PT
p !2
P
=
D
PT
= exp (2k2 x)
(h)
32

where x is the barrier width and according to Figure 4.10, x = x2 x1 = w
4.8 Below is a sketch for the principle of the ST M technique. If the work
function () and the tunneling gap column (z) are 4 eV and 0:3 nm, respectively,
calculate the probability for an electron to tunnel from the probe tip to the metal
sample.
Solution:
5:1268 nm 1 :eV
k2
k2
= 10:254nm
1=2
(Uo E)
1=2
= 5:1268 nm 1 :eV
1=2
1=2
(4 eV )
and
PT
PT
= exp (2k2 z) = exp 2 10:254 nm 1 (0:3 nm) = 2:13 10

' 0:21%
4.9 Calculate the electron energy (E) if the tunneling probability (PT ) is
0:106 and the barrier height (Uo ) 4:5 eV . Assume a barrier width of 0:4 nm.
Solution:
PT
k2
= exp (2k2 w)
= ln (PT ) =2w = ln (0:106) = (2x0:4) = 2:81 nm
k2
E
E
= Uo (2:81=5:1268) = 4:5 eV (2:81=5:1268) eV

= 4:2 eV
Then,
5:1268 nm 1 :eV
1=2
2
1=2
(Uo E)
4.1. PROBLEMS
33
4.10 Assuming that there is no wave reection, eq. (4.20), at the boundary
2
x = 0, derive PR = jB=Aj and PT for E > Uo . Use the continuity of the wave
function and its derivative at the origin.
Solution:
From eq. (4.20),
1 (x) = A exp (ik1 x) + B exp (ik1 x)
d1 (x)
= ik1 A exp (ik1 x) ik1 B exp (ik1 x)
dx
2 (x)
2 (x)
d2 (x)
dx
d2 (x)
dx
= C exp (ik2 x) + D exp (ik2 x)

= C exp (ik2 x) since D = 0
= ik2 C exp (ik2 x) ik2 D exp (ik2 x)
= ik2 C exp (ik2 x)
since D = 0
At x = 0;
(0)1
A+B
d1 (0)
dx
AB
= (0)2
= C
d2 (0)
=
dx
ik2
=
C
ik1
or
B
A
B
1+
A
1+
=
=
C
A
k2 C
k1 A
Combining eqs. (1) and (2) gives

B
1+
A
k2 B
1
k1 A
B
A
B
k2 k2 B
1+
=
+
A
k1 k1 A
k2
= 1+
k1
1 + k2 =k1
=
1 k2 =k1
=
k2
k1
(1)
(2)
34

Then,
2
B
1 + k2 =k1 2
PR = =
A
1 k2 =k1
and
PT + PR
PT
PT
= 1
= 1 PR
1 + k2 =k1 2
= 1
1 k2 =k1
4.11 Assuming that the wave amplitude, eq. (4.23), C = 0 when x ! 1,

2
derive PR = jB=Aj and PT for E < Uo . Use the continuity of the wave function
and its derivative at the origin. Explain.
Solution:
From eq. (4.31) through ) (4.34),
A+B
ik1 (A + B)
C exp (k2 w) + D exp (k2 w)
k2 [C exp (k2 w) D exp (k2 w)]
=
=
=
=
C +D
k2 (C + D)
F exp (ik1 w)
ik1 F exp (ik1 w)
(4.31)
(4.32)
(4.33)
(4.34)
=
=
=
=
C +D
k2 (C + D)
F exp (ik1 w)
ik1 F exp (ik1 w)
(a)
(b)
(c)
(d)
Divide these eqs. by A so that

A+B
ik1 (A + B)
k2 [C exp (k2 w) D exp (k2 w)]
and
1 (x) = A exp (ik1 x) + B exp (ik1 x)
d1 (x)
= ik1 A exp (ik1 x) ik1 B exp (ik1 x)
dx
2 (x) = C exp (ik2 x) + D exp (ik2 x)
2 (x) = D exp (ik2 x) since C = 0
d2 (x)
= ik2 D exp (ik2 x)
dx
4.1. PROBLEMS
35
At x = 0;
(0)1
A+B
d1 (0)
dx
AB
= (0)2
= D
d2 (0)
=
dx
ik2
=
D
ik1
(1)
(2)
Divide eqs. (1) and (2) by A so that

B
A
B
1
A
1+
D
A
k2 D
=
k1 A
=
(3)
(4)
Eliminate D=A
B
k2
B
ik2 k2 B
1+
=
1+
=
A
k1
A
ik1 k1 A
B
k2
k2
1+
= 1
A
k1
k1
B
1 + k2 =k1
=
A
1 + k2 =k1
Then,
PR
PT + PR
PT
B
1 + k2 =k1 2
=1
= =
A
1 + k2 =k1
= 1
= 11=0
The particle will always be reected at x = 0. This means that the particle
can not penetrate into the classically forbidden barrier (region 2, Figure 4.10 )
and therefore, there is no particle transmission.
4.12 ForE < Uo , use eq. (4.23) to show that
F
A
PT
4ik1 k2 exp (ik1 w)

2
(k2 + ik1 ) exp (k2 w) (k2 ik1 ) exp (k2 w)

16k12 k22
h
i
2
2
(k1 + k2 ) e 2k2 w + (k1 + k2 ) e2k2 w + [12k12 k22 2 (k24 + k14 )]
36

Solution:
(w)2
d2 (w)
dx
k2 C exp (k2 w) k2 D exp (k2 w)
= (w)3
= F exp (k1 w)
d 3 (w)
=
dx
= ik1 F exp (ik1 w)
(3)
(4)
Divide eqs. (a) through (d) by A and group them to be algebraically manipulated.
A+B
= C +D
k2
k2
AB =
C
D
ik1
ik1
C exp (k2 w) + D exp (k2 w) = F exp (k1 w)
ik1
C exp (k2 w) D exp (k2 w) =
F exp (ik1 w)
k2
(5)
(6)
(7)
(8)
The tedious work: Divide by A

B
A
ik1 ik1 B
k2
k2 A
1+
C
exp (k2 w) +
A
C
exp (k2 w)
A
=
=
D
exp (k2 w) =
A
D
exp (k2 w) =
A
C
D
+
A
A
C
D
A
A
F
exp (k1 w)
A
ik1 F
exp (ik1 w)
k2 A
(9)
(10)
(11)
(12)
Add eqs. (11) and (12) to get
C
exp (k2 w) =
A
C
=
A
ik1
F
+1
exp (ik1 w)
k2
A
F k2 + ik1
exp (ik1 w) exp (k2 w)
A
2k2
(13)
Next, subtract eqs. (11) (12)

2
D
exp (k2 w) =
A
D
=
A
ik1 F
1
exp (ik1 w)
k2 A
F k2 ik1
exp (ik1 w) exp (k2 w)
A
2k2
(14)
4.1. PROBLEMS
37
Add eqs. (10) + (9) to get
C
A
C
A
=
=
ik1 ik1 B
B
+1+
k2
k2 A
A
k2 + ik1
k2 ik1 B
+
2k2
2k2
A
(15)
Subtract eqs. (9) (10) so that

2
D
A
D
A
ik1
ik1
1
+ 1+
k2
k2
k2 ik1
k2 + ik1 B
=
+
2k2
2k2
A
=
(16)
Now, equate eqs. (13) = (15)

F
A
k2 + ik1
2k2
k2 ik1
2k2
B
A
F
B
(k2 + ik1 ) exp (ik1 w) exp (k2 w) = (k2 + ik1 ) + (k2 ik1 )
(17)
A
A
exp (ik1 w) exp (k2 w) =
k2 + ik1
+
2k2
Equate eqs. (14) = (16)

F
A
k2 ik1
2k2
k2 ik1
+
2k2
k2 + ik1
2k2
B
A
F
B
(k2 ik1 ) exp (ik1 w) exp (k2 w) = (k2 ik1 ) + (k2 + ik1 )
(18)
A
A
exp (ik1 w) exp (k2 w) =
Rearrange eqs. (17) and (18) so that

F
B
(k2 + ik1 ) exp (ik1 w) exp (k2 w) (k2 + ik1 ) = (k2 ik1 )
A
A
F
B
(k2 + ik1 ) exp (ik1 w) exp (k2 w) (k2 ik1 ) = (k2 + ik1 )
A
A
(19)
(20)
Now divide eqs. (19)=(20) to eliminate B=A

F
A
F
A
(k2 + ik1 ) exp (ik1 w) exp (k2 w) (k2 + ik1 )

k2 ik1
=
k2 + ik1
(k2 + ik1 ) exp (ik1 w) exp (k2 w) (k2 ik1 )
Solve for F=A
(21)
38
2
F
F F
= =
A
A A
4k1 k2 eik1 w
=
2 k2 w
(k2 + ik1 ) e
(k2 ik1 )2 ek2 w
4k1 k2 e ik1 w
=
(Conjugate)
2 k2 w
2
(k2 ik1 ) e
(k2 + ik1 ) ek2 w
4k1 k2 e ik1 w
i
= h
2 k2 w
2
(k2 ik1 ) e
(k2 + ik1 ) ek2 w
PT
F
A
F
A
F F
A A
4k1 k2 eik1 w
i
xh
2 k2 w
(k2 + ik1 ) e
(k2 ik1 )2 ek2 w
Algebiaic work for the denominator:

2
[(k2 ik1 ) (k2 + ik1 )] e

[(k2 ik1 ) (k2 ik1 )]2 e
2
22
k2 w k2 w
k2 w k2 w
2k2 w
= 4ik1 k23 k24 k14 4ik13 k2 + 6k12 k22
(k2 + ik1 ) (k2 + ik1 ) ek2 w2 e
2
= k12 + k22 e
k2 w
= 4ik13 k2 k24 4ik1 k23 k14 + 6k12 k22
2
[(k2 + ik1 ) (k2 ik1 )]2 = k12 + k22 e2k2 w
X
Y
X
= 4ik1 k23 k24 k14 4ik13 k2 + 6k12 k22 + 4ik13 k2 k24 4ik1 k23 k14 + 6k12 k22
= 12k12 k22 2k24 2k14
= Y
Then, the full-blown tunneling probability equation becomes
PT
2
F
F F
= =
A
A A
PT
PT
16k12 k22
2
+ (k1 + k2 ) e2k2 w + 12k12 k22 2k24 2k14

16k12 k22
h
i
2
2
(k1 + k2 ) e 2k2 w + (k1 + k2 ) e2k2 w + [12k12 k22 2 (k24 + k14 )]
(k1 + k2 ) e
2k2 w
4.1. PROBLEMS
39
Test:
If k1 = 14; k2 = 7 and w = 1:2, then
16k12 k22
PT
PT
= 1:761 9 10
(k1 + k2
2
) e 2k2 w
(k1 + k2 ) e
h
2
(k1 + k2 ) e
2k2 w
+ (k1 + k2 ) e2k2 w + 12k12 k22 2 (k24 + k14 )
2k2 w
+ (k1 + k2 ) e2k2 w = 8:721 4 109
12k12 k22 2 k24 + k14 = 33; 614

2
+ (k1 + k2 ) e2k2 w
8:721 4 109
> > 12k12 k22 2 k24 + k14

> > 33; 614
According to these results, the full-blown equation can be simplied as

PT =
16k12 k22
(k1 + k2
If e2k2 w >> e
tained as
2k2 w
2
) e 2k2 w
+ (k1 + k2 ) e2k2 w
= 1:761 9 10
, then a further simplication of the PT equations on-
PT =
16k12 k22
= 1:761 9 10
(k1 + k2 ) e2k2 w
Thus,
2
F
F F
16k12 k22
PT = = =
2 exp (k2 w)
A
A A
(k22 k12 )
40
Chapter 5
KINETICS OF
ACTIVATION
POLARIZATION
5.1
PROBLEMS/QUESTIONS
5.1 What are the three conditions for galvanic corrosion to occur?
Answer: Dissimilar metals, corrosive media, and electrical contact.
5.2 If the state of equilibrium of an electrochemical cell is disturbed by an
applied current density ix , then ia = ic = icorr no longer holds. Let ix be a
cathodic current density and the slope of the corresponding polarization curve
be dE=d log (ix ), which increases approaching the Tafel constant c . Determine
a) the value of ix when ic = 10 3 A=cm2 and ia = 10 9 A=cm2 and b) the
value of c when icorr = 10 5 A=cm2 and = 0:20 V .
Solution:
a) ix = ic ia ic = 10 3 A=cm2
b) The cathodic overpotential is given by
c
c
c
= c log
ix
icorr
c
0:20
=
=
log (ix =icorr )
log (10 3 =105 )
= 0:10 V
5.3 According to the Stockholm Convention Cell F e F e+2 jH + ; H2 j P t,

the corrosion potential of iron (F e) is 0:70 VSCE at pH = 4:4 and 25o C in a
41
42
CHAPTER 5. KINETICS OF ACTIVATION POLARIZATION
deaerated (no oxygen is involved) acid solution. Calculate a) the corrosion rate
in mm=y when
io;H = 10 6 A=cm2
io;F e = 10 8 A=cm2
c = 0:10 VSHE
EF e = 0:50 VSHE
b) the Tafel anodic slope a and c) draw the kinetic diagram E vs: log i.
Solutions:
F e ! F e+2 + 2e
The possible reactions are 2H + + 2e ! H2
F e + 2H + ! F e+2 + H2
a) From Table 2.7 and Nernst equation,
Ecorr
EH
EH
EH
EH
)
)
)
EF e = 0:50 V
EH =?
E = EF e + EH
= 0:70 + 0:241 0:46 VSHE
RT
[H2 ]
4:606RT
o
o
= EH
ln
= EH
+
log H +
2
+
zF
zF
[H ]
4:606RT
o
= EH
(pH)
zF
(4:606) (8:314 J=mol:K) (298K)
= 0
(pH)
(2) (96; 500 J=mol:V )
= (0:0591) (4:4) = 0:26 V
Thus, the cell potential and the overpotentials becomes

E
a
c
= EF e + EH = 0:50 V 0:26 V = 0:76 V

= EF e Ecorr = 0:46 V + 0:50 V = 0:04 V
= EH Ecorr = 0:26 V + 0:46 V = 0:20 V
Using eq. (5.35) yields the corrosion current density
io;H
c = c log
icorr
icorr
icorr
icorr
icorr
= io;H 10c = c
= 10 6 A=cm2 100:2=0:10
= 10 6 A=cm2 102
= 10
A=cm2
Using eq. (5.48) gives the iron corrosion rate

4
10 A=cm2 (55:85 g=mol)

icorr Aw
CR =
=
zF
(2) (96; 500 A:s=mol) (7:86 g=cm3 )
9
CR = 3:68x10 cm=s = 1:16 mm=y
43
b) From eq. (5.32),
icorr
io;F e
icorr
= a = log
io;F e
= (0:04 V ) = log 10 4 A=cm2 =10 8 A=cm2

= 0:01 V
= a log
a
a
a
c) The required diagram is
-0.20
-0.30
E (V)
-0.40
(io,E)H
c
(io,E)Fe
(i,E)coorr
-0.50
-0.60
10-10
10-8
10-6
10-4
10-2
i (A/cm2)
5.4 Let the following anodic and cathodic reactions be, respectively
M = M +2 + 2e
EM = 0:941 VSCE
io;M = 10 2 A=cm2
+
2H + 2e = H2
EH = 0:200 VSHE
io;H = 0:10 A=cm2
where icorr = 102 A=cm2 and Ecorr = 0:741 VSCE . a) Construct the corresponding kinetic diagram and b) determine both a and c from the diagram
and from the denition of overpotential equations.
Solutions:
From Table 2.7,
EM
Ecorr
= 0:941 + 0:241 = 0:70 V

= 0:741 + 0:241 = 0:50 V
Thus, the required diagram is
44
0
(io,E)H
-0.20
E (V)
-0.40
c
(i,E)coorr
-0.60
-0.70
a
10-4
(io,E)M
10-2
a
100
102
104
i (A/cm2)
From the diagram,
a
a
c
c
Ecorr EM
(0:50 V ) (0:70 V )
=
4 decades
4
= 0:05 V
Ecorr EH
(0:20 V ) (0:50 V )
=
=
3 decades
3
= 0:10 V
=
From the overpotential eq. (5.32),
a
c
a
c
= Ecorr EM = 0:20 V
= Ecorr EH = 0:30 V
icorr
= a log
io;M
icorr
= c log
io;H
Then,
and
icorr
io;M
= a = log
a
a
= (0:20 V ) = log
= 0:05 V
10 A=cm2 =10 2 A=cm2
icorr
io;H
= c = log
c
c
= (0:30 V ) = log
= 0:10 V
45
10 A=cm2 = 0:10A=cm2
5.5 A steel tank is hot dipped in a deaerated acid solution of 5x10 4

mol=cm3 molality zinc chloride (ZnCl2 ) so that a 0:15-mm zinc coating is deposited on the steel surface. This process produces a galvanized steel tank. Calculate the time it takes for the zinc coating to corrode completely at a pH = 4:
Data: EZn = 0:8 V; io;Zn = 10 A=cm2 , io;H = 10 3 A=cm2 , a = 0:08 V ,
c = 0:12 V; T = 25o C.
Solution:
The possible half-cell reactions and their respective standard potential are
Zn ! Zn+2 + 2e
2H + + 2e ! H2
Zn + 2H + ! Zn+2 + H2
=)
=)
=)
EZn = 0:80 V
EH =?
E = EZn + EH
The activity of hydrogen ions and the hydrogen potential are, respectivily
pH = log H +
+
H
= 10 pH = 10
mol/l
EH = 0:059pH = 0:059 (4) = 0:24 V

Using the denition of overpotential along with the condition a = c yields
icorr
a = E EZn = a log
io;Zn
icorr
c = E EH c log
io;H
icorr
icorr
EZn + a log
= EH c log
io;Zn
io;H
which leads to
1
[EZn + EH + a log (io;Zn ) + c log (io;H )]
a + c
1
log (icorr ) = 0:08+0:12
(0:80) + 0:236 + 0:08 log (10) + 0:12 log 10 3
log (icorr ) =
46
log (icorr ) = 1:40

icorr = 101:40 A=cm2 = 25:12 A=cm2
From eq. (5.48),
CR
25:12x10 6 A=cm2 (65:37 g=mol)

icorr Aw
=
zF
(2) (96; 500 A:s=mol) (7:14 g=cm3 )
= 1:192x10 9 cm=s = 0:38 mm=y

x
CR =
t
x
0:15 mm
t =
=
= 0:40 years = 146 days
CR
0:38 mm=y
CR
5.6 Calculate the activity and the corrosion rate of iron (F e) immersed in
an aerated aqueous solution of pH = 9: The dissociation constant for ferrous
hydroxide, F e (OH)2 , is 1:64x10 14 . Given data:
io;F e = 10 2 A=cm2
Aw;F e = 55:85 g=mol
Ecorr = 0:30 V
F e = 7:86 g=cm3
a = 0:10 V
Solution:
The possible half-cell reactions and standard potentials are
F e = F e+2 + 2e
1
2 O2 + H2 O + 4e = 2OH
1
F e + 2 O2 + H2 O = F e+2 + 2OH
F e+2 + 2OH = F e (OH)2
=)
=)
=)
EFo e = 0:440 V
o
EH
= 0:401 V
2O
o
E o = EFo e + EH
= 0:039 V
2O
EFo e(OH) = 0:039 V
2
Thus, the oxidation of iron may be represented by the following reaction

F e (OH)2 = F e+2 + 2OH
From Table 2.6, [OH ] = 10pH
ferrous iron becomes
KF e(OH)2
+2
Fe
14
= 10
+2
2
Fe
[OH ]
[F e (OH)2 ]
[F e (OH)2 ] KF e(OH)2
=
2
[OH ]
F e+2 = 1:64x10 4 mol=l
mol=l so that the activity of
[1] 1:64x10
2
[10 5 ]
14
47
Using eq. (5.32) gives the corrosion density
= Ecorr EFo e(OH)2 = 0:30 V 0:039 V

= 0:339 V
icorr
a = a log
io;F e
icorr
0:339 V
log
=
= 3:39
io;F e
0:10 V
icorr = io;F e 10 3:39 = 10 8 A=cm2 10 3:39

a
a
icorr
= 4:07x10
12
A=cm2
From eq. (5.48), the corrosion rate is
CR
CR
4:07x10 12 A=cm2 (55:85 g=mol)

icorr Aw
=
=
zF
(2) (96; 500 A:s=mol) (7:86 g=cm3 )
= 1:50x10 16 cm=s = 4:73x10 8 mm=y = 0:0473 m=y
5.7 Plot the anodic data given below and determine the polarization resistance (Rp ) and the anodic Tafel slope ( a ) for a metal M . Use c = 0:07 V
and icorr = 0:019 A=cm2 .
M = M +2 + 2e
2H + + 2e = H2
i A=cm2
0:08
0:10
0:15
0:18
0:20
E (VSHE )
0:32
0:30
0:25
0:22
0:20
Solution:
Linear least squares on the given data gives E = 0:4 V + 1:0V:cm2 =A i
48
-0.1
-0.15
-0.2
E (V)
-0.25
-0.3
Slope = 1.0 V.cm2/A
-0.35
-0.4
0.05
0.1
0.15
0.2
0.25
i (A/cm2)
The polarization resistance and the anodic Tafel slope are
Rp
Rp
= slope = 1:0 ohm:cm2
=
icorr
ac
=
= 0:019 V
2:303 ( a + c )
Thus,
a = 0:12 V
5.8 Why does a pearlitic steel corrode rapidly in an acidic solution?
Answer: Because of the galvanic eects between the body-centered cubic
ferrite (BCC -F e) and tetragonal cementite (F e3 C) crystal structures. In
fact, this type of corrosion is benecial for revealing the steel microstructure.
5.9 Why will the tip and the head of an iron nail behave as anodes relative
to the shank? See Figure 1.10a.
Answer: Because the tip and the head of the nail are highly strained areas
containing large amounts crystal defects, such as dislocations, voids, and possibly
microcracks. These areas contain large amounts of stored strain energy.
5.10 It is known that the standard electrode potential (E o ) for pure crystalline zinc is 0:763 V . Will this value change by cold working and impurities?
Explain.
Answer: Cold working causes microstructural changes and crystal defects,
which in turn change the mechanical properties and increases corrosion. On
49
the other hand, impurities also change properties due to segregation along grain
boundaries. Therefore, E o must change and it is dierent at grain boundaries
(atomic mismatch) due to the straining eects induced during cold working than
the potential within grains. Consequently, the grain boundaries and possibly
secondary phases become anodic sites to grains.
5.11 An electrolyte contains a very low activity 8x10 9 mol=l of silver

cations (Ag+ ) and an unknown concentration of copper cations. If the cell
potential dierence between the copper anode and the silver cathode is 0:04
V , determine a) which cation
will be reduced (electroplated) on the cathode
and b) the concentration of Cu+2 in g=l at 40o C. Neglect the eects of other
ions that might react with silver.
Solution:
The possible half-cell reactions and standard potentials are
2Ag + + 2e = 2Ag
Cu = Cu+2 + 2e
2Ag + + Cu = 2Ag + Cu+2
=)
=)
=)
o
EAg
= 0:799 V
o
ECu
= 0:337 V
o + E o = 0:462 V
o
E = EAg
Cu
The free energy change is
Go
Go
= zF E o = (2) (96; 500 J=mol:V ) (0:462 V )

= 89; 166 J=mol
Therefore, silver (Ag) will be reduced since Go < 0: Using the Nernst
equation yields the copper ion concentration
RT
ln (K)
zF
J
(2) 96; 500 mol:V
(0:462 V + 0:04 V )
zF (E o E)
=
J
RT
8:314 mol:o K (313o K)
= Eo
ln (K) =
ln (K) = 37:23
K = 1:48x1016
50

Then,
K
Cu+2
Cu+2
Cu+2
[Ag]
Cu+2
[Ag + ] [Cu]
2
K [Ag + ] [Cu]
2
[Ag]
1:48x1016 8x10
mol=l
2
[1 mol=l]
[1 mol=l]
= 0:95 mol=l
= Cu+2 Aw;Cu = (0:95 mol=l) (63:55 g=mol)

' 60 g=l
CCu+2
CCu+2
5.12 Suppose that a cold worked copper electrode has 8; 000 J=mol stored
energy and dissolves in an aqueous electrolyte. Calculate the overpotential.
Solution:
Cu = Cu+2 + 2e
=)
E o = 0:337 V
From eq. (2.24),
G = zF E
G
8; 000 J=mol
E =
=
J
zF
(2) 96; 500 mol:V
E
a
a
o
= 0:042 V > ECu
= E E o = 0:042 V 0:337V
' 0:38 V
5.13 What is the signicant dierences between the overpotential () and

the Ohmic potential (E)?
Answer: Mathematically, both potentials have dierent physical trend. Thus,
the overpotential is nonlinear with respect to the current or current density since
= log (I=Icorr ) : If 6= 0, the anode electrode is polarized and is a measure
of the energy required for polarization since G = zF . On the other hand,
Ohms law, E = IR is linear and it may include other terms, such as overpotential and solution (electrolyte) potential, s = IRs . Equation (3.25) describes
the Ohms potential in details.
E = Ecorr a c s = IR
51
5.14 If a sheet of zinc (Zn) is placed in hydrochloric acid (HCl), Zn goes

into solution. Why?
Answer: Localized anodic and cathodic areas must exist on the sheet surface
so that the following reactions occur
Zn = Zn+2 + 2e
2H + + 2e = H2
Zn + 2H + = Zn+2 + H2
=)
=)
=)
o
EZn
= 0:763 V
o
EH
=0
o + E o = 0:763 V
E o = EZn
H
The standard free energy change must be Go < 0 in order for the above
reactions to occur. Using eq. (2.24) yields
Go
Go
= zF E o = (2) (96; 500 J=mol:V ) (0:763 V )

= 147:26 kJ=mol
5.15 Calculate the equilibrium constant at 25o C for the electrochemical cell
shown in Figure 2.4.
Solution:
Combining eqs. (2.24) and (2.31b) along with E o = 1:10 V gives

zF E o
= RT ln (K)
zF E o
ln (K) =
RT
(2) (96; 500 J=mol:V ) (1:10V )
ln (K) =
= 85:69
(8:314 J=mol:o K) (298o K)
K
= 1:64x1037
5.16 Show that G = zF a log (ia =icorr ) where the local potential E can
be dened by the Nernst equation.
Solution:
Using eqs. (3.31) and (2.24) yields
RT
ln (K)
zF
o
zF (E E)
RT
= Eo
ln (K) =
52

But,
G = RT ln (K)
zF (E o E)
G = RT:
RT
G = zF (E E o ) = zF a
But,
a
= a log
ia
icorr
ia
G = zF a log
icorr
5.17 If an electrochemical cell operates at 10 amps, 25o C; and 101 kP a for

30 minutes, calculate a) the number of moles and b) the weight of copper would
be produced.
Solution:
The reduction reaction is Cu+2 + 2e = Cu. From eq. (5.12b),
N=
It
(10 A) (1; 800 s)
=
= 0:093moles
zF
(2) (96; 500 A:s=mol)
From eq. (5.12c),

W
W
ItAw
= N Aw = (0:093mol) (63:55 g=mol)
zF
= 5:93 grams
=
5.18 (a) Derive the Arrhenius equation from the general denition of the
activation energy of any rate reaction process, (b) determine the Arrhenius
constants B and Ae using the derived equation and the following data for the
dissociation constants: Ksp@300 = 1011 , Ksp@350 = 3Ksp@300 between 300o K
and 350o K. It is assumed that the activity coecients approach 1 in diluted
electrolyte solution and that Ksp follows an Arrhenius type trend. Recall that
Ksp can be expressed in terms of concentrations. (c) Plot the given data below
and draw the trend line in the close interval [200,400] for the temperature axis
and [0,4]x1011 for the reaction constant Ksp axis.
T (o K)
200
250
280
300
330
350
360
Dissociation Constant Ksp

0:02x1011
0:22x1011
0:50x1011
1:00x1011
1:95x1011
3:00x1011
3:65x1011
53
Solution:
(a) From eq. (5.20),
G
dT
T2
T 2 dT
Ksp
B
Ksp
ln
d (ln Ksp )
dT
Rd (ln Ksp )
G
Z
R
d (ln Ksp )
G
R
(ln Ksp ln B)
G
G
RT
G
B exp
RT
= RT 2
(b) Using the derived expression for two dierent rates yields
Ksp@300
Ksp@350
Ksp@300
Ksp@350
G
= B exp
RT300
G
= B exp
RT350
G
1
1
= exp
RT
T350 T300
Thus,
R ln (Ksp@300 =Ksp@350 )
1=T350 1=T300
(8:314) ln (1=3)
= 19; 181 J/mol
1=350 1=300
and
B
B
B
Check:
G
= Ksp@300 exp
RT300
11
19181 J/mol
= 10 exp
[8:314 J/(mol.K)] (300 K)
= 2:1869 1014
54
Ksp@300
Ksp@300
Ksp@350
Ksp@350
Ksp@300
G
= B exp
RT300
19181
= 2:1869 1014 exp
= 1 1011
(8:314) (300)
19181
= 2:1869 103 exp
= 3 1011
(8:314) (350)
3 1011
=
=3
1 1011
19181
(c) Plot Ksp = 2:1869 103 exp 8:314T

= 2186:9 exp 2307:1
T
Ksp
0
200
250
300
350
400
T (Degree Kelvin)
5.19 Plot the given conductivity data vs: the aqueous Cu+2 SO4 concentration at 25o C and 1 atm. (The data was taken from Ref. [5]). Conduct a
nonlinear regression analysis on these data and explain the resultant curve.
C
mol=cm3
x10 6
0
25:00
50:00
75:00
100:00
102:50
200:00
202:50
55
Kc
ohm 1 cm 1
x10 3
0
3:00
5:10
7:40
8:50
10:00
15:00
16:00
Linear least squares on the given data yields
Kc = 1:1922x10 3 ohm 1 cm 1 + 73:46 mol=cm3 C
Kc (x10-3 ohm-1.cm-1)
25
20
15
10
5
50
100
150
200
250
C (x10-6 mol/cm3)
In fact, Cu+2 SO4 solution is a weak electrolyte due to the interactions
among Cu+2 and SO4 ions. However, Kc increases because the number of
charge carriers per unit volume increase with the electrolyte concentration.
5.20 An electrochemical cell operates at a small overpotential and the corroding metal is exposed to a H + ion-containing electrolyte. Use the given data
= 0:005 V
i = 3:895 10 8 A=cm2
io = 10 7 A=cm2
CR = 5:8277x10 4 mm=y
T = 25o C
= 7:14 g=cm3
D = 10 5 cm2 =s
56
in order to determine a) the corroding metal by calculating the atomic weight

Aw and determining its anodic reaction. Assume that there is a linear relationship between the current density and the overpotential. b) The activity of the
corroding metal if aH + = 1 mol=l, c) the free energy change G. Will the
reaction you have chosen occur?, d) the ionic velocity of the corroding metal.
As a crude approximation, neglect the ionic velocity of other ions in solution.
e) The ionic mobility B and f) electrolyte conductivity by neglecting other ions
present in the electrolyte.
Solution:
a) From eq. (5.16c),
i = io
z
z
zF
RT
(3.16c)
3:895x10 8 A=cm2 (8:314 J=mol:o K) (298o K)

iRT
=
=
io F
(10 7 A=cm2 ) (96; 500 J=mol:V ) (0:005 V )
= 2

CR
Aw
Aw
iAw
= 5:8277x10 4 mm=y = 1:848x10 12 cm=s
zF
(2) (96; 500 A:s=mol) 7:139 g=cm3 1:848x10

zF CR
=
=
i
(3:895 10 8 A=cm2 )
= 65:38 g=mol
=
12
(3.48)
cm=s
Therefore, the corroding metal is zinc and its anodic reaction is

Zn = Zn+2 + 2e
b) According to the results obtained in part a), the reactions and potentials
taking place at 25o C are
Zn = Zn+2 + 2e
2H + + 2e = H2
Zn + 2H + = Zn+2 + H2
=)
=)
=)
o
EZn
= 0:763 V
o
EH
=0
o + E o = 0:763 V
E o = EZn
H
Using the Nernst equation, eq. (2.32), along with = E E o = 0:005 V

gives the activity of Zn+2 ions
57
RT
ln (K)
(2.32)
zF
Zn+2 [H2 ]
RT
=
ln
2
zF
[Zn] [H + ]
2
+2
[Zn] [H + ]
zF
Zn
=
exp
[H2 ]
RT
2
+2
[1 mol=l] [1 mol=l]
(2) (96; 500 J=mol:V ) (0:005 V )
Zn
=
exp
[1 mol=l]
(8:314 J=mol:o K) (298o K)
+2
Zn
= 0:677 mol=l = 6:77x10 4 mol=cm3
E
= Eo
c) From eq. (2.24),

G
E
G
G
=
=
=
=
(2.24)
zF E
+ E o = 0:005 V + 0:763V = 0:768 V
(2) (96; 500 J=mol:V ) (0:768 V )
148:224 kJ=mol
Therefore, the above reactions occur because G < 0.

d) Using eq. (5.95) yields the zinc ionic velocity
i = zF vj Cj = zF vZn+2 CZn+2 = zF vZn+2 Zn+2

i
vZn+2 = vj =
zF CZn+2
3:895x10 8 A=cm2
vZn+2 =
(2) (96; 500 A:s=mol) (6:77x10 4 mol=cm3 )
vZn+2
= 2:98x10
10
(3.95)
cm=s
e) Using eq. (5.97) yields the zinc ionic mobility

DZn+2
BZn+2
BZn+2
= kT BZn+2
DZn+2
10 5 cm2 =s
=
=
23
kT
(1:38x10
J=mol:o K) (298o K)
cm2 :mol
cm2
= 2:43x1015
= 2:43x1015
J:s
V:s
(3.97)
f) Using eq. (5.93) gives the zinc ionic conductivity

Kc;Zn+2
Kc;Zn+2
Kc;Zn+2
= zF BZn+2 CZn+2
15 cm
= (2) (96; 500 A:s=mol) 2:43x10
6:77x10
V:s
= 3:18x1017 ohm 1 :cm
mol=cm3
58
5.21 If an electrochemical copper reduction process is carried out at 5

amperes. for 20 minutes, determine a) the electric charge (amount
of coulombs
of electricity), b) the number of electrons if there are 1= 1:6022x10 19 =

6:24x1018 electron=C, c) the number of moles, d) Faradays weight reduced
on a cathode, and the reduction rate (production rate in Chapter 7). Data:
Aw = 63:55 g=mol and T = 35o C:
Solution:
a) The reactions and potentials taking place at 35o C are
Cu = Cu+2 + 2e
2H + + 2e = H2
Cu + 2H + = Cu+2 + H2
=)
=)
=)
o
ECu
= 0:337 V
o
EH
=0
o + E o = 0:763 V
E o = ECu
H
From eq. (5.12a),

Q = It = (5 A) (1; 200 s) = 6; 000 C
b)
Ne
Ne
= (6; 000 C) 6:24x1018 electron=C

' 4x1022 electrons
c) From eq. (5.12b),

N=
Q
6; 000 C
=
= 0:0311 moles
zF
(2) (96; 500 C=mol)
d) From eq. (5.12c),

W
W
= N Aw = (0:0311 moles) (63:55 g=mol)

= 1:98 grams
e)
PR =
W
1:98 g
=
= 1:65x10
t
1; 200 s
g=s = 5:94 g=h
5.22 Calculate the overpotential that causes hydrogen evolution on a at

platinum (P t) electrode surface immersed in an acid solution, when the applied
cathodic and exchange current densities are 6; 000 A=cm2 and 100 A=cm2 ,
respectively. Assume a symmetry factor of 0:50 at room temperature (25o C).
Solution:
2H + + 2e = H2
=)
o
EH
=0
59
From eq. (5.20b),

RT
ic
ln
zF
io
8:314 mol:J o K (298o K)

6; 000
=
ln
(1) (96; 500 J=mol:V ) (0:5)
100
= 0:21V
=
c
c
c
5.23 Consider a discharge (chemical desorption) mechanism as the rate

determining for N i+2 + 2e = N i at 25o C in a nickel battery. Calculate the
cathodic Tafel slope per decade if the symmetry factor is 0:50, the exchange
current density is constant, and the cathodic overpotential is c < 0.
Solution:
From eq. (5.20b),
c
c
dc
d log (ic )

RT
ic
=
ln
zF
io

2:303RT
ic
=
log
zF
io
2:303RT
=
zF
Thus,
c
c
(2:303) 8:314 mol:J o K (298o K)

d c
=
=
d log (ic )
(2) (96; 500 J=mol:V ) (0:5)
= 0:06 V =decade
5.24 Plot the normalized current prole as a function of both symmetry

factor () and overpotential; that is, i=io = f (; ) when the oxidation state
is dened is z = 2 and = 0:35; 0:50 and 0:75 at room temperature (25o C).
Explain the polarization behavior very succinctly.
Solution:
i
io
i
io
zF
(1 ) zF
= exp
exp
RT
RT
= exp [77:90] exp [ (1 ) 77:90]
60
15
i/io
= 0.75
Cathodic
Region
10
0.50
0.35
Tafel Region
-5
Anodic
Region
-10
-15
-0.06
-0.04
-0.02
0.02
0.04
0.06
0.08
(V)
The normalized current density (i=io ) shows the expected linearized Tafel region at small values of the anodic and cathodic overpotentials (). However, the
departure from this linearity is obvious at large and the shape of the curves
change signicantly. Therefore, variations of the current density (i) strongly
depend on the overpotential () and the shape of the curves depend on the symmetry factor (). The slopes of the curves at large are characteristics of
since it arises due to changes in the electric double layer structure.
5.25 Calculate the mass and number of moles a) of a battery zinc (Zn)
casing and b) of the manganese dioxide (MnO2 ) in the electrolyte if the battery
has a stored energy of 36 kJ=V and a power of 3 W atts. c) Find the time it
takes to consume the stored energy if the battery operates at a current of 2 A
and the potential (voltage). The thickness of the cell is x = 1 mm and other
dimensions are indicated below. The discharging reaction is
M nO2 + H + + e ! MnOOH
0.3 mm
61
2 mm
60 mm
MnO2
Carbon
( )
15 mm
Solution:
Q = 36 kJ=V = 36; 000 A:s = 36; 000 Coulombs
2
As = 2Lr = (2) (6 cm) (1:5 cm)
= 56:55 cm
2
3
V = xAs = (0:1 cm) 5:6549 cm = 5:65 cm
a) The mass and moles of Zn
MZn
XZn
= V = 5:65 cm3 7:14 g=cm3 = 40:34 g

MZn
40:34 g
=
=
= 0:62 mol
Aw;Zn
65:37 g=mol
b) The mass and moles of M nO2 are

XMnO2
XMnO2
MMnO2
MMnO2
Q
36; 000 A:s
=
zF
(1) (96; 500 A:s=mol)
= 0:37 mol
= XMnO2 Aw;MnO2 = (0:37 mol) (86:94 g=mol)
= 32:17 g
=
c) The time for discharging the stored energy is

Q
36; 000 A:s
=
= 5 hours
I
2A
= P=I = (3 V:A) = (2 A) = 1:5 V
t =
E
5.26 A plate of pure nickel (N i) oxidizes in an electrochemical cell containing an acid solution at 25o C. The total surface area of the nickel plate is 100
cm2 . If 2x1016 electrons per second (e=s) are relieved on the plate surface, then
calculate a) the corrosion rate in mm=y and b) the mass of nickel being lost in
a year..
Solution:
62

N i = N i+2 + 2e
r = 2x1016 e=s
qe = 1:6022x10 19 A:s=e
z=2
= 8:90 g=cm3
Aw = 58:71 g=mol
As = 100 cm2
a) From eq. (5.50),

I
= rqe = 2x1016 e=s 1:6022x10
19
= 3:20x10 3 A
I
3:20x10 3 A
i =
=
= 32 A=cm2
As
100cm2
A:s=e
Then,
32x10 6 A=cm2 (58:71g=mol)

iAw
=
zF
(z) (96; 500 A:s=mol) (8:90g=cm3 )
CR
CR
= 1:10x
cm=s = 0:35 mm=y
b)
I
zF m
=
As
As tAw
zF m
zF CR
=
As tAw
Aw
m = CR As t = 8:90 g=cm3 (0:035 cm=s) 100 cm2 (1 y)

m = 31:15 grams
i =
5.27 Use the data listed in Table 3.3 to perform a least squares analysis
and subsequently, determine the polarization proportionality constant . Let
the atomic weight and the density of the steel be Aw;steel = Aw;F e = 55:85
g=mol and = 7:85 g=cm3 , respectively.
Solution:
Curve tting:
2
Rp = 3:8502 10
ohm:cm3
1
ohm:cm + 30:147
y
CR
2
63
140
Rp (ohm.cm2)
120
100
80
60
S = 30.147 ohm.cm3/y
40
20
0
1/CR (y/cm)
Combining eqs. (3.25a) and (3.48) yields

Rp
S
Aw
1
=
zF CR
Aw
=
zF
(2) 3:06x10
zF S
=
=
Aw
= 0:03 V
A:y=mol 7:85 g=cm3 30:147 ohm:cm3 =y

55:85 g=mol
5.28 Equal amounts of CuSO4 and NiSO4 are dissolved with water to
make up an electrolyte. Hypothetically, the ion velocities and concentrations
are
vCu+2 = 0:22 cm=s
vSO2 = 0:1 cm=s
4
CCu+2 = 10 5 mol=cm3
CNi+2 = 10 5 mol=cm3
CSO2 = 10 5 mol=cm3
2
If+2the
current density is 1 A=cm , calculate the velocity of the nickel ions
Ni
.
Solution:
64

From eq. (5.86),
i =
zj+ F vj+ Cj+ +
X
z F v C
j
j
j
h
i
i = F (zvC)Cu+2 + (zvC)Ni+2 + (jzj vC)SO2
4
h
i
i = 2F (vC)Cu+2 + (vC)Ni+2 + (vC)SO2
4
If zCu+2 = zNi+2
mol=cm3 , then
= zSO2 = 2 and C = CCu+2 = CNi+2 = CSO2 = 10

4
4
h
i
i = 2F C vCu+2 + vNi+2 + vSO2
4
Solving for vNi+2 yields

vNi+2
vNi+2
vNi+2
i
vCu+2 vSO2
4
2CF
1
=
mol
(2) 10 5 cm
96; 500
3
= 0:20 cm=s
=
A:s
mol
0:22
cm
cm
0:1
s
s
5.29 An electrochemical cell operates at 10 A, Rx = 0:25 ohm; and ! = 50

Hz. Determine a) the electrolyte resistance (Rs ), b) the potential Ex when the
external resistance and the capacitance are Rx = 0:25 ohm and Cx = 20 A:s=V
at 300 C and c) the electrolyte conductivity Kc : The distance between electrodes
is L = 15 cm and the eective electrode surface is A = 8; 000 cm2 :
Solution:
a) From eq. (5.103),
Z (w)x
Rx2 +
1
!Cx
1
(0:25 ohm) +
(50 s 1 ) (20A:s=V )
Z (w)x
Z (w)x
= 0:25 ohm
Therefore, Rs = Z (w)x = 0:25 ohm:

b) From eq. (5.104),
Ex
Ex
= Ix Z (w)x
= (10 A) (0:25 ohm) = 2:5 V
65
c) From eq. (5.99),
= L=A = (15 cm) = 8; 000 cm2
= 1:88x10 3 cm
Kc =
=
Rs
Z (w)x
1:88x10 3 cm
0:25 ohm
Kc
= 7:50x10
ohm 1 :cm
5.30 Determine and analyze the impedance prole by varying the angular
frequency for xed Rx = 0:25 ohm and Cx = 20 A:s=V .
Solution:
This problem requires use of eq. (5.103). The intent here is to show how the
impedance depends on the angular frequency at very low values.
s
2
1
2
Z (w)x = (0:25) +
20!
5
Z(w) 3.75
2.5
1.25
0
0
0.05
0.1
0.15
0.2
0.25
0.3
5.31 Assume that an electrolytic cell is used for recovering magnesium from
a solution containing 10 4 mol=cm3 of M g+2 at 350 C: The nickel ionic mobility
and the electric-eld strength are B = 55x10 5 cm2 V 1 s 1 and Fx = 10 V =cm
[Taken from reference 5], respectively, calculate (a) the ionic velocity (v), (b)
the solution electric conductivity (Kc ) and the electric resistivity (c ). [Solution:
(a) v = 0:0055 cm=s, (b) Kc = 0:0106 ohm 1 :cm 1 and (c) c = 94:21 ohm:cm].
Solution:
66

a) From eq. (5.92),
v = BFx = 55x10
cm2
V:s
V
10
= 0:0055 cm=s
cm
b) Using eq. (5.93) yields

Kc
Kc
Kc
= zF BC
A:s
= (2) 96; 500
55x10
mol
= 0:0106 ohm 1 :cm
cm2
V:s
10
mol
cm3
and from eq. (5.89)

c = 1=Kc = 94:21 ohm:cm
5.32 It is known that current ows when there exists a gradient of electric
potential (d=dx) within an electric conductor, such as an electrolyte. Consider
a current-carrying homogeneous conductor with constant cross-sectional area
(Ac ) so that the electric-eld strength (Ex ) is constant at every point in the
conductor. Derive an expression for the current as a function of the gradient
of electric potential. In this particular problem "x" stands for direction as well
as length of the electric conductor. Start with the following current density
denition i = Kc Ex , where Kc is the electric conductivity (ohm 1 :cm 1 ).
Solution:
Using eq. (2.2a) and the given current density equation yields
Ex
d
dx
(a)
i = Kc Ex = Kc
I
Ac
I
= Kc
d
dx
d
dx
= Ac Kc
(b)
(c)
d
dx
(d)
This expression agrees with the above statement because I = f (d=dx). For
a homogeneous conductor, eq. (d) becomes
x
where x becomes the length of the conductor.
I = Ac Kc
67
EXTRA
5.EX1 Determine the atomic weight of 82M g-10Al-8Zn alloy.
Solution:
The state of oxidation and the atomic weight of each element are
zMg
zAl
zZn
= 2 & Aw;Mg = 24:31 g=mol

= 3 & Aw;Al = 26:98 g=mol
= 2 & Aw;Zn = 65:37 g=mol
From the given weight percent of the alloy, the weight fraction for M g, Al
and Zn are
fMg = 0:82
fAl = 0:10
fZn = 0:08
Then the atomic weight of the alloy is

Aw;alloy
Aw;alloy
X fj Aw;j
=
zj
= 13:48 g=mol
fMg Aw;Mg + fAl Aw;Al + fZn Aw;Zn

zMg + zAl + zZn
5.EX2 An electrochemical ionic concentration cell shown below was used

as a concentration cell in order to measure the current due to the dierence in
ionic concentration between the anodic half-cell and the cathodic-half cell. Determine the corrosion rate in terms of electrons/second and the number of anodic
reactions/second if the measured current is 3:23x10 7 A = 3:23x10 7 C=s.
68
Solution:
The oxidation of copper (corrosion) and the reduction of copper (electroplating) are, respectively
2+
Cu
Cu ! Cu2+ + 2e
+ 2e ! Cu
Clearly, the oxidation state is z = 2: Thus, the corrosion rate is

r=
I
3:23x10 7 C=s
=
2x1012 electrons=s
qe
(1:6022x10 19 C=electrons)
Also,
I
=
zqe
2
= 1012 reactions=s
electrons
reactions
3:23x10 7 C=s
(1:6022x10 19 C=electrons)
5.EX3 Use the Evans diagram given below to determine (a) the linear corrosion rate prole, CR = f (ix ), at 10 8 A=cm2 ix 10 3 A=cm2 and (b) the
non-linear counterpart, CR = f (Ea ), at 0:45 V Ea 0:25 V for iron (Fe)
immersed in a acid solution. Use CR in units mm=yr and let ix be the applied
current density. The atomic weight and density of iron are Aw = 55:85 g=mol
and 7:87 g=cm3 , respectively. Explain.
69
Solutions:
(a) From eq. (5.48),
ia Aw
= ix
zF
Aw
55:85
V:cm3
=
=
= 3:6770 10 5
zF
2 96500 7:87
A:s
3
V:cm
CR =
3:6770 10 5
(60 60 24 365) (10) ix
A:s
CR = 11; 596ix (inmm=yr)
CR
(a)
The slope of this plot represents the volume of F e2+ ions per electric charge.
Hence,
dCR
dix
dCR
dix
= = 3:6770 10
' 0:038
cm3
(slope)
A:s
mm3
A:s
The upper and lower CR values are

CR
CR
= 11:60 mm=yr @Ecorr (upper limit )

= 1:16 10 4 mm=yr @EF e (lower limit)
70
Therefore, corrosion can be minimized signicantly as ix ! iF e = 10 8

A=cm2 . Upon decreasing ix into the cathodic region at E < EF e , reduction of
iron, F e2+ + 2e ! F e, occurs and CR = 0. This electrochemical process leads
to the principles of cathodic protection (CP ) large structures. The theory of CP
is dealt with in a later chapter.
(b) Combining eq. (a) and (5.37a) gives
CR
ia
CR
CR
ia Aw
= ia
zF
2:303 (Ea Ecorr )

= icorr exp
a
2:303 (Ea Ecorr )

= icorr exp
a
= (11:60 mm=yr) exp (57:58Ea + 14:39)
=
(b)
(c)
The non-linear corrosion rate prole is given by eq. (c) and it is depicted in
the gure below.
The upper and lower CR values in this case are

CR
CR
= 11:54 mm=yr @Ecorr (upper limit )

= 1:15 10 4 mm=yr @EF e (lower limit )
Basically, these results are the same as in part (a).
Chapter 6
MASS TRANSPORT BY
DIFFUSION AND
MIGRATION
6.1
PROBLEMS
6.1 Why convective mass transfer is independent of concentration gradient

@C=@x in eq. (6.2)?
Answer: Because it arises due to uid motion in which @C=@x doe not
play an important role. Only the bulk concentration and uid velocity are the
controlling parameters at a plane for convective motion.
6.2 Use the information given in Example 6.3, part b, to determine the
concentration rate in the x-direction at 1 mm from the columns interface. Given
data: D = 10 5 cm2 =s, Co = 10 4 mol=cm3 and t = 10 sec : [Solution: @C=dt =
1:96x10 16 mol=cm3 :s].
Solution:
From Example 6.2,

@C
@x
@2C
@x2
Co
x2
= p
exp
4Dt
4Dt
xCo
x2
p
=
exp
4Dt
4Dt Dt
71
72 CHAPTER 6. MASS TRANSPORT BY DIFFUSION AND MIGRATION

Thus, Ficks second law becomes
@C
@t
@C
@t
@2 C
@x2
xCo
x2
p
exp
4Dt
4t Dt
"
#
4
2
(0:1 cm) 10 mol=cm3
(0:1 cm)
p
exp
(4) (10 5 cm2 =s) (10 s)
(4) (10 s) () (10 5 cm2 =s) (10 s)
= D
=
@C
@t
@C
@t
= 1:96x10
16
mol
cm3 :s
6.3 Whats the action of hydrogen on a steel blade exposed to an aqueous

solution of hydrogen sulde if the following reaction takes place F e + H2 S =
F eS + 2H? Assume that the steel blade gets damaged during service.
Answer: Evolution of atomic hydrogen (H) on the steel surface may occur
according to the reactions
F e ! F +2 + 2e
H2 S ! 2H + + S 2 + 2e
F e + H2 S ! F e+2 + S 2 + 2H + + 2e
and
F e+2 + S
+ 2H + + 2e ! F eS + 2H
Atomic hydrogen readily diuses into the steel (iron matrix) and locates there
in voids, vacancies, and dislocations where H + H ! H2 occurs within the
lattice. The formation of molecular hydrogen (H2 ) in voids combine with other
hydrogen molecules, building up a high pressure (P ) that may exceed the yield
strength (ys ) of the steel blade. If P > ys , then blistering and ssures may
occur and the steel strength and ductility decrease. This phenomenon is known
as hydrogen embrittlement.
6.4 An aerated acid solution containing 10 2 mol=l of dissolved oxygen (O2 )
moves at 2x10 4 cm=s in a stainless steel pipe when a critical current density
of 103 A=cm2 passivates the pipe. Calculate a) the thickness of the Helmholtz
ionic structural layer (), b) the limiting current density (iL ) if the three modes
of ux are equal in magnitude, and c) Will the pipe corrode under the current
conditions? Why? or Why not? Data:
O2 + 2H2 O + 4e = 4OH
DO2 = 10
cm2 =s
T = 25o C
(Cathode)
F = 96; 500 A:s=mol
6.1. PROBLEMS
73
Solutions:
a) From eq. (6.1) along with Cb = 10
uxes are
J (x; t)c
J (x; t)c
J (x; t)d
J (x; t)m
mol=l = 10
mol=cm3 , the molar
= Cb v (x; t) = 10 5 mol=cm3 2x10

mol
= 2x10 9
cm2 :s
mol
@C
DCb
= 2x10 9
=D
=
cm2 :s
@x
mol
zF
DC
d
b
= 2x10 9
=
cm2 :s
RT dx
cm=s
Thus, the total molar ux becomes

J (x; t) = J (x; t)d + J (x; t)m + J (x; t)c
J (x; t) = 3J (x; t)c
mol
J (x; t) = 3Cb v (x; t) = 6x10 9
cm2 :s
But,
DCb
= Cb v (x; t) = J (x; t)c

D
10 5 cm2 =s
=
v (x; t)
2x10 4 cm=s
= 0:05 cm = 0:5 mm
=
b) From eq. (6.8)

i = zF J (x; t)
A:s
9 mol
i = (4) 96; 500
6x10
mol
cm2 :s
A
A
i = iL = 2:32x10 3
= 2:32x103
cm2
cm2
c) Corrosion will not occur because iL = 2:32x103 A=cm2 > icrit = 103
A=cm2 .
6.5 a) Determine the oxygen concentration for Problem 6.4 that will promote corrosion of the stainless steel pipe. b) How long will it take for corrosion
to occur?
Solutions:

a) For a diusional process only, From eq. (6.9a) yields along with @C=@x '
DCb = and i = ic ,
3
10 A=cm2 (0:05 cm)

ic
=
zF D
(4) (96; 500 A:s=mol) (10 5 cm2 =s)
Cb
Cb
= 1:30x10
mol=l = 1:30x10
mol=cm3
This result indicates that approximately 100% 1:30x10

23% increase in oxygen content will cause corrosion.
10
=1:30x10
b) From eq. (6.52),

zF C
p b
Dt
2
D zF Cb
t =
ic
5
"
(4) (96; 500 A:s=mol) 1:30x10
10 cm2 =s
t =
10 3 A=cm2
ic
mol=cm3
#2
t = 80:15 s = 1:34 min:
6.6 Use the given data to calculate a) the diusivity of copper ions in a
cathodic process at 25o C and b) the valence z. The original concentration in
an acidic solution is 60 g=l.
t
(sec)
0
5
10
15
20
i 2
A=cm
0
0:1455
0:1029
0:0840
0:0728
@C=@x4
mol=cm
0
0:07532
0:05326
0:04349
0:03766
Solution:
Cb = 60 g=l = (60g=l) (63:55 g=mol) = 0:9443 mol=l
Cb = 9:443x10 4 mol=l
a) Linear regression analysis:From eq. (6.48),
@C
= 1:801 5 10
@x
mol
mol:s1=2
+
0:16842
t
cm4
cm4
1=2
6.1. PROBLEMS
75
0.08
Eq. (4.48)
dC/dx (mol/cm4)
0.07
0.06
0.05
Slope = 0.1684 mol.s1/2.cm-4
0.04
0.03
0.2
0.25
0.3
-1/2
0.35
0.4
0.45
-1/2
(sec
From eq. (6.48),
Cb
Cb
p
= p
t 1=2
Dt
D
C
mol:s1=2
p b = 0:16842
cm4
D
2
2
1 Cb
1
9:443x10 4 mol=cm3
=
S
0:16842 mol:s1=2 =cm4
@C
@x
= 10
cm2 =s
b) Polynomial t:
i = 4:8903 10
A=cm2 + 0:30648 A:s1=2 =cm2 t
1=2
Eq. (4.52)
i (A/cm2)
0.14
0.12
0.1
S = 0.30648 A.s1/2/cm2
0.08
0.06
0.2
0.25
0.3
-1/2
0.35
(sec
0.4
0.45
-1/2
From eq. (6.52),

i =
i =
S
zF DCb
p
Dt
zF DCb 1=2
p
t
D
zF DCb
p
= 0:30648 A:s1=2 =cm2
D
p
p
0:30648 A:s1=2 =cm2
=10 5 cm2 =s
S =D
=
F Cb
(96; 500 A:s=mol) (9:443x10 4 mol=cm3 )
2
6.7 It is desired to reduce copper, Cu+2 + 2e = Cu, at 35o C from an

electrolyte containing 60 g=l of Cu+2 ions. Calculate a) the total molar ux that
arises from equal amounts of diusion and migration mass transfer under steadystate conditions, b) the gradients dc=dx; d=dx; and d=dx, and c) approximate
the thickness of the diusion layer at the cathode electrode surface. Operate
the electrowinning cell for 10 minutes and let the diusivity for Cu+2 ions be
10 5 cm2 =s:
Solutions:
Cb = 60 g=l = (60 g=l) (63:55 g=nol)
Cb = 0:944 mol=l
Cb = 9:44x10 4 mol=cm3
D = 10 5 cm2 =s
t = 10 min = 600 sec

z=2
F = 96; 500 A:s=mol
k = 1:38x10 23 J=o K
6.1. PROBLEMS
77
a) From eq. (6.52),

i =
zF DCb
p
= zF Cb
Dt
D
t
i = (2) (96; 500A:s=mol) 9:44x10

i = 1:33x10
A=cm2
mol=cm
(10 5 cm2 =s)

() (600 sec)
From eq. (6.8),

i = zF J
i
1:33x10 2 A=cm2
J =
=
zF
(2) (96; 500 A:s=mol)
mol
J = 6:88x10 8
cm2 :s
b) Both diusion and migration uxes are equal. Thus,
J
= Jd + Jm
= Jm = J=2 = 3:44x10
Jd
From eq. (6.48),
@C
@x x=0
@C
@x
x=0
mol
cm2 :s
C
9:44x10 4 mol=cm3
p b =p
Dt
() (10 5 cm2 =s) (600 sec)
moil
= 3:88x10 3
cm4
=
From eq. (6.15), the ionic mobility is

B
B
D
10 5 cm2 =s
=
kT
(1:38x10 23 J=o K) (308o K)
cm2
V:cm2
= 2:35x1015
= 2:35x1015
J:s
C:s
=
Now, using eq. (6.12) yields

d
dx
Jm
zqe Cb B
d
dx
d
dx
= 4:83x10
(2) (1:602x10
2
19
V =cm
mol
3:44x10 8 cm
2 :s
mol
4
C) 9:44x10 cm3 2:35x1015
V:cm2
C:s

From eq. (6.11),
d
dx
d
dx
d
dx
d
dx
= (2) 1:602x10
= zqe
= 1:55x10
20
19
J=V
J=cm
4:83x10
V =cm
c) From eq. (6.53),
p
=
Dt
p
=
() (10 5 cm2 =s) (600 s)
= 0:137 cm = 1:37 mm
6.8 Show that Jx=o = DCo =:

Solution:
Using eq. (6.40) for activation polarization (Co > Cb = C1 ) yields
= Co (Co Cb ) erf (y)
x
dx
y = p
dy = p
4Dt
2 Dt
2
x
y2 =
4DtZ
y
2
erf (y) = p
exp y 2 dy
o
Cx
Rearranging eq. (6.40) along with C = Cx and Co > Cb = C1 gives
Z y
2
C = Co Co p
exp y2 dy
o
Z y
2
x2
dx
p
C = Co Co p
exp
o
4Dt 2 Dt
Z y

Co
x2
C = Co p
exp
dx
4Dt
Dt o
(4.40)
(a)
(b)
(c)
(d)
Thus,
@C
@x
@C
@x
@C
@x x=o
Z y

Co @
x2
= p
exp
dx
4Dt
Dt @x o
Co
x2
= p
exp
4Dt
Dt
Co
= p
Dt
(e)
6.1. PROBLEMS
79
Combining eqs. (6.3) and (e) yields

Jx=o
Jx=o
@C
= D
@x x=o
DCo
DCo
= p
=
Dt
((4.51))
p
6.9 Show that dC=dx = Cb = Dt:
Solution:
Using eq. (6.38) for activation polarization (Cb = C1 >> Co ) yields
= Co + (Cb Co ) erf (y)
= Co + Cb erf (y)
x
dx
y = p
dy = p
4Dt
2 Dt
x2
2
y =
4DtZ
y
2
erf (y) = p
exp y 2 dy
o
Cx
Cx
Rearranging eq. (6.40) along with C = Cx gives
Z y
2
2
C = Co + Cb p
exp y dy
o
Z y
2
x2
dx
p
C = Co + Cb p
exp
o
4Dt 2 Dt
Z y

Cb
x2
C = Co + p
exp
dx
4Dt
Dt o
(4.38)
(a)
(b)
(c)
(d)
(e)
Thus,
@C
@x
@C
@x
@C
@x x=o
=
=
=
Z y

C
@
x2
p b
exp
dx
4Dt
Dt @x o
C
x2
p b exp
4Dt
Dt
Cb
p
Dt
(e)
6.10 Prove that the diusivity D is constant in the Ficks second law, eq.
(6.17).

Solution:
From eq. (6.39),
Cx Co
Cb Co
Cx Co
Cb Co
= erf (y)
x
= erf p
4Dt
For xed values of distance x, time t, temperature T and concentration Cx ;
Cx Co
x
= Constant = erf p
Cb Co
4Dt
Therefore, the diusivity is
D
D
E
= Do exp
= Constant
RT
6= f (Cx )
6.11 Assume that the total molar ux of a specie j is due to diusion and
convection. The convective force acting on the specie is Fx = (1=NA ) (dG=dx),
where NA is Avogadros number and dG=dx is the molar free energy gradient.
Recall that the volume fraction is equals to the mole fraction divided by molar
concentration; that is, V = X=C. Based on this information, show that
dC
d ln (C=Co )
=C
dx
dx
where Jd = Jc , K = C=Co < 1 and Co = Constant.
Solution:
Combining eqs. (6.5) and (6.13) yields
Jc
Jc
= Cv = CBFx
CB dG
=
NA dx
Thermodynamically, the free energy change is dened by eq. (2.31a)

G = Go + RT ln (K)
G = Go + RT ln (C=Co )
dG
d [ln (K)]
= RT
dx
dx
6.1. PROBLEMS
81
where K is the rate constant. Thus,

Jc
Jc
CBRT d [ln (C=Co )]

NA
dx
d [ln (C=Co )]
= CkBT
dx
=
since k = R=NA = Boltzmann constant. Ficks rst law gives

Jd = D
@C
@x
If Jd = Jc , then
@C
@x
@C
kBT
@x
@C
@x
D
d [ln (C=Co )]
= CkBT
dx
d [ln (C=Co )]
= CkBT
dx
d [ln (C=Co )]
= C
dx
since D = kBT as in eq. (6.15). This concludes the solution of the problem.
6.12 Use the information given in Problem 6.11 to show that
dG
RT dC
=
dx
C C
Solution:
G = Go + RT ln (K)
dG
d ln (C=Co )
= RT
dx
dx
But,
1 dC
d ln (C=Co )
=
C dx
dx
Then,
dG
RT dC
=
dx
C dx
6.13 Use the information given in Problem 6.12 to show that
vx =
D dC
C dx

Solution:
From eqs. (6.13) and Problem 6.11,
v
Fx
= BFx
1 dG
=
NA dx
(4.13)

G = Go + RT ln (K)
dG
d ln (C=Co )
= RT
dx
dx
But,
1 dC
d ln (C=Co )
=
C dx
dx
Then,
dG
RT dC
=
dx
C dx
Thus, eq. (6.13) yields the drift velocity as
v
v
BkT dC
C dx
D dC
=
C dx
=
where D = BkT:
6.14 If the migration ux is neglected in eq. (6.2), approximate the total
ux at low and high temperatures. Assume that Cx >> Co at a distance x from
an electrode surface.
Solution:
J
J
dC
+ Cv
dx
Co C
= D
+ Cv
x
= D
If C >> Co , then
J =
DC
+ Cv
x
6.1. PROBLEMS
83
In addition,
E
D = Do exp
RT
and
Mathematically,
CDo
E
J =
exp
+ Cv
x
RT
@ If T ! 0, then D ! 0 andJ = Jc ' Cv

@ If T ! 1, then D ! Do and
J '
CDo
+ Cv
x
This analysis indicates that the diusivity D and the molar ux J increase
with increasing temperature.
6.15 Consider the concentration plane shown below. This is a transient
electrochemical system having nite dimensions. Derive a solution for Ficks
second law, @C=@t = D@ 2 C=@x2 ; based on this information
Solution:
Following the analytical procedure in Appendix A yields
x
y= p
2 Dt
ax
y1 = p
2 Dt
bx
y2 = p
2 Dt
Start with eq. (A6) and (A8):

Z Cb
Z 1
p
dC = B
exp y2 dy = B
o
1
p
Cb =
B
Cb
B = p

Then,
Z
dC
dC
C
Cb
Z y2
C
pb
exp y2 dy
y1
Z y2
Z y2
2
2
Cb 2
2
p
exp y dy p
exp y dy
2
o
o
1
[erf (y2 ) erf (y1 )]
2
6.16 Derive Ficks second law if the volume element in Figure 6.2 has a unit
cross-sectional area and a thickness x.
Solution:
Jx;in
Jx;out
@C
@x x
@C
@C
@C
= D
= D
D
@x x+dx
@x x
@x dx
= D
The concentration rate is

@C
@t
@C
@t
@C
@t
@C
@t
@Jx
@Jx;in @Jx;out
=
@x
@x @x
2
@2 C
@2C
@ C
= D
+
D
+
D
@x2 x
@x2 x
@x2 dx
2
@ C
= D
@x2 dx
=
= D
@2C
@x2
6.17 What does Ficks rst law mean in terms of atoms or ions of a single
phase?
Answer: Ficks rst law, Jx = D
from high to low concentration regions.
@C
@x
, means that atoms or ions diuse
6.18 What will Ficks rst law mean if D does not vary with x or C?
Answer: Ficks rst law will mean that Jx = D @C
@x becomes a linear re
lationship under steady-state condition @C

=
0
and
hat
atoms or ions diuse
@t
from high to low concentration regions.
6.1. PROBLEMS
85
6.19 Derive Ficks second law if the volume element in Figure 6.2 has a unit
cross-sectional area and the diusing plane is located between x and x + dx,
where Jx is the entering molar ux at x and Jx+dx is that leaving at x + dx.
Solution:
Using Ficks rst law and the continuity equation yields
@C
@t
Jx
@C
@t
@C
@t
@Jx
@x
@C
= D
@x
1
@C
=
D
@x
@x
@D @C
@2C
=
+D 2
@x @x
@x
=
If D is constant, then Ficks second law becomes

@C
@2C
=D 2
@t
@x
6.20 Find an expression for x when
Cx Cb
= 0:5205 = erf
Co Cb
x
p
4Dt
Solution:
Cx Cb
x
= 0:5205 = erf p
Co Cb
4Dt
Cx Cb
= 0:5205 = erf (y)
Co Cb
0:5205 = erf (y)
From Table 6.2,
x
p
4Dt
1
x
p
=
2
2 Dt
p
x =
Dt
y
6.21 Derive eq. (6.85).

Solution:

Using eq. (6.82) for oxidation yields
dCx
Cx d
i = zF D
+
dx
RT dx
2
di
d C
C d2
1 dC d
= zF D
+
+
=0
dx
dx2
RT dx2 RT dx dx
(a)
From eq. (6.48) along with constant D at xed time t and with C = Cb =
constant at x ! 1 in the bulk electrolyte,
dC
dx
2
d C
dx2
C
p b
Dt
= 0
(b)
(c)
Inserting eqs. (b) and (c) into (a) yields

d2
1 d
+p
=0
2
dx
Dt dx
(4.62)
6.22 Show that d=dx = 7o = 19 Dt in a coupled diusion and

p
migration mass transfer. let x = Dt:
Solution:
x
= o exp p
Dt
d
o
x
= p
exp p
dx
Dt
Dt
p
!
d
o
Dt
= p
exp p
dx
Dt
Dt
d
dx
d
dx
d
dx
= p o exp (1)
Dt
0:368o
= p
Dt
7o
= p
19 Dt
6.23 For activation polarization, the concentration gradient is given by eq.

(6.50). If Co >> Cb , then show that
6.1. PROBLEMS
87
C
1
=p
Co
4Dt
Solution:
x3
x
12Dt
From eq. (6.49) along with Co >> Cb ,
dC
Co
x2
= p
exp
dx
4Dt
4Dt
a) Taylors series: Letting y = x2 = (4Dt) and expanding the exponential

P
function, exp(y) = (y)k =k! ' 1 y, yields
dC
dx
dC
dx
dC
dx
Co
= p
(1 y)
4Dt
Co
x2
= p
1
4Dt
4Dt
2
Co
x
= p
1
4Dt 4Dt
b) Using the rst three terms of McClaurin series yields

f 0(0)
f 00(0) 2 f 000(0) 3
f (x) = f (0) +
x+
x +
x + ::::
1!
2!
3!
x2
f (x) = exp
4Dt
x2
f (x = 0) = exp
=1
4Dt x=0
2x
x2
0
f (x = 0) =
exp
=0
4Dt
4Dt x=0
1
x2
x2
x2
f 00(x = 0) =
exp
+
exp
2Dt
4Dt x=0 4D2 t2
4Dt x=0
1
f 00(x = 0) =
2Dt
x2
x2
f (x) = exp
=1
4Dt
4Dt
Then,
1
Co
dC
Co
dC
C
Co
1
x
p
1 dx
4Dt 4Dt
Z x 2
1
x
p
1 dx
4Dt
4Dt o
3
1
x
p
x
4Dt 12Dt

6.24 Derive eq. (5.122) by converting eq. (3.29) into chemical potential
() if only one ion participates in a reaction. The reaction constant is dened
by Kr = C, where is the activity coecient and C is the concentration. Let
the molar diusion and migration be equal and Jc = 0 in eq. (6.10).
Solution:
= o + kT ln (Kr ) = o + kT ln (C)
= o + kT ln () + ln (C)
d
kT
=
dC
C
Let
d
d dC
kT dC
=
=
dx
dC dx
C dx
and
Jd
dC
D
dx
D
= Jm
= CB
d
dC
= BkT
dx
dx
= BkT
6.25 Follow the statement given in Example 6.3 for determining the average
concentration as the starting point in this problem. Let Co;1 and Co;2 be the
original concentrations of columns 1 and 2, respectively.
Solution:
Start with
Average concentration:
Cx C
= erf
Co;1 C
C
x
p
Dt
Co;1 + Co;2
Co
=
2
2
Co
2
6.1. PROBLEMS
89
Thus,
Cx
Co
Cx
Co
=
=
1
x
erf p
2
Dt
1
@ x=0
2
The rest of the problem is worked out in Example 6.3.

6.26 This problem requires the determination of the total molar ux and
current density proles due to diusion, migration and convection for the reduction of nickel from an electrolyte containing 8x10 4 mol=cm3 of N i+2 cations.
The electrochemical cell has a continuos and direct uid ow system of 20 cm=s
at 35o C. The diusivity of N i+2 cations is D = 1:44 10 5 cm2 =s. a) Use
0 t 100 seconds for Jx = f(t; x = 0) at the electrode surface and b)
0 x 10 centimeters for Jx = f (x; t = 10), and c) analyze the resultant
proles very succinctly and determine which molar ux dominates in this hypothetical reduction process for N i+2 cations from solution. Can this process
achieve a steady-state?
Solution:
N i+2 + 2e = N i
z=2
Cb = 8 x10 4 mol= cm3
vb = 20 cm= s
D = 1:44 10 5 cm2 = s
F = 96; 500 A:s=mol
Electrode Surface: Using eqs. (6.5), (6.64a), and (6.54b) yields the molar
uxes on the electrode surface (x = 0)
Jc = Cb vb = 0:002 mol=cm2 :s
p
p
Jm = (DCb ) = Dt = 1:712 8 10 3 = t
p
p
Jd = (DCb ) = Dt = 1:712 8 10 3 = t
Jx = Jd + Jm + Jc
Jx
Jx
(2) 1:712 8 10 3
p
+ 0:002
t
3:4256 10 3
p
+ 0:002
t

where t is in seconds and Jx in mol:cm 2 s 1 . Thus, the Jx vs: t prole is
shown below.
0.8
0.7
0.6
0.5
Jx 0.4
0.3
0.2
0.1
0
-0.1
-0.2
-0.3
-0.4
-0.5
-0.6
-0.7
0
10 20 30 40 50 60 70 80 90 100
Problem 4.26a
This prole indicates that Jx ! 1 as t ! 0 and this is a transient process.

However Jx ! 0 as t ! 1 which is the condition for a steady-state process.
These theoretical analysis can further be conrmed by letting t = 10 seconds and
vary the distance x from the electrode surface. Hence,
Fixed Time: Using eqs. (6.5), (6.64), (6.4) and (6.3) yields
Jc = Cb vb = 0:002 mol=cm2 :s
t = 10 s
p
1
= o exp (x=) = RT (zF ) exp x= Dt
p
1
p
d=dx = RT zF Dt
exp x= Dt
Jm = (DCb ) (RT ) 1 d=dx
p
1
p
Jm = (DCb )
Dt
exp x= Dt
Jm = 5:416 2 10 7 exp (47:016x)
p
1
Jd = D@Cx =@x = DCb

31:416D
exp x2 (40D) 1
Jd = 5:416 2 10 7 exp 1736:1x2

Jx = Jd + Jm + Jc
6.1. PROBLEMS
91
Jx = 5:416 2 10 7 exp 1736:1x2 + 5:416 2 10 7 exp (47:016x) +

0:002
0.1
Jx
10
This conrms that a steady-state is achieved at t 10 seconds. It can also

be concluded that the convective molar ux controls the electrodeposition since
Jx Jc 0:002 mol=cm2 :s. Therefore, an eective electrolyte ow system is
important in electrodeposition. Similarly proles result for the current density.
(2) 1:712 8 10 3
3:425 6 10
p
p
Jx =
+ 0:002 =
t
t
Using eq. (6.9) yield i in A=cm2 and time t in seconds
i = zF Jx = (2) (96500)
3: 425p
6 103
t
+ 0:002
+ 0:002

0.175
0.15
i
0.125
0.1
0.075
0.05
0.025
0
0
0.0125
0.025
0.0375
0.05
t (sec)
This prole indicates that the current density in A=cm2 is suciently high,
but it rapidly decreases as the electrochemical process progresses. For instance,
at t = 0:01 sec the current density is i = 3:63x10 2 A=cm2 . In addition,
i = zF Jx
5:416 2 10 7 exp 1736:1x2
i = (2) (96500)
7
exp (47:016x) + 0:002
+ 5:416 22 10
i = 0:104 53 exp 1736:1x + 0:104 53 exp (47:016x) + 386:0
i = 386 A=cm2
390
i 387.5
385
382.5
380
0
2.5
7.5
10
6.27 (a) Derive an expression for the concentration in g=l as a function

of temperature T and distance x from an oxidizing pure copper electrode in
an electrolyte under an electrostatic eld. Use the chemical potential gradient,
d=dx = (zF ) d=dx with an electric potential decay, x = o exp (x) Let
6.1. PROBLEMS
93
the free energy change be dened as G = Gx @ x and G = G1 @ x = 1.

(b) Plot the concentration Cx prole at two dierent temperatures. Let
1 = 0
3
o = 8:314x10
V
o
T = 298 K curve
T = 318o K ( curve)
= 0:2 cm 1
0 x 3:8 cm
C1 = 1:57x10 3 mol=l = 0:1 g=l
F = 96; 500 J=mol:V
Solution:
a) The oxidation reaction is Cu = Cu+2 + 2e. Combining eqs. (a) and (b)
yields
Z
d = zF
x 1
x 1
(c)
= zF x
= zF o exp (x)
(d)
(e)
From eq. (2.27),

Gx
G1
= x;prod x;react = x;prod

= 1 ;prod 1 ;react = 1 ;prod
(f)
(g)
since x;prod = 1 ;react = 0 for the oxidation reaction. From eq. (2.31b),
the change
Gx
G1
= RT ln (Kx ) = RT ln (Cx )
= RT ln (K1 ) = RT ln (C1 )
(h)
(i)
Combining eqs. (f) through (i) gives

x
1
x 1
= RT ln (Cx )
= RT ln (C1 )
C1
= RT ln
Cx
(j)
(k)
(l)
Finally, equating eqs. (e) and (l) yields

Cx
Cx
zF o
= f(x; T ) = C1 exp
exp (x)
RT
193
= (0:1 g=l) exp
exp (0:2x)
T
(m)
(n)
0.2
C x 0. 1 g/l exp
Cx
(g/liter)
193
T
exp0. 2x
0.175
T 298 o K
0.15
T 318 o K
0.125
0.1
x (cm)
6.28 Derive an expression for iL = f (Cx ; T; vx ) and explain its physical signicance with respect to concentration polarization and metal reduction. Plot
c = f (i=iL ) when iL = 5 10 3 A and iL = 10 2 A to support your explanation. When is the concentration polarization process discernible (apparent)?
Solution:
Combining eqs. (6.92), (6.97), (6.72), and (6.76) yields the sought expression
along with the overpotential equation
iL
zF Cx vx T
p
= f (Cx ; vx ; T )
Fx Dt
2:303RT
i
log 1
zF
iL
(a)
(b)
The schematic polarization diagram is shown below for two dierent cases.
6.1. PROBLEMS
95
Thus, iL = f (Cx ; vx ; T ) represents the maximum rate of reduction, and it is

the limiting diusion current density. In fact, iL = f (Cx ; vx ; T ) is signicant
during reduction processes and negligible during metal dissolution. With respect
to iL = f (Cx ; vx ; T ), it increases with increasing concentration, species velocity
and temperature as predicted by equation (a). Finally, concentration polarization
becomes apparent when i ! iL and c ! 1 and c ! 0 when iL ! 1. The
latter can be dened as
!
p
2:303RT
iFx Dt
c =
log 1
(c)
zF
zF Cx vx T
It is also apparent that concentration polarization is possible when jc j > 0
due to presence of Fx for ionic mobility at an ionic velocity vx .
Chapter 7
CORROSIVITY AND
PASSIVITY
7.1
PROBLEMS
7.1 Determine (a) the electric potential E in millivolts, (b) the time in seconds,
and (c) the growth rate in m=s for electroplating a 3-m thick Cr lm on a
Ni-undercoated steel part, provided that the electrolyte contains 10 4 mol=l
of Cr+3 cations at 25o C, the N i-steel part has a 10-cm2 surface area, and the
cell operates at 50% current eciency and at a passive current of 0:8 amperes.
Assume that the oxide passive lm has a density of 7:19 g=cm3 .
Solution:
o
Cr+3 + 3e = Cr
ECr
= 0:744 V
z=3
x = 3x10 4 cm
= 7:19 g=cm3
Aw;Cr = 52 g=mol
i = I=As = 0:08 A=cm2
As = 10 cm2
= 0:50
[Cr+3 ] = aCr+3 = 10 4 mol=l
(a) Using Nernst equation yields
E
E
E
RT
ln (aCr+3 )
zF
(8:314 J=mol:K) (298 K) 4
> Eo = 0:744V +
ln 10
(3) (96; 500 J=mol:V )
> Eo = 0:823 V
> Eo = E o +
(b) Integrating equation eq. (7.21) yields the time

Z
zF
iAw
zF x
iAw
0
(3) (96; 500 A:s=mol) 7:19 g=cm3 3x10

t =
(0:50) (0:08 A=cm2 ) (52 g=mol)
t = 300:22 sec ' 5 min
t =
dx =
97
cm
98
CHAPTER 7. CORROSIVITY AND PASSIVITY

(c) The lm growth rate is
dx
dt
dx
dt
x
3 m
=
t
300:22 sec
m
= 0:01
sec
=
7.2 (a) If chromiun oxide lm frow rate is 0:03 m= sec, how long will it
take to grow a 5 m lm on a Ni-substrate. Assume that the cell operates at
50% current eciency. Calculate (b) the current density.
Solution:
(a) The time is
dx
dt
t =
x
t
x
5m
=
= 100 sec
dx=dt
0:05 m= sec
(b) From eq.(7.51), the current density is
i =
(3) (96500) (7:19) 5 10 4

zF x
=
tAw
(0:8) (100) (52)
i = 0:25 A=cm2
7.3 Briey, explain why the corrosion rate and the corrosion potential increase on the surface of some metallic materials in contact with an oxygencontaining acid solution. In this situation oxygen acts as an oxidizer. Use a
schematic polarization diagram to support your explanation. Let the exchange
current densities and the open-circuit potentials be io;O2 < io;H2 < io;M and
Eo;O2 > io;H2 > io;M . What eect would have oxygen on the metal dissolution
if io;O2 << io;H2 < io;M and Eo;O2 > io;H2 > io;M .
Solution:
NO OXYGEN: The polarization diagram below implicitly explain the reason why the corrosion rate increases in the presence of oxygen in an acid solution. According to the gure below, the corrosion rate in terms of current
density and the corrosion potential are
i0
corr
i0
net
0
Ecorr
= i0
No oxygen
H
0
0
= icorr iH = 0 at equilibrium
0
= EH
No oxygen
7.1. PROBLEMS
99
WITH OXYGEN: However, when oxygen is present as an oxidizer the corrosion rate and corrosion potential become
icorr
Ecorr
= (iH + iO2 ) > i0

corr
0
> Ecorr
Consequently, hydrogen evolution decreases because iH < i0

H and oxygen
evolution evolves consuming additional electrons from the metal. In certain
cases when io;O2 << io;H2 < io;M the presence of oxygen as an oxidizer would
have insignicant eect on the rate of metal dissolution.
Evans Diagram
EO2
E (V)
i O2
iH iO2
Eo,H
Ecorr
Stern Diagram
ia = ir if
io,H
Corrosion Point
Ecorr
icorr
Eo,M
io,M
icorr
ic = if ir
iL
Log (iL)
7.4 Assume that a stainless steel pipe is used to transport an aerated acid
solution containing 1:2x10 6 mol=cm3 of dissolved oxygen at room temperature
and that the electric-double layer is 0:7 mm and 0:8 mm under static and owing
velocity, respectively. If the critical current density for passivation and the
diusion coecient of dissolved oxygen are 300 A=cm2 and 10 5 cm2 =s, then
determine (a) whether or not corrosion will occur under the given conditions
and (b) the passive lm thickness at 5-minute exposure time if ip = 50 a=cm2 .
Also assume that the density of the lm and the molecular weight of the stainless
steel are 7:8 g=cm3 and 55:85 g=mol, respectively and that the predominant
oxidation state is 3. Given data:
Solution:
Given data:
100

Cx = 1:2x10 6 mol=cm3
(static) = 0:07 cm
(flowing) = 0:008 cm
= 7:8 g=cm3
F = 96; 500 A:s=mol

z=3
D = 10 5 cm2 =s
icrit = 300 A=cm2
The reduction reaction is
O2 + 2H2 O + 4e = 4OH
with
o
EO
= 0:401 VHSE
2
(a) From eq. (6.99), the limiting current density for both conditions is
iL
iL
iL
3 (96500 A:s=mol) 10 5 cm2 =s 1:2x10 6 mol=cm3

zF DCx
=
0:07 cm
' 49:63 A=cm2 < icrit for corrosion under static solution
' 43:43 A=cm2 > icrit for passivation under owing solution
=
(b) The limiting current density for passivation under owing solution becomes the passive current density, then the passive lm thickness can be estimated using eq. (7.51) along with a density of 7:8 g=cm3 and a molecular weight
of 55:85 g=mol. Hence,
ip Aw t
zF
50x10 6 A=cm2 (55:85 g=mol) (300 s)

x =
(3) (96; 500 A:s=mol) (7:8 g=cm3 )
x = 0:371 m = 371 nm
x =
This is a reasonable result despite the crude approximation technique being

used in this example problem. The passive oxide lm may be CrOx (OH)3 2x :nH2 O
as per Figure 7.20.
7.5 For the reinforced concrete specimen (concrete slab) shown in Example
7.2, calculate (a) the chloride ion penetration depth (x) when the potential
gradient due to diusion and migration are equal and (b) the potential gradients.
[Solution: (a) x = 1:03 mm].
Solution:
(a) From eqs. (6.12) and (6.13),
d
dx dif f usion

d
dx electric
RT
xF
E
L
7.1. PROBLEMS
101
Equating these equation yields

x=
RT L
(8:314) (298) (8)
=
= 1:03 mm
EF
(2) (96500)
Then the potential gradients are
d
dx
d
dx
electric
electric
d
dx
d
dx
dif fusion
dif fusion
RT
(8:314) (298)
=
xF
(0103) (96500)
= 2:49 10
V =cm
7.6 For a reinforced concrete slab having a concrete cover 50-mm deep,
the threshold and the surface concentrations of chloride anions are Cth = 0:60
Kg=m3 and Cs = 19 Kg=m3 . Also, D = 32 mm2 =yr is the diusivity of chloride
anions. Determine (a) the chloride molar ux, (b) the time (Ti ) to initiate
corrosion on an uncoated reinforcing steel surface (Figure 7.21c). Explain. (c)
Plot the concentration prole of chloride anions at the corrosion initiation time
Ti . Calculate (d) the rate of iron hydroxide F e(OH)2 production (molar ux
and mass ux) at the anodic regions for an anodic current density of 1:5 A=cm2 ,
(e) the corrosion rate (CR ) of steel in mm=yr, (f) the time required for cracking
and spalling due to the formation of a critical rust (F e(OH)3 ) volume if the bar
diameter is reduced only 25 m and (g) the time for repair and the apparent
mass of rust per area.
Solution:
(a) The chloride molar ux at ti = 11 years can be calculated using eq.
(6.8). Thus,
JCl =
i
1:5 A=cm2
=
' 1:5510
zF
(1) (96; 500 A:s=mol)
11
mol
cm2 : sec
(b) The time to initiate corrosion, eq. (7.63), is
ti
ti
ti
2
x2
Cth
erf 1 1
4D
Cs
2
(50 mm)
0:6 Kg=m3
1
=
erf
1
4 (31:61 mm2 =yr)
18 Kg=m3
' 13:43 years
=
(c) The concentration prole of chloride ions, C (x; ti ) at the approximated

initiation time of 13:43 years can be determined using the solution of Ficks
second law of diusion, eq. (7.59).
102
x
p
C (x; t) = Cs 1 erf
(7.59)
2 Dt
"
!#
10x
p
C (x; t) = 19 Kg=m3 1 erf
2
2 (32 mm =yr) (13:43 yr)
C (x; t) = y = 19:0 erfc (0:241 19x)
20
15
10
0
0
1.25
2.5
3.75
x
(d) From eq. (7.69) along with ia = icorr ,
JF e(OH)2
JF e(OH)2
icorr
1x10 6 A=cm2
=
zF
(2) (96500 A: sec =mol)
= 5:18 10 12 mol= cm2 : sec

=
Multiplying this result by the iron molar mass, 55:85 g=mol, yields
JF e(OH)2
JF e(OH)2
= 2:893 10 10 g= cm2 : sec = 9:123 10
' 91:23 g= m2 :yr ' 0:091 Kg= m2 :yr
Thus, the rate of rust [F e(OH)3 ] production, eq. (7.68), is
g= cm2 :yr
7.1. PROBLEMS
103
JF e(OH)3
JF e(OH)3
JF e(OH)3
MF e(OH)3
=
JF e(OH)2
(Rust)
MF e(OH)2
106:85 g=ml
=
91:23 g= m2 :yr
89:85 g=mol
' 108:49 g= m2 :yr

(Rust)
(e) The uniform corrosion rate (CR ) of ferrous ions (F e2+ ), eq. (7.74) at
the end of the 11th year
1:5 10 6 A=cm2 (55:85 g=mol)

ia Aw
=
zF
(2) (96500 A:sec=mol) (7:86 g=cm3 )
CR
CR
CR
= 5:5225 10
= 17 m=yr
11
cm= sec ' 0:017 mm=yr
Therefore, the corrosion rate, 127 m=yr, is rather low, but sucient to be
noticed after 13:43 years. This corrosion rate corresponds to pitting formation
at the 13th year; however, if the chloride ion supply continues, then the corrosion
eventually propagates.
(f ) If the reduction in diameter of the uncoated steel bar is 25 m, then the
time for some rust formation that causes cracking and spalling, eq. (7.64), is
tc =
25 m
= 1:47 yr
17 m=yr
(g) The repair time, eq. (7.65), is

tr
tr
= ti + tc = 13:43 yr + 1:47 yr
= 14:9 yr
Therefore, the rst concrete repair is required at 14:9 years. On the other
hand, The apparent mass of rust per area is
mrust
mrust
= Jrust :tc = 108:49 g= m2 :yr (1:47 yr)

= 159:48 g=m2 = 0:159 g=cm2
7.7 Assume that all electrochemical reactions are governed by the Nernst
equation, which species the relationship between the potential of an electrode
and the concentrations of the two species F e3+ and F e+2 involved in the reversible redox reaction at the working electrode. Assume a hydrogen-rich electrolyte. (a) Write down the electrochemical reaction for F e3+ and F e2+ and
104
the potential equation. (b) What is the driving force when the concentrations of
the species at the working electrode surface are equal? (c) What is the driving
force at the working electrode surface when CF e3+ (1; t) > 2CF e3+ (0; t) and
CF e2+ (0; t) = 0:5CF e3+ (0; t), where t > 0 at 25o C? (d) Derive the current
equation for the case described in part (c). Recall that the current is simply the
ow rate of electrons. (e) Draw schematic concentration proles for CO = CF e3+
when I = 0, I > 0 for reduction (F e3+ cation moves to the electrode surface)
and I < 0 for oxidation so that the F e3+ cation moves away from the electrode
surface.
Solution:
(a) The electrochemical reaction for O and R and the potential equation are
O + ze
F e3+ + e
E
= R
= F e2+ for z = 1
RT
CF e2+
= Eo
ln
zF
CF e3+
(b) There is no driving force because CF e3+ = CF e2+ and E = E o since

ln (CF e2+ =CF e3+ ) = ln (1) = 0. Therefore, there is no driving force for transport
of analyte to or from the working electrode surface.
(c) For CF e3+ (1; t) > 2CF e3+ (0; t),
F e3+ + e
E
E
E
= F e2+ for z = 1
RT
CF e2+ (0; t)
= Eo
ln
zF
CF e3+
RT
0:5C
F e3+ (0; t)
= Eo
ln
zF
CF e3+
RT
= Eo
ln (0:5)
zF
From Table 2.2, E o = 0:77 VSHE and the driving force is
E
E
8:314510 J:mol 1 K 1 (298 K)

= 0:44 VSHE
ln (0:5)
(1) [96; 500 J= (mol:VSHE )]
= 0:46 VSHE
(d) The current equation at the working electrode surface (x = 0) is

J
= D
Q = zF N
@C
@x
x=0
7.1. PROBLEMS
105
Figure 7.1:
where N is the mole number. Then, the fundamental relationship for the
current in any amperometric experiment derived as
dQ
@C
I=
= zF As J = zF As D
dt
@x x=0
(e) The schematic concentration proles for CO = CF e3+ is
7.8 Consider the reversible reaction O + ze = R (as in F e3+ + e = F e2+ )
for deriving the half-wave potential (E1=2 ) using I = 0:5IL , where IL is the
limiting current for a voltammogram. Assume that the initial solution contains
only the species O and that diusion is the form of mass transport so that the
current in a voltammetric cell is
I
I
= KO ([O]b [O]x=0 )
= KR ([R]x=0 [R]b ) = KR [R]x=0
(a)
(b)
where KO = zF As DO = and KR = zF As DR =, [R]b = 0 in the bulk solution

initially. Use the Nernst equation for dening the voltammetric cell potential.
Recall that the applied potential reduces O to R and that the current depends
on the rate at which O diuses through the diusion layer ().
Solution:
The Nernst equation gives the potential at the electrode surface. Thus,
E = Eo
[R]x=0
RT
ln
zF
[O]x=0
(c)
Initially, [O]x=0 = 0 in eq. (a) so that the current becomes the limiting
current (IL )
IL = KO [O]b
(d)
106
From eqs. (b) and (d),

[R]x=0 =
I
KR
(e)
Substitute eq. (d) into (a) yields

I
[O]x=0
= IL KO [O]x=0
IL I
=
KO
(f)
Substitute eqs. (e) and (f) into (c) gives
E
E
E
[R]x=0
RT
ln
zF
[O]
x=0
RT
I KO
= Eo
ln
zF
KR IL I
RT
KO
I
= Eo
ln
zF
KR
IL I
= Eo
and
RT
E=E
ln
zF
o
KO
KR
Use I = 0:5IL to get E = E1=2 and

E1=2 = E o
RT
ln
zF
RT
ln
zF
KO
KR
I
IL I
since ln [I= (IL I)] = ln [0:5IL = (IL 0:5IL )] ln [1] = 0. Hence,
Chapter 8
DESIGN AGAINST
CORROSION
8.1
PROBLEMS/QUESTIONS
CATHODIC PROTECTION
8.1 Why cathodic protection is not generally recommended for stress corrosion problems on high-strength ferritic steels?
Answer: Hydrogen embrittlement may be the main cause of corrosion on
ferritic steel cathodes when the hydrogen evolution occurs. In this case, cathodically discharged atomic hydrogen readily diuses into the iron matrix, specically
in voids, making the steel susceptible to hydrogen embrittlement due to a high
pressure (P ) build-up by molecular hydrogen within voids. This phenomenon
may be represented by the reaction H + H ! H2 . If P > ys (yield strength),
then the steel loses its strength and ductility.
8.2 A steel structure exposed to seawater is to be cathodically protected
using the sacricial anode technique. calculate a) the number of Zn anodes (N )
that will be consumed in a year if the Zn anode capacity is 770 A:h=Kg (average
value as per Table 8.2) and the current is 0:70 amps; and b) the individual weight
(M) of anodes so that N M W , where W is the total theoretical weight of the
anodes.
Solution:
Zn = Zn+2 + 2e
Ca = 770 A:h=Kg = 2:772x106 A:s=Kg
t = 1 year = 31:536x106 sec
Aw = 65:37 g=mol I = 0:7 A
z=2
F = 96; 500 A:s=mol
107
108
CHAPTER 8. DESIGN AGAINST CORROSION
Using Faradays law, Eq. (3.12c) or (8.60), the total theoretical weight of
anodes is
W
W
W
ItAw
zF
(0:70 A) 31:536x106 s (65:37 g=mol)

=
(2) (96; 500 A:s=mol)
= 7:48 Kg
=
Using the anode life (Ld = t) equation given in Table 8.4 yields the theoretical
number of anodes. Hence,
N
N
N
7Ca Aw
3zF
(7) 2:772x106 A:s=Kg (65:37 g=mol)

=
(3) (2) (96; 500 A:s=mol)
' 1
=
Then,
M>
W
= 7:48 Kg
N
8.3 Cathodically protect a vertical pressurized steel tank (ys = 414 MP a

and P = 12 M P a) using one ush mounted M g-Al-Zn bracelet (Bi = 0:9525
cm). Assume 2% tank coating damage per year and neglect any installation
damage if the tank is coated after installation. Use a bracelet with dimensions
equal to (0:50 cm) x (3 cm) x (6 cm). Calculate (a) the maintenance current
and current density if the initial current density and the design lifetime are
0:43 A=cm2 and 25 years. Will it be convenient to protect the tank having a
thickness of 1:8 cm? The tank height and the internal diameter are 65 cm and
15:24 cm, respectively. (b) Will the tank explode at the end of the anode life
time? Assume that the anode M g-alloy and x = 5; 000 ohm:cm for the soil.
Given data for the M g-alloy anode: = 1:74 g=cm3 , Aw = 24:31 g=mol and
Ca = 1; 230 A:h=Kg for the M g-Al-Zn anode (Table 8.2).
Solution:
The tank and the anode surface areas are, respectively
At
At
Aa
= di ht = () (15:24 cm) (25:40 cm)

= 1; 216 cm2
= N wL = (1) (3 cm) (6 cm) = 18 cm2
The initial current for polarizing the structure is
Ii = Aa i = 18 cm2 0:43 A=cm2 = 7:74 A
109
From Table 8.4, the average initial weight of the anode is

Wi
Wi
Wi
3Ii Ld
7Ca
(3) 7:74x10 6 A (219; 000 h)

=
(7) (1; 230 A:h=Kg)
= 1:86 grams
=
From Table, 8.5, the anode electrical resistance is

Rf
Rf
x
p
10 Aa
() 5x103 ohm; cm
p
= 370:24 ohm
10 18 cm2
Using Ohms law yields the initial potential (Ei ) using a rectier having a
capacity greater than Ei
Ei = Ii Rf = 7:74x10 6 A (370:24 ohm)

Ei = 2:87 mV
Erect > Ei
From Table 8.3, the polarized current density is chosen as 0:5 A=cm2 so
that
Ip = Aa ip = 18 cm2 0:5 A=cm2 = 9 A

The nal current for maintaining the structure polarized and cathodically
protected is
= (1 i c Ld ) (Aa i)
2%
= 1 10
(25) (Aa i)
100%
= 0:5Aa i = 0:5Ii
= (0:5) 18 cm2 0:43 A=cm2 = 3:87 A
If
If
If
If
(8.61)
For maintenance, the current and the nal current density are, respectively
I
if
Ip + If
9 A + 3:87 A
=
= 6:44 A
2
2
I
6:44 A
=
= 0:36 A=cm2
Aa
18 cm2
Finally, the maintenance or nal potential is
Ef = IRf = 6:44x10 6 A (370:24 V =A)

Ef = 2:38 mV
110
a) There will be a potential drop and a current change of
E
I
= Ei Ef = Ei = 2:87mV 2:38 mV = 0:49 mV

= Ii I = 7:74 A 6:44 A = 1:30 A
Both E and I represent a 17% reduction. Therefore, it is convenient to

cathodically protect the steel tank. The initial and nal corrosion rates of the anode in terms of current density are 0:43 A=cm2 and 0:36 A=cm2 , respectively.
The initial corrosion rate of the anode in mm=y is
0:43x10 6 A=cm2 (24:31 g=mol)

ii Aw
=
zF
(2) (96; 500 A:s=mol) (1:74 g=cm3 )
CR;i
CR;i
= 3:11x10
11
cm=s = 0:0010 mm=y
and the nal corrosion rate becomes
0:36x10 6 A=cm2 (24:31 g=mol)

if Aw
CR;;f =
=
zF
(2) (96; 500 A:s=mol) (1:74 g=cm3 )
CR;;f
= 2:61x10
11
cm=s = 0:0008 mm=y
b) The nal thickness of the M g-alloy anode is Bf = (0:0008 mm=y) (25 y) =

0:02 mm, which is a thin foil and it must be replaced by a new anode.
The hoop stress in the steel tank is
h
h
=
<<
Pd
(12 MP a) (15:24 cm)
=
= 50:8 M P a
2B
2 (1:8 cm)
ys
As a result, he steel tank will not deform neither explode because h << ys
and there are no cracks; therefore, it will not corrode at all the end of the design
life of 25 years.
8.4 A 2-m diameter steel tank containing water is pressurized at 200 kP a.
The hoop stress, thickness, and height are 420M P a, 2 cm, and 8 cm, respectively. If the measured corrosion rate is 0:051 mm=y, determine a) the tank life
and b) the developed current. Data: = 7:86 g=cm3 and Aw = 55:86 g=mol.
Solutions:
F e ! F e+2 + 2e
P = 200 kP a
= 420 M P a
CR = 0:051 mm=y
d=2m
B = 2 cm
h=8m
111
a) From eq. (8.64),

CR
iAw
Pd
=
zF
2t
(200 kP a) 2x103 mm
Pd
=
2CR
(2) (420; 000 kP a) (0:051 mm=y)
t =
(8.64)
t = 9:34 years = 2:94x108 sec

b) From eq. (8.61),
i =
i =
zF B
tAw
(2) (96; 500 A:s=mol) 7:86 g=cm3 (2 cm)

(2:94x108 s) (55:85 g=mol)
i = 1:84x10
(8.63)
A=cm2 = 184 A=cm2
For a lateral area As = dh, the current becomes

I
I
I
= As i = dhi
= () 2x102 cm 8x102 cm 1:84x10

= 92:49 A
A=cm2
8.5 (a) Derive eq. (8.58) and (b) calculate the theoretical anode capacity
(Ca ) for magnesium (Mg) and zinc (Zn).
Solutions:
(a) From eqs. (5.30) with = 1 and Table 8.4,
m =
W
ItAw
zF
3It
7Ca
eq. (5.30)
Table 8.4
Let m = W since both represent mass. Thus, the anode capacity equations
is
ItAw
zF
Ca
3It
7Ca
3zF
7Aw
112
(b) Anode capacity for M g and Zn:

Mg
Ca;Mg
Ca;Mg
= M g+2 + 2e
3zF
(3) (2) (96; 500 A:s=mol)
=
=
7Aw
(7) (24:31 g=mol)
A:h
= 2; 969
Kg
and
Zn = Zn+2 + 2e
3zF
(3) (2) (96; 500 A:s=mol)
Ca;Zn =
=
7Aw
(7) (65:37 g=mol)
A:h
Ca;Zn = 1; 104
Kg
8.6 Show that =
Solution:
p
Rs =RL .
From eq. (8.20),

x
dx
dx
d2 x
dx2
= o exp (x)
(8.20)
= o exp (x)
(a)
= 2 o exp (x)
(b)
Substituting eqs. (a) and (b) into (8.18) yields
d2 x
Rs
=
x
dx2
RL
Rs
2 o exp (x) =
o exp (x)
RL
r
Rs
=
RL
(8.18)
(c)
(d)
8.7 Use an annealed (@ 792o C) 1040 steel plate of B = 0:635 cm thickness

to design a cylindrical pressurized vessel using a safety factor (SF ) of 2. The
annealed steel has a yield strength of 355 M P a. Calculate (a) the average
allowable pressure according to the theory for thin-walled vessels. Will the
vessel fail when tested at 2 M P a for 10 minutes? If it does not fail, then
proceed to cathodically protect the cylindrical pressure vessel as a domestic
or home water heater having a cylindrical magnesium (M g) anode rod. All
113
dimensions shown below. Calculate (b) the applied hoop stress, the current,
the potential for polarizing the heater and the resistance of the system, (c) the
theoretical anode capacity and the anode lifetime of the anode in years and (d)
how much electric energy will delivery the Mg anode rod? The steel vessel has a
98% internal glass coating (vitreous porcelain enamel lining) for protecting the
steel inner wall against the corrosive action of portable water. Assume a water
column of 76:20 cm and an internal pressure of 1 M P a. Assume that the exterior
surface of the steel vessel is coated with an appropriate paint for protecting it
against atmospheric corrosion and that the anode delivers 1:5 VCu=CuSO4 : The
NACE recommended potential for steels is 85 VCu=CuSO4 .
Hot H2O
emf: (+) (-)

Electric Heating Cold
Elements
H2O
Steel Tank
H = 85 cm
Di = 40.64 cm
w = 900 ohm.cm
Aw, s = 55.85 g/mol
PS = 7. 86 g/cm3
Drain Valve
+
+
-
Anode
Mg Anode Rod
L = 0.75H cm
d = 5.08 cm
Aw,Mg = 24.31 g/mol
Mg = 1.74 g/cm3
Di
Solution:
(a) The design hoop stress (tangential stress) is given
=
ys
355 MP a
=
= 177:50 M P a
SF
2
The hoop stress (average tangential stress) equation is used for determining
the average allowable pressure
P Di
2B
2B
(2) (0:635cm) (177:50 M P a)
=
= 5:55 MP a
Di
40:64 cm
Assuming that the pressure vessel, as well as the glass coating, is crack-free
one can deduce that the pressure vessel will not fail because P > Ptest = 2 M P a.
114
(b) Since the steel major element is iron, the reaction F e+2 + 2e = F e is
assumed in this problem. Using eqs. (8.66) and (8.65) yield the applied hoop
stress and the protective current density, respectively
i =
P Di
(1 M P a) (40:64 cm)
=
= 32 M P a
2B
(2) (0:635 cm)
(2) (96; 500 A: sec =mol) 7:86 g=cm3 (0:635 cm)

zF B
=
tAw;F e
(6:312 108 sec) (55:85 g=mol)
i = 27:33 A=cm2
The current and the potential for protecting the steel tank are based on the
lateral area of the tank in contact with water. Letting the water column be
h = 76:20 cm yields
As
As
As
I
=
=
=
=
Ao (1 s )
Di h (1 s ) = () (40:64 cm) (76:20 cm) (1 0:98)
194:58 cm2
iAs = 27:33 A=cm2 194:58 cm2 = 5:32 mA
The cell potential along with the NACE recommended potential of 0:85
VCu=C SO4 is
E = Ec + Ea = 0:85 V + 1:5 V = 0:65 V
Thus, the system resistance is
Rs =
E
0:65 V
=
= 122:18 ohm
I
5:32x10 3 A
(c) The anode lifetime is based on the oxidation reaction Mg ! M g+2 + 2e.
From eq. (8.4), the anode capacity is
Ca =
zF
(0:50) (2) (96; 500 A:s=mol)
=
= 1; 103 A:h=Kg
Aw
24:31 g=mol
Thus, anode eective length is La = 0:75H = (0:75) (85 cm) = 63:75 cm so

that the anode mass becomes
Va
ma
ma
d2 La
() (5:08 cm)2 (63:75 cm)
=
= 1; 292:10 cm3
4
4
= a Va = (0:50) 1:74 g=cm3 1; 292:10 cm3

= 1:12 Kg
=
From Table 8.4, the average anode lifetime is
Ld
Ld
115
7Ca ma
(7) (1; 103 A:h=Kg) (1:12 Kg)
=
3Ia
(3) (5:32x10 3 A)
= 172:468:11 h = 19:7 years
=
This result seems reasonable.

(d) A 1:12 Kg of anode mass will deliver an electric energy of
EE
EE
EE
= Ca ma
= (1; 103 A:h=Kg) (1:12 Kg) = 1; 235:36 A:h
= 4:45 MJ
Recall that 1 J = 1 A:s.

ANODIC PROTECTION
8.8 For anodic protection, the interface potential of the structure is increased to passive domain, provided that the metal exhibits active-passive behavior. Thus, prevention of corrosion is through impressed anodic current.
Explain including the mathematical denition of the applied anodic current
density.
Explanation: The impressed anodic current imparts an initial corrosion
rate (icorr ) is shifted to a low value at ipass (passive current density). Otherwise,
passivation will not occur. The applied anodic currents density
i = iox ired
where iox is the oxidation and ired is the reduction current densities.
8.9 What are the implications of cathodic protection of steels in acid solutions?
Answer: The cathodic protection currents in acid solution can lead to hydrogen liberation (H2 ) and embrittlement of steels. This makes anodic protection
the most preferred choice for protection of chemical process equipment.
8.10 Why is passivation important for anodic protection? What is the
mechanisms that explains the electron motion for reactions to take place?
Answer: First of all, passivation is the process for oxide lm formation on
the metal exposed to an acid solution. Once passivation is completed, an anodic
current-potential pair has to be kept within a reasonable range to keep the metal
116
in its passivated stated. The mechanism is quantum mechanical electron tunneling through a thin oxide lm, which may be an insulator or a semiconductor.
However, ionic tunneling seems to be restricted by the lm width acting as a
barrier.
8.11 What are the passive lm preferred break-down sites?
Answer: Grain boundaries (if any), nonmetallic inclusions and aws on
the metal oxide surface.
8.12 Calculate (a) the potential for the two titanium reactions given below. These reactions represent the passivation process for titanium-oxide lm
formation. Thus, anodic protection is natural because the T iO2 lm acts as
a semiconductor barrier to protect the underlying metallic T i from corrosion,
T i ! T i2+ + 2e at E o = 1:63 VSHE . (b) Determine the P h.
T i + O2
T i + 2H2 O
= T iO2
Go = 852:70 kJ=mol
= T iO2 + 4H + + 4e Go = 346:94 kJ=mol
Solutions:
(a) The potential for T i + O2 = T iO2 ,
E=
G
(852:70 kJ=mol)
=
= 4:42 mV
zF
2 (96500 J=mol:V )
Using the Nernst equation,
E
E
RT
RT
[T iO2 ]
ln Ksp = E o
ln
zF
zF
[T i] [O2 ]
= E o since [T iO2 ] = [T i] = [O2 ] = 1
= Eo
For T i + 2H2 O = T iO2 + 4H + + 4e at E o = 0:860 V (Table 2.3 ),

E=
G
(346:94 kJ=mol)
=
= 1:80 mV
zF
2 (96500 J=mol:V )
(b) Using the Nernst equation for T i + 2H2 O = T iO2 + 4H + + 4e gives

the pH
4
E
E
RT
RT
[T iO2 ] [H + ]
ln Ksp = E o
ln
2
zF
zF
[T i] [H2 O]
4RT +
= Eo
ln H
since [T iO2 ] = [T i] = [H2 O] = 1
zF
= Eo
117
Thus,
zF (E E o )
= exp
4RT
+
2 (96500) (0:0018 + 0:86)
H
= exp
4 (8:314) (298)
+
8
H
= 5:1417 10
Then,
H+
pH
pH
= log H + = log 5:1417 10 8

= 16:78
8.13 The eect of sulfuric acid (H2 SO4 ) concentration on polarization behavior of a metal at 25o C can be assessed obtaining experimental potentiodynamic polarization curves. Below is a data set for the critical current density
(ic ) of a hypothetical metal.
C (%)
ic (A=cm2 )
0
46
20
30
30
23
40
17
50
12
60
8
70
5
Plot ic = f (C) and explain whether or not passivation is aected by the

concentration of sulfuric acid.
Solution:
Curve tting yields a polynomial t: ic = 46:096 0:907 23C + 4:552 3
10 3 C 2 with R2 = 0:98. The plot is
118
For anodic protection, ic must exist for passivation to take place by the formation of an oxide lm. The plotted data indicates that ic nonlinearly decrease
with increasing percent concentration. This trend means that passivation is readily as ic decreases because at the applied current density i = ic ! ipass until
E ! Epass > Ecorr . Therefore, passivation is enhanced by increasing H2 SO4
concentration.
8.14 Below is a data set taken from Table 12.7 in reference [10] for determining the eect of concentration of sulfuric acid (H2 SO4 ) at 24 C on the
critical current density of 316 (UNS S31600) stainless steel at 24o C.
%C
H2 SO4
ic mA=cm2
CR:icorr (mm=y)
0
4:7
0
40
1:6
2:2
45
1:4
5:6
55
1:0
8:9
65
0:7
7:8
75
0:4
6:7
(a) Do non-linear curve tting on ic versus %CH2 SO4 and plot ic = f (%CH2 SO4 ).
(b) Assume that F e, Cr, M o and Mn oxides simulteneously go into solution.
Now calculate CR for these four elements using the given experimental ic values,
do curve tting on the new CR data set and the experimental CR:icorr values
versus %CH2 SO4 . Plot the CR functions for F e, Cr, Mo and Mn, and plot
the experimental CR:icorr data ant its linear curve t equation in order to compare the corrosion behavior of the stainless steel at icorr and these elements ic .
Explain.
Solution:
(a) Non-linear curve tting. Let y = ic and x = %CH2 SO4

ic = 4:6924 9:8094 10 2 C + 5:5224 10 4 C 2
with a correlation coecient R2 = 0:97. The plot is
119
y 3.75
2.5
1.25
0
0
20
40
60
80
x
Actually, Aw has been used as the atomic weight of an element, but now Aw
becomes the molecular weight of the alloy.
Element
%
Aw
Aw
Fe
62
C
0.08
Cr
18
Mn
2
Mo
3
Ni
14
Si
1
P
0.045
S
0.03
1 X
1
fi Aw;i =
(62 55:845 + 0:08 12 + 18 51:996 + ::::)
100
100
= 75:684g=cm3
=
Oxidation of iron (Fe):

Aw;F e = 55:85 g=mol
F e = 7:857 g=cm3
z=2
CR;F e;ic =
CRF e =
ic AwF e
zF F e
F e ! F e2+ + 2e with
ic AwF e
(55:85 g=mol) (ic )
=
zF F e
(2) (96500 A:s=mol) (7:857 g=cm3 )
(55:85)(0:4)(103 )
(2)(96500 )(7:857)
%C
H2 SO4
ic mA=cm2
CR;F e:ic (mm=y)
0
4:7
54.59
(10) (60 60 24 365) = 4:6460
40
1:6
18.58
45
1:4
16.26
55
1:0
11.62
65
0:7
8.13
75
0:4
4.65
Polynomial t: yF e = 6:4166 10 3 x2 1:1395x + 54:501 with R2 = 0:97

Oxidation of chromium (Cr):
120

Cr = 7:19 g=cm3
Aw;Cr = 52 g=mol
CR;Cr;ic =
CRF e =
Cr ! Cr3+ + 3e with z = 3
ic AwCr
(52 g=mol) (ic )
=
zF Cr
(3) (96500 A:s=mol) (7:19 g=cm3 )
(52)(0:4)(103 )
(3)(96500 )(7:19)
(10) (60 60 24 365) = 3:1513
%C
H2 SO4
ic mA=cm2
CR;Cr:ic (mm=y)
0
4:7
37.03
40
1:6
12.61
45
1:4
11.03
55
1:0
7.88
65
0:7
5.51
75
0:4
3.15
Polynomial t: yCr = 4:5731 10 3 x2 0:772 92x + 36:862 with R2 = 96

Oxidation of molybdenum (Mo):
Aw;Mo = 95:96 g=mol
Mo = 10:22 g=cm3
z=3
CR;Mo;ic =
CRF e =
M o ! M o3+ + 2e with
ic AwMo
(95:96 g=mol) (ic )
=
zF Mo
(3) (96500 A:s=mol) (10:22 g=cm3 )
(95:96)(0:4)(103 )
(3)(96500 )(10:22)
%C
H2 SO4
ic mA=cm2
CR;Mo:ic (mm=y)
(10) (60 60 24 365) = 4:0913

0
4:7
48.07
40
1:6
16.37
45
1:4
14.32
55
1:0
10.23
65
0:7
7.16
75
0:4
4.09
Polynomial t: yMo = 5:3368 10 3 x2 0:967 2x + 47:000 with R2 = 0:98

Oxidation of manganese (Mn):
Aw;Mn = 54:94
Mn = 7:44 g=cm3
CR;Mn;ic =
CRF e =
M n ! Mn2+ + 2e with z = 2
ic AwMn
(54:94 g=mol) (ic )
=
zF Mn
(2) (96500 A:s=mol) (10:22 g=cm3 )
(54:94)(0:4)(103 )
(2)(96500 )(7:44)
%C
H2 SO4
ic mA=cm2
CR;Mn:ic (mm=y)
(10) (60 60 24 365) = 4:8264

0
4:7
56.71
40
1:6
19.31
45
1:4
16.89
55
1:0
12.07
65
0:7
8.45
75
0:4
4.83
Plots: y = CR;ic and x = %CH2 SO4 . Red dot are experimental data from
the icorr point of the polarization curves. So ic > icorr at CH2 SO4 < 55%.
Red (2):
yF e = 6:4166 10 3 x2 1:1395x + 54:501
Green (4): yCr = 4:5731 10 3 x2 0:772 92x + 36:862
Purple (3): yMo = 5:3368 10 3 x2 0:967 2x + 47:000
Black (1 Top Curve): yMn = 6: 6637 10 3 x2 1:1836x + 56:618
Experimental: yCR ;exp = 0:148 87x 5:1658 10 4 x2 0:32656
with R2 = 0:85
121
50
y
37.5
25
12.5
0
0
20
40
60
80
x
The above gure shows that the AISI 316 stainless steel is a corrosion resistant alloy, but the curves for F e, Cr, M o and M n indicate that these elements
oxide very rapidly at CH2 SO4 < 55%. Beyond this concentration the experimental data and the calculated CR values are similar. In other words, when
CH2 SO4 55% the icorr and ic position on the polarization curves are not far
apart on the normal log scale (x-axis).
8.15 This problem deals with the nature of the anodic oxide lm that forms
on titanium in 0:9% NaCl. This media is isotonic with human blood for surgical
implants made out of titanium and its alloys. Normally, the passive oxide lm
on titanium mainly consists of T iO2 . The table given below contains data for
the passive current density (ip ) as a function of sweep rate (de/dt in mV/s) [52]
on titanium in 0:9% N aCl containing electrolyte. (a) Convert the ip data to
corrosion rate CR in mm=y. Then plot both ip and CR as functions of sweep
rate v = dE=dt. (b) Explain if this titanium material would be suitable for a
human transplant for a prolong time.
v = dE=dt
(mV=s) 10
50
100 300 500
ip mA=cm2
0:13 0:25 0:50 1:58 2:10
Solution:
The oxidation reaction for titanium is T i ! T i2+ +2e @ Eo = 1:630 VSHE .
The corrosion rate is
CR =
ip Aw
zF
122
For Aw = 47:867 g=mol and = 4:54 g=cm3 ,

Aw
47:867 g/mol
= 5:4629 10
=
zF
(2) (96500 A.s/mol) 4:54 g/cm3
cm3
A:s
Thus,
CR = 5:4629 10
cm3
A:s
ip
v = dE=dt
(mV=s)
10
50
100
300
500
ip mA=cm2 0:13 0:25 0:50 1:58

2:10
CR 10 8 mm=y 7:10 13:66 27:32 86:31 114:72
Let y = ip and x = v. The plot for ip = f (v) is
3
2.5
y
2
1.5
1
0.5
0
0
125
250
375
500
625
x
Curve tting gives

mA
ip = 0:09932
+ 4:2327 10
cm2
with a correlation coecient R2 = 0:99.

Let y = CR and x = v. The plot for CR = f (v) is
mA s
cm2 mV
123
v = dE=dt
(mV=s)
10
50
100
300
500
ip mA=cm2 0:13 0:25 0:50 1:58

2:10
CR 10 8 mm=y 7:10 13:66 27:32 86:31 114:72
Polynomial t: y = (0:23122x + 5:4276) 10 8 mm=y with a correlation

coecient R2 = 0:99
150
125
100
75
50
25
0
0
125
250
375
500
625
x
These results indicate that a titanium transplant is suitable for a human

being. For instance, the lowest and highest corrosion rates are
CR;min
CR;max
= (0:23122 (10) + 5:4276) 10 8 = 7:74 10 8 mm=y
= (0:23122 (500) + 5:4276) 10 8 = 1:21 10 6 mm=y
The corrosion rates are extremely low and therefore, the titanium transplant
would not cause detrimental health eects in humans.
124
Chapter 9
ELECTRODEPOSITION
9.1
PROBLEMS
9.1 Copper cations are reduced on a cathode for 8 hours at a current of 10

amps. and 25o C: Calculate a) the theoretical weight of copper deposited on the
cathode and b) the number of coulombs of electricity in this electrodeposition
process. Data: Aw;Cu = 63:55 g=mol and F = 96; 500 C:
Solution:
Cu+2 + 2e = Cu
a) From eq. (9.8g) with F = 96; 500 C = 96; 500 A:s=mol

W
W
ItAw
(10 A) (8x60x60 s) (63:55 g=mol)
=
zF
(2) (96; 500 A:s=mol)
= 94:83 grams @ 100% ef f iciency
=
b) From eq. (9.8b),

Q = It = (10 A) (8x60x60 s)
Q = 288; 000 C (= A:s)
9.2 An electrochemical cell operates at 6 A, 25o C and 85% current eciency
in order to electrolytically deposit copper ions (Cu+2 ) from a leaching solution
in a 8 hour shift. Calculate a) the amount of electrolytically deposited Cu
and b) the thickness of the deposit layer of copper. Data: As = 100 cm2 (total
cathode surface area), Aw;Cu = 63:55 g=mol, = 8:96 g=cm3 and F = 96; 500
C=mol:
Solutions:
Cu+2 + 2e = Cu
125
126
CHAPTER 9. ELECTRODEPOSITION
a) From eq. (9.9) with F = 96; 500 C = 96; 500 A:s=mol

W
W
ItAw
(0:85) (6 A) (8x60x60 s) (63:55 g=mol)
=
zF
(2) (96; 500 A:s=mol)
= 48:36 grams
=
b) Letting m = W = 48:36 grams yields

V
= xAT =
m
48:36 g
=
AT
(8:96 g=cm3 ) (100 cm2 )
x = 0:54 mm
x =
9.3 It is desired to electroplate chromium (Cr) onto a ferritic-martensitic

carbon steel automobile bumper for an attractive appearance and corrosion
resistance. An electroplating cell is operated at I = 6:68 A and 25o C. The
Cr+3 cations are reduced on the bumper (cathode) to form a thin lm of 1:5 m
thick. How long will it take to produce a 1:5 m thick electroplated chromium
lm on the bumper if the total surface area is 100 cm2 and = 60%?
Solution:
Cr+3 + 3e = Cr
a) Using eq. (9.9) with F = 96; 500 C = 96; 500 A:s=mol; = 7:20 g=cm3
and Aw = 52 g=mol yields
W
W
W
=
=
t =
t =
ItAw
(0:85) (6 A) (8x60x60 s) (63:55 g=mol)
=
zF
(2) (96; 500 A:s=mol)
V = As x = 100 cm2 1:5x10 4 cm 7:20 g=cm3

0:1080 g
zF W
(2) (96; 500 A:s=mol) (0:1080 g)
=
IAw
(0:60) (6:68 A) (52 g=mol)
100 sec
9.4 An electrowinning cell contains 2x10 4 mol=cm3 of Cu+2 ions and

operates for 10 minutes at 40o C and 1 atm. Assume an ionic copper diusivity
equals to 2:34x10 5 cm2 =s. Calculate the current density due to diusion mass
transfer. Compare your result with a typical industrial current density value of
200 A=m2 . Explain any discrepancy.
Solution:
Cu+2 + 2e = Cu
9.1. PROBLEMS
127
From eq. (9.68),

Jd
Jd
Jd
DC
p o = Co
Dt
D
t
= 2x10 4 mol=cm3
= 2:23x10
(2:34x10 5 cm2 =s)

() (600 s)
mol
cm2 :s
From eq. (9.71),

id
id
= zF Jd = (2) (96; 500 A:s=mol) 2:23x10

= 4:30x10
A=cm2 ' 43 A=m2
mol
cm2 :s
Obviously, the assume diusion mechanism for reducing copper ions is just
part of the total mass transfer. In fact, id = 43 A=m2 represents approximately
22% of the total current density. If the electrolyte is continuously replenished
with fresh electrolyte, then the remaining 78% current density has to come from
migration and convection mass transfer.
The total molar ux using 200 A=m2 current density is
Jx
Jx
i
200x10 4 A=cm2
=
zF
(2) (96; 500 A:s=mol)
mol
= 1:04x10 7
cm2 :s
=
Thus, the migration and convection molar ux becomes

Jm + Jc = Jx Jd = 8:13x10
mol
cm2 :s
9.5 Calculate the amount of silver that can be electroplated in an electrochemical cell containing Ag+ ions and operates at 7 A, 25o C and 101 kP a for
10 minutes. Assume a current eciency of 95%.
Solution:
Ag + + e = Ag
From eq. (9.9),
W
W
ItAw
(0:95) (7 A) (10x60 s) (107:87 g=mol)
=
zF
(1) (96; 500 A:s=mol)
= 4:46 grams
=
128
9.6 What are the dierences between galvanic and electrolytic cells? Recall
that both are electrochemical cells.
Answer: Figure 2.2 shows the dierences between these cells. However,
in a galvanic cell, a chemical reaction generates an electric current ow and
consequently,chemical energy is converted into electrical energy and the cathode
is the positive electrode. On the other hand, in an electrolytic cell, electrical
energy is converted into chemical energy and the cathode is the negative electrode
since the supply of electrons comes from an external source, such as a galvanic
cell or dc generator.
9.7 Consider the bipolar electrode for electrorening metal M . Thus, the
rate of formation (reduction) and dissolution (oxidation) are treated as steadystate quantities. Despite that the initial formation of a thin lm at the cathode
face and dissolution rates are controlled by reactions at the electrode-electrolyte
interfaces, assume a steady-state diusion mechanism. Derive expressions for
the weight gain at the cathode side and the weight loss at the anode side.
x'
JM
JM
Electrode
Solution:
Reduction
0
JM =D@C=@x
0
= D0 Co Cx0 =x0
Co > Cx0
W 0= V 00= x0A00
Eliminating x0and x yields

0
W 0= A00D0 Co Cx0 =JM
x
JM+2
Oxidation
JM +2 = D@C=@x
0
JM +2 = D Cx Co =x
Cx > Co
W = V = xA
W = AD Cx Co =JM +2
According to the given conditions, W 0 = W since A0 = A, 0 = and

JM = JM +2 .
9.8 A steel plate is Ni-plated for corrosion protection, but its appearance is
not so appealing. Therefore, a chromium electroplating process is carried out for
decorative purposes. Eventually, 0:25 g of Cr+6 cations are electroplated on the
9.1. PROBLEMS
129
Ni-plated surface for a period of 15 minutes at 8 amps. If the density and atomic
weight of chromium are 7:19 g=cm3 and 52 g=mol, respectively, calculate (a)
the thickness of the electroplated lm of chromium from its highest oxidation
state and (b) the deposition rate. Data: As = 100 cm2 (cathode area).
Solution:
Cr+6 + 6e
H+
= Cr
(a) Thickness:
W
0:25 g
=
2
As
(100 cm ) (7:19 g=cm3 )
x = 3:48 m
x =
(b) Production rate:

PR
PR
W
0:25 g
=
= 2:78x10
t
900 s
= 1 g=h
=
g=s
(c) From eq. (9.16),

zF W
ItAw
A:s
(6) 96; 500 mol
(0:25 g)
=
= 0:39
(8 A) (900 s) (52 g=mol)
= 39%
=
This is a low, but typical current eciency in Cr electroplating.

9.9 It is desired to produce a 20 m thick lm of chromium on a Ni-plated
steel part, which has a surface area of 65 cm2 . This can be accomplished by
setting up an electroplating cell to operate at 7 amps and current eciency
of 70%. The density and atomic weight of chromium are 7:19 g=cm3 and 52
g=mol, respectively. Calculate a) the amount of Cr being plated and b) the time
it takes to plate the 20 m thick lm of chromium from a solution containing
Cr+6 cations at 30o C.
Solution:
Cr+6 + 6e = Cr
a) Amount of Cr:
W
W
W
= V = xAs
= 7:19 g=cm3 20x10

= 0:94 g
cm 65 cm2
130
b) From eq. (9.16),

zF W
IAw
A:s
(6) 96; 500 mol
(0:94 g)
t =
= 2; 124:67 sec
(0:70) (7 A) (52 g=mol)
t = 35:40 min
t =
9.10 Predict (a) the electric potential E, (b) the time in minutes, and (c)
the lm growth rate in m= min for electroplating a 10 m-thick Cr lm on
a N i-undercoated steel part when the electrolyte contains 10 4 mol=l of Cr+3
cations at 25o C. The Ni-plated steel part has a 10 cm2 surface area. The cell
operates at 50% current eciency and at a passive current density of 5:12x10 3
A=cm2 .
Solution:
Cr+3 + 3e = Cr
= 7:19 g=cm3
As = 10 cm2
o
ECr
= 0:744 V
z=3
Aw;Cr = 52 g=mol
= 0:50
aCr+3 = 10 4 mol=l
(a) Using Nernst equation yields

E
E
E
RT
ln (aCr+3 )
zF
(8:314 J=mol:K) (298 K) 4
> Eo = :0744V +
ln 10
(3) (96; 500 J=mol:V )
> Eo = 0:82 V
> Eo = E o +
(b) Integrating eq. (7.21) yields the time
zF
zF x
dx =
iAw
iAw
0
(3) (96; 500 A:s=mol) 7:19 g=cm3 10 4 cm

t =
(0:50) (5:12x10 3 A=cm2 ) (52 g=mol)
t = 26 min
t =
(c) The lm growth rate is

dx
dt
dx
dt
x
10 m
=
t
26 min
m
= 0:38
min
=
9.1. PROBLEMS
131
9.11 The dissociation of silver hydroxide, AgOH, is 1:10x10 4 at 25 C in

an aqueous solution. (a) Derive an expression for the degree of dissociation as a
function of total activity [CT ] and plot the resultant expression for 0 < [CT ] <
0:50 mol=l, (b) calculate the degree of dissociation constant 1 when the molar
concentration is [CT ] = 0:144 mol=l, and (c) determine the Gibbs free energy
change Go .
Solution:
a) The expression and the plot are
AgOH
Ke
= Ag+ + OH
[Ag+ ] [OH ]
=
= 1:10x10
[AgOH ]
From eq. (2.67) with x = y = 1;

1
1
1=(x+y)
Ke x x y y
[CT ]
1=2
= 1:05x10 2 [CT ]
=
1+1=(x+y)
1=2
= Ke1=2 [CT ]
0.25
0.2
0.15
0.1
0.05
0.125
0.25
0.375
C T (mol/liter )
b) The degree of dissociation:
1 = 1:05x10 2 [0:144]
c) The free energy change is
1=2
= 0:028
0.5
132
Go
Go
= RT ln (Ke ) = 8:314
J
mol:o K
22:58 kJ=mol
(298o K) ln 1:1x10 4
Therefore, the reaction as written will proceed since Go < 0.

9.12 Calculate (a) the concentration of AgOH, Ag + and OH at 25 C
and (b) the pH if [CT ] = 0:144 mol=l and 1 = 0:028.
Solution:
a) AgOH = Ag + + OH and K = 1:10x10
[Ag + ] = [OH ] for charge balance so that
(From Example 2.11). Let

2
[Ag+ ] [OH ]
[OH ]
Ke =
=
[AgOH]
[AgOH]
p
OH
=
K [AgOH]
(a)
(b)
The dissociation of water ant its rate constant are

H2 O
Kw
= H + + OH
[H + ] [OH ]
=
= 10
[H2 O]
(c)
14
(d)
From eq. (2.64a) along with [H2 O] = 1 mol=l,
OH
= x1 [CT ] = (1) (0:028) [0:144 mol=l] = 4:03x10 3 mol=l
mol
g
COH = OH Aw;OH = 4:03x10 3
17
= 6:85x10
l
mol
+
Ag
= OH = 4:03x10 3 mol=l
mol
g
g
CAg+ = Ag+ Aw;Ag = 4:03x10 3
107:87
= 0:43
l
l
l
From eq. (2.64c),
[AgOH] = (1 1 ) [CT ] = 0:14 mol=l

CAgOH = [AgOH] Aw;[AgOH] = (0:14 mol=l) (124:87 g=mol)
CAgOH = 17:48 g=l
From eq. (d),
(e)
2
g
(f)
l
(g)
(h)
9.1. PROBLEMS
H+
133
Kw
10 14
=
= 2:48x10 12 mol=l
[OH ]
4:03x10 3 mol=l
= log H + = log 2:48x10 12 = 11:61
pH
9.13 An electrochemical cell contains 75 g=l of Cu+2 ions at 35o C. Calculate (a) the Reynold and Sherwood numbers,(b) the diusion ux (Jx ), (c) the
current density (i) and (d) the the applied potential (E). Data:
d
L=x
w
N
Kv
D
vx
P
Characteristic distance
Cathode height
Cathode width
Number of cathodes
Kinematic viscosity
diusivity
Flow velocity
Electrical Power
= 12 cm
.
= 100 cm
.
= 80 cm
.
= 50
.
= 0:80 cm2 =s
.
= 1:24x10 5 cm2 =s
= 46:90 cm=s
.
= 32 kW
.
Solution:
Cu+2 + 2e = Cu z = 2
CCu+2 = (75g=l) = (63:55 g=mol) = 1:18 mol=
CCu+2 = 1:18x10 3 mol=cm3
= 0:85
F = 96; 500 Aa:s=mol
(a) From eq. (9.4), (7.5) and (7.25), the Reynold and Sherwood numbers are
Re
Sc
Sh
vx d
(46:90 cm=s) (12 cm)
=
= 703:50
Kv
(0:80 cm2 =s)
Kv
0:80 cm2 =s
=
= 64; 516:13
D
1:24x10 5 cm2 =s
2
1=3
1=2
(Sc ) (Re )
= 709:19
3
(b) The diusion ux Jx :
Jx
Jx
Jx
@C
DCCu+2
= D
=
=
@x
x
1:24x10 5 cm2 =s 1:18x10

=
100 cm
10 mol
= 1:46x10
cm2 :s
(c) From (7.13), the current density is
mol=cm3
134
i = zF Jx Sh
A:s
i = (2) 96; 500
1:46x10
mol
i = 2x10
A=cm2 = 200 A=m2
10
mol
cm2 :s
(709:19)
(d) From elementary physics, the electrical power divided by the current is
the applied potential. Thus,
Ac
As
As
I
E
E
= wL = (80 cm) (100 cm) = 8; 000 cm2
= 2N Ac = (2) (50) 8; 000 cm2

= 800; 000 cm2 = 80 m2
= iAs = 200 A=m2 80 m2 = 16 kA

P
32 kW
32 kV=A
=
=
=
I
16 kA
16 kA
= 2 volts
9.14 An electrolyte containing P b+2 ions at 35o C is used in an electrowinning cell. The electrolyte is under steady laminar force convection. Use the
data given below to determine (a) the the Sherwood number, (b) the diusion
ux and (c) the current.
Cb
D
L=x
Sc
Re
As
Bulk concentration
diusivity
Cathode length
Schmidt Number
Reynolds Number
Total cathode area
Current eciency
= 75 g=l
.
= 1:24x10 5 cm2 =s
= 100 cm
= 64; 516:13
.
= 703:50
.
= 800; 000 cm2
= 85%
Solution:
P b+2 + 2e = P b
Cb = (75 g=l) = (207:19 g=mol)
Cb = 0:362 mol=l = 3:62x10 4 mol=cm3
(a) From eq. (9.25), the Sherwood number is
Sh
Sh
2
1=3
1=2
(Sc ) (Re )
3
2
1=3
1=2
(64; 516:13) (703:50)
= 709:19
3
9.1. PROBLEMS
135
(b) The diusion ux is

Jx
Jx
Jx
@C
DCb
= D
=
=
@x
x
5
2
1:24x10 cm =s 3:62x10
=
100 cm
11 mol
= 4:49x10
cm2 :s
mol=cm3
(c) The current is

i = zF Jx Sh
A:s
i = (2) 96; 500
4:49x10
mol
11
mol
cm2 :s
(709:19)
i = 6:14x10 3 A=cm2
I = iAs = 6:14x10 3 A=cm2 800; 000 cm2

I = 4:91 kA
9.15 A hypothetical rotating-disk cell is shown below for electrowinning
copper cations from a solution containing Co = 65 g=l at 40o C and 101 kP a.
Assume that the diusivity and the electrolyte kinematic viscosity are 10 5
cm2 =s and 0:60 cm2 =s, respectively. Each disk has a radius of 50 cm; a width
of 6 cm, and only a 160o segment is immersed in the electrolyte. Assume a cell
current eciency range of 0:50 1:
Theoretically, analyze the eect of a) the angular velocity ! on the current

density and b) the angular velocity (!) and the current density () on the
production rate of metal powder, and c) the potential (E) and the current
density () on the energy consumption .
Solution:
Data: Cu+2 + 2e = Cu @ T = 40o C
136
Co = 65 g=l = 65x10 3 g=l = (63:55 g=mol)

Co = 1:02x10 3 mol=cm3
D = 10 5 cm2 =s
= 160o
Aw = 63:55 g=mol
r = 50 cm
Kv = 0:60 cm2 =s
w = 6 cm
Total eective surface area:

h1 = r cos (=2) = 8:68 cm
h2 = r = h1 = 41:32 cm
2
o
Aseg = r2 180
o
r2
2
L = r sin (=2) = 49:24 cm

S = ro =180o = 139:63 cm
sin
()
= 3; 063:13 cm2
180o
Aseg
Aarc
As
= wL = 295:44 cm2
= 4 (2Aseg + Aarc ) = 25; 686:80 cm2 ' 2:57 m2
a) From eq. (9.107),
i =
i =
p
0:62zF Co D2=3 !
K 1=6
(0:62) (2) (96; 500 A:s=mol) 1:02x10
mol=cm3
(0:60 cm2 =s)
A:s1=2 p
i =
616:87
!
m2
1=6

10
2=3 p
cm2 =s
!
8000
i
(A/m2)
7000
6000
5000
4000
3000
2000
1000
0
20
40
60
(Rad/sec)
80
100
9.1. PROBLEMS
137
12
10
8
PR
(g/s)
6
4
2
0
0.5
0.6
0.7
0.8
0.9
300
400
200
100
(Hz)
Figure 9.1:
b) From 7.16,
PR
iAs Aw
=
zF
616:87
PR
PR
616:87
A:s1=2
m2
A:s1=2
m2
p
As Aw !
zF
p
2:57 m2 (63:55 g=mol) !
(2) (96; 500 A:s=mol)
p
1=2
=
0:52 g:s =s !
12
10
PR
(g/s)
0.9
0.8
0.7
8
6
4
2
0
100
200
300
(Hz)
400
500
138
c) From eq. (9.18),
zF E
Aw
(2) (96; 500 A:s=mol) E
=
(63:55 g=mol)
A:s E
=
3; 036:98
g
kW:h E
=
0:84
where E is in volts
Kg
8
7
(kW.h/Kg)
4
E (V)
4
3
2
1
0
0.5
0.6
0.7
0.8
0.9
The energy consumption does not depend directly on the angular velocity,
but on the applied potential and current density, which in turn, depends on the
applied current density.
9.16 Use the hypothetical rotating-disk voltammetry data given in the table
below for determining the diusivity D of a metal cation M +2 in solution at
room temperature.
! (1= sec)
!1=2 s1=2
i mA=cm2
100 225 400

625
10
15
20
25
4:81 7:22 9:58 12:10
Co = 2:21x10 6 mol=cm3
Kv = 0:056 cm2 =s
z=2
900
30
14:38
1; 225
35
16:80
9.1. PROBLEMS
139
Solution:
Linear least squares on the given data, i vs: !1=2 , yields the Levich plot
i = 0:488 57mA:cm 2 + 0:49771 mA:s1=2 :cm 2 !1=2
20
18
16
14
2
i (mA/cm )
12
10
8
6
4
2
0
10
20
1/2
30
40
(Hz)
From eq. (9.107),
p
0:62zF Co D2=3 Kv 1=6
!
Slope =
0:62zF Co D2=3 Kv 1=6
!3=2
Slope
D =
1=6
0:62zF Co Kv
"
0:49771x10 3 A:s1=2 :cm 2
D =
A:s
mol
(0:62) (2) 96; 500 mol
2:21x10 6 cm
(0:056 cm2 =s)
3
i =
1=6
#3=2
= 3:97 10 5 cm2 =s
9.17 It is desired to produce copper according to the electrolytic cell diagram
() Steelj Cu+2 =Cu; H + =H2 jH2 O=O2 jP bO2 (+)
for 24 hours at which time the cathodes are mechanically stripped (removed).
Copper is reduced from an aqueous copper sulfate (Cu SO4 ) and sulfuric acid
140
(H2 SO4 ) solution at 35o C. The anodes operate at 100% current eciency with
respect to oxygen evolution and that for the cathodes is = 90% due to hydrogen
evolution. These type of electrodes are connected in parallel within 100 tanks
that operate at 2:4 volts each and the electrodes have a specic submerged
area Ae . Use the following relevant data to perform some calculations given
below. Cost of electricity per kW.h: Ce = 0:30 $=kW:h, Market price of copper:
Cmarket = $0:70=Kg, and
P = 72 kW (Power)
E = 2:4 V
NT = 100 (Tanks)
Na = 30 (Anodes per tank)
Nc = 29 (Cathodes per tank)
Ae = 0:80 m2 (Electrode area)
Aw = 63:54 g=mol
DCu+2 = 1:24x10 5 cm2 =s
Kv = 0:80 cm2 =s
vx = 0:312 cm=s (Velocity of Cu+2 )
d = 6 cm (electrode distance)
Ce = 0:30 $=kW:h (Electricity)
(a) Write down all the reactions and the standard half-cell potential involved
in this electrowinning process. What should the applied potential be? Calculate
(b) the total current, the anodic and cathodic current densities, and (c) Scp
, Re ,
Sh and Cb in g=l per tank. Let the anode characteristic length be L = Ae .
Use the Sherwood number (Sh < 100) and the Reynolds number (Re < 2; 300)
to assure force laminar ow. Determine (d) the production rate (PR ) and the
total weight produced (WT ) in 24 hours, (e) the energy consumption (). Use
your engineering economics skills to estimate (f ) the cost of energy consumed
(Cte ), the total cost of production (Cprod ) and the gross income (GI ) in 24
hours if the industrial cost of electric energy and the market price of copper
are Ce = $0:30 kW:h and Cmarket = $3:193=lb = $7:041=Kg, respectively.
o
2
[Solutions: (a) EHalf
cell 1:57 V , (b) ic = 0:001293 A=cm , (c) Sh 39
and Cb = 78:80 g=l].
are
Solution:
(a) The reactions, the standard half-cell potential and the applied potential
Anode:
Cathode:
Cathode:
Overall :
o
EHalf
cell
o
EHalf
cell
2H2 O ) 4H + + O2 + 4e
Cu+2 + 2e ) Cu
2H + + 2e ) H2
2H2 O + Cu+2 + 2H + ) Cu + 4H + + O2 " +H2 "
o
o
o
= EH
+ ECu
+ EH
= 1:23 V 0:337 V + 0
2O
2
1:57 V
o
EHalf
cell
(b) The total current
9.1. PROBLEMS
141
I=
P
72 103 A V
=
= 3:0 104 A
E
2:4 V
Electrode areas per tank :

Aa
Ac
= NT Na Ae = (100) (30) 8; 000 cm2 = 24:0x106 cm2

2
= NT Nc Ae = (100) (29) (8; 000 cm) = 23:2x106 cm2
Current densities per tank :
ia
ic
I
3:0 104 A
=
= 0:001250 A=cm2 = 1:250
Aa
24:0x106 cm2
I
3:0 106 A
=
= 0:001293 A=cm2 = 1:293
Ac
23:2x106 cm2
A
m2
A
m2
(c) Assume force laminar ow. The Schmidt ( Sc ), Reynolds ( Re ) number

and the anode length are
Sc
Re
= Kv =D = 0:80 cm2 =s = 1:24x10 5 cm2 =s = 64:52x103
= vx d=Kv = (0:312 cm=s) (6 cm) = 0:80 cm2 =s = 2:34
From eq. (9.101) along with the anode characteristic length (L), the Sherwood number is
p
p
Ae = 0:8 m2 = 0:8944 m2 = 89:44 cm2
#1=3

1=3 "
2
9
vx d2
9
(0:312 cm=s) (6 cm)
=
=
5
LD
5
(89:44 cm) (1:24x10 5 cm2 =s)
L =
Sh
Sh
39
or from eq. (9.97)
Sh
Sh

1=3
9
d
=
(Sc Re )
5
L

1=3
9
6
=
64:52 103 (2:34)
39
5
89:44
Using eq. (9.97) for one tank yields the cathodic current density as the
limiting current density ( ic = iL ) and the bulk concentration ( Cb ) in g=l per
tank.
142
ic
Cb
1=3
9zF Cb vx d2 D2
5
L4
1=3
5ic
L4
9zF vx d2 D2
"
(5) 0:001293 A=cm2

A:s
(9) (2) 96; 500 mol
0:312
(89:44 cm)
2
cm
(6 cm) 1:24x10
s
Cb
Cb
Cb
= 1:24 10 3 mol=cm3 = 1:24 mol=l

= (1:24 mol=l) (63:55 g=mol) ' 78:80 g=l
2
5 cm2
s
#1=3
Alternatively, using eqs. (9.94) and (7.87b) with C = Cb gives per tank
Sh
Cb
Cb
Cb

1=3
2
2
1=3
1=2
1=2
=
(Sc ) (Re )
=
64:52x103
(2:34)
41
3
3
A
0:001293 cm
(89:44 cm)
ic L
2
=
=
2
A:s
zF DSh
(2) 96; 500 mol 1:24 10 5 cm
(41)
s
= 1:18x10 3 mol=cm3 = 1:18 mol=l
= (1:18 mol=l) (63:55 g=mol) = 75 g=l
Both equations give fairly similar results. Lets use the results given by eq.
(4.94) in eq. (9.87b).
(d) Production rate ( PR ) and total weight produced ( WT ) in 24 hours:
PR
PR
WT
wt
wc
=
=
=
=
g
A
(0:90) 0:001293 cm
23:2x106 cm2 63:55 mol
ic Ac Aw
2
=
zF
(2) (96; 500 A:s=mol)
8:8897 g= sec = 32:003 Kg=h = 768:07 Kg=day (Total)
(32:003 Kg=h) (24 h) = 768:07 Kg (Total)
WT =NT = (768:07 Kg) =100 = 7:68 Kg (Per tank)
(7:68 Kg) =29 = 0:26483 Kg = 264:83 grams (Per cathode)
The energy consumption is
P
72 kW
=
= 2:25 kW:h=Kg
PR
32:003 Kg=h
= 0:0225 kW:h=Kg (Per tank)
= 7:76x10 4 kW:h=Kg (Per cathode)
=
(Total)
9.1. PROBLEMS
143
If the cost of electricity per kW.h is Ce = 0:30 $=kW:h, then the cost of
energy consumed is
Cte
Cte
Ct
Cc
=
=
=
=
Ce WT = (0:30 $=kW:h) (2:25 kW:h=Kg) (768:07 Kg)

$518:45 (Total)
Cte =NT = ($518:45) =100 = $5:1845 (Per tank)
Cte = (Nc ) = ($518:45) =29 = $17:88 (Per Cathode)
Thus, the cost of production is
Cprod
Cprod
Cte
$518:45
=
WT
768:07 Kg
= $0:68=Kg
=
If the market price is Cmarket = $3:193=lb = $7:041=Kg, then the gross

income in 24 hours is
GI
GI
= (Cmarket Cprod ) (WT ) = ($7:041=Kg $0:68=Kg) (768:07 Kg)

= $4; 885:70 (For a 24-hour run)
This result is rather low. What can be improved for a higher GI ?

9.18 A Hall-Heroult (HH) cell is used to produce molten aluminum containing hydrogen. The hydrogen content can be removed by allowing a thin lm
of molten aluminum ow down on an inclined plane during pouring in vacuum.
The incline plane is shown below and it is in the L-w- space, where is the
lm thickness and w is the width.
The weight-induced and gravity-induced free uid ow occurs in the xdirection. Using Newtons law of viscosity yields the force acting on the uid
in the direction of the ow, together with the moment balance. Thus, this
phenomenon is described by an ordinary dierential equation.
144
d2 vx
= g cos ()
dy 2
with BCs
vx = 0 @ y =
vx > 0 @ y > 0
where v = Fluid viscosity, vx = Fluid velocity and = Density of the

uid: Solve this dierential equation and calculate the average a) value of the
boundary layer, b) velocity vx , c) molar ux of hydrogen due to both diusion
and convection eects, d) time it takes to remove the dissolved hydrogen along
the channel length L and the amount of hydrogen being removed, and e) the
Reynolds number. Given data:
= Al = 2:5 g=cm3
v = 40 g:cm 1 s 1
DH = 5x10 3 cm2 =s
CH;b = 30 mol=cm3
CH = 0 @ y = 0
w = 50 cm
L = 100 cm
= 2o
m = 100 g=s
g = 981 cm=s2
Solution:
The solution of the above dierential equation is
dvx
dy
vx
dvx
vx
vx;max
g cos ()
y
v
Z
g cos () y
=
ydy
v
g cos () 2
=
y2
2v
=
g 2 cos ()
2 v
The average uid velocity is
vx
vx
vx
vx
1 g cos () 2
y 2 dy
0
2 v
0
1 g cos ()
y3
2 y
2v
3 o
1
vx dy =
g 2 cos ()
3 v
2
vx;max
3
The cross-sectional of the owing uid is A = w and the average mass ow

rate is
9.1. PROBLEMS
145
m = vx A
g 3 w cos ()
m =
3 v
a) Thus, the average boundary layer becomes
"
3v m
=
gw cos ()
#1=3
= 0:46 cm
b) The average uid velocity is

vx =
g 2 cos ()
= 4:34 cm=s
3 v
c) The average molar ux mathematical model is dened in Chapter 4. Using

eq. (4.9a) along with d=dx = 0 gives
Jx
= Jd + Jc = DH
Jx
= DH
@C
+ vx CH;b
@x
Cs Cx
+ vx CH;b
Using the boundary conditions Cs = 0 at y = 0 and Cx = CH;b at y =

yields
Jx
Jx
DH CH;b
+ vx CH;b
DH
mol
= CH;b
+ vx = 130:53
cm2 s
=
d) The average time along the channel length is

L
= 23:04 sec
vx
Then, the amount of hydrogen removed is
t=
m = tm = 2; 304 g 2:30 Kg
e) Using eq. (9.78) yields the Reynolds number along with d =

Re =
vx
= 0:13
v
9.19 An electrowinning cell produces 10 Kg=h of nickel (Ni) at a current

eciency () of 80%: The cell contains 20 cathodes and operates at a current of
146
215 A=m2 and a potential of 2 V . Determine (a) the energy consumption, (b)
the ow rate of the electrolyte and (c) the cathode length for a width of 1 m.
The concentration of nickel cations is 35 g=l. (d) Plot eq. (9.25) and explain
the result.
Solution:
N i2+ + 2e = N i
@ E = 2 V and i = 215 A=m2 with z = 2
4
PR = 10 Kg=h = 10 g=h;
N = 20;
Aw;Ni = 58:71 g=mol
4
3
Co = 35 g=l = 5:96x10 mol=cm
(a) From, eq. (9.23),
As
I
P
=
=
=
=
zF Pr = (iAw ) = 53:10 m2
iAs = 11; 416:20 A
EI = 22:83 kW
P=PR = 2:28 kW:h=Kg
(b) The ow rate of the electrolyte:

Fr = Pr =Co = 4:76 l=min
(c) The cathode length:
Ac = As = (2N ) = 1:3275 m2
L = Ac =w = 1:3275 m
(d) From eq. (9.25), the simplied energy consumption equation becomes
= 1:83=
(in kW:h=Kg)
which is plotted in gure given below indicating that the energy consumption
is strongly dependent on the current eciency since is inversely proportional
to : However, this strong dependency begins to have a lesser eect when 0:25
and when > 0:80 the energy consumption is signicantly reduced.
Let y = and x = so that y = 1:83=x.
9.1. PROBLEMS
147
50
y 37.5
25
12.5
0
0
0.2
0.4
0.6
0.8
9.20 Below is an electrolytic cell diagram used in an electrowinning factory

for producing solid copper on cathode electrodes.
() Steelj Cu+2 =Cu; H + =H2 jH2 O=O2 jP bO2 (+)
Recall that the cathodes are mechanically stripped (removed) after the electrowinning run is accomplished. The electrolyte used in this electrowinning
operation contains aqueous copper sulfate (Cu SO4 ) and sulfuric acid (H2 SO4 )
solution, and it is maintained at 35o C. Assume that the anodes operate at 100%
current eciency with respect to oxygen evolution and that for the cathodes is
= 88% due to hydrogen evolution. These type of electrodes are connected in
parallel within 80 tanks that operate at 2:6 volts each and the electrodes have
a specic submerged area Ae . Use the following relevant data to perform some
calculations given below. The average retail price of electricity (cost of electricity) per kWh: Ce = 0:14 $=kW:h, Market price of copper: Cmarket = $0:17=Kg,
and
P = 72 kW (Power)
E = 2:6 V
NT = 100 (Tanks)
Na = 30 (Anodes per tank)
Nc = 29 (Cathodes per tank)
Ae = 0:80 m2 (Electrode area)
Aw = 63:54 g=mol
DCu+2 = 1:24x10 5 cm2 =s
Kv = 0:80 cm2 =s
vx = 0:312 cm=s (Velocity of Cu+2 )
d = 6 cm (electrode distance)
Ce = 0:14 $=kW:h (Electricity)
(a) Write down all the reactions and the standard half-cell potential involved in this electrowinning process. What should the applied potential be
148
compared to the half-cell potential? Is the given operating potential (2:6 volts)
suitable for this electrowinning? Calculate (b) the total current, the anodic
and cathodic current densities, and (c) Sc , Rpe , Sh and Cb in g=l per tank.
Let the anode characteristic length be L = Ae . Use the Sherwood number (Sh < 100) and the Reynolds number (Re < 2; 300) to assure force laminar
ow. Determine (d) the production rate (PR ) and the total weight produced
(WT ) in 24 hours, (e) the energy consumption (). Use your engineering economics skills to estimate (f ) the cost of energy consumed (Cte ), the total cost
of production (Cprod ) and the gross income (GI ) in 24 hours if the industrial cost of electric energy and the market price of copper are Ce = $0:30
kW:h and Cmarket = $3:193=lb = $7:041=Kg, respectively. [Solutions: (a)
o
2
EHalf
cell 1:57 V , (b) ic = 0:001194 A=cm , (c) Sh 39 and Cb = 73:08
g=l].
are
Solution:
(a) The reactions, the standard half-cell potential and the applied potential
Anode:
Cathode:
Cathode:
Overall :
o
EHalf
cell
o
EHalf
cell
2H2 O ) 4H + + O2 + 4e
Cu+2 + 2e ) Cu
2H + + 2e ) H2
2H2 O + Cu+2 + 2H + ) Cu + 4H + + O2 " +H2 "
o
o
o
= EH
+ ECu
+ EH
= 1:23 V 0:337 V + 0
2O
2
1:57 V
o
EHalf
cell
The applied potential should be E EHalf

cell . So the given operating
potential
(2:6
volts) is suitable for this electrowinning cell because 2:6 volts >
o
EHalf cell .
(b) The total current
I=
P
72 103 A V
=
= 27; 692 A
E
2:6 V
Electrode areas per tank :
Aa
Ac
= NT Na Ae = (100) (30) 8; 000 cm2 = 24:0x106 cm2

2
= NT Nc Ae = (100) (29) (8; 000 cm) = 23:2x106 cm2
Current densities per tank :
9.1. PROBLEMS
ia
ic
149
I
27; 692 A
=
= 0:001154 A=cm2 = 1:250
Aa
24:0x106 cm2
I
27; 692 A
=
= 0:001194 A=cm2 = 1:293
Ac
23:2x106 cm2
A
m2
A
m2
(c) Assume force laminar ow. The Schmidt ( Sc ), Reynolds ( Re ) number

and the anode length (L) are
Sc
Re
= Kv =D = 0:80 cm2 =s = 1:24x10 5 cm2 =s = 64:52x103
= vx d=Kv = (0:312 cm=s) (6 cm) = 0:80 cm2 =s = 2:34
From eq. (9.101) along with the anode characteristic length (L), the Sherwood number is
p
p
Ae = 0:8 m2 = 0:8944 m2 = 89:44 cm2
#1=3

1=3 "
2
9
vx d2
9
(0:312 cm=s) (6 cm)
=
=
5
LD
5
(89:44 cm) (1:24x10 5 cm2 =s)
L =
Sh
Sh
39
or from eq. (9.97)
Sh
Sh

1=3
9
d
=
(Sc Re )
5
L

1=3
9
6
=
64:52 103 (2:34)
39
5
89:44
Using eq. (9.97) for one tank yields the cathodic current density as the
limiting current density ( ic = iL ) and the bulk concentration ( Cb ) in g=l per
tank. Thus,
ic
Cb
1=3
9zF Cb vx d2 D2
5
L4
1=3
5ic
L4
9zF vx d2 D2
"
(5) 0:001194 A=cm2

A:s
(9) (2) 96; 500 mol
0:312
(89:44 cm)
2
cm
(6 cm) 1:24x10
s
Cb
Cb
Cb
= 1:15 10 3 mol=cm3 = 1:24 mol=l

= (1:15 mol=l) (63:55 g=mol) = 73:08 g=l
2
5 cm2
s
#1=3
150
Alternatively, using eqs. (9.94) and (7.87b) with C = Cb gives per tank

1=3
2
2
1=3
1=2
1=2
=
(Sc ) (Re )
=
64:52x103
(2:34)
41
3
3
A
0:001194 cm
(89:44 cm)
ic L
2
=
=
2
A:s
zF DSh
(2) 96; 500 mol 1:24 10 5 cm
(41)
s
Sh
Cb
= 1:189x10 3 mol=cm3 = 1:19 mol=l

= (1:19 mol=l) (63:55 g=mol) = 75:63 g=l
Cb
Cb
Both equations give fairly similar results. Lets use the results given by eq.
(4.94) in eq. (9.87b).
(d) Production rate ( PR ) and total weight produced ( WT ) in 24 hours:
PR
PR
WT
wt
wc
=
=
=
=
g
A
(0:88) 0:001194 cm
23:2x106 cm2 63:55 mol
ic Ac Aw
2
=
zF
(2) (96; 500 A:s=mol)
8:0266 g= sec = 28:90 Kg=h ' 694 Kg=day (Total)
(28:90 Kg=h) (24 h) = 694 Kg (Total)
WT =NT = (694 Kg) =100 = 6:94 Kg (Per tank)
(6:94 Kg) =29 = 0:23931 Kg = 239:31 grams (Per cathode)
The energy consumption is
P
72 kW
=
= 2:49 kW:h=Kg (Total)
PR
28:90 Kg=h
= (2:49 kW:h=Kg) =100 = 0:0249 kW:h=Kg (Per tank)
= 8:59x10 2 kW:h=Kg (Per cathode)
=
If the cost of electricity per kW.h is Ce = 0:14 $=kW:h, then the cost of
energy consumed is
Cte
Cte
Ct
Cc
=
=
=
=
Ce WT = (0:14 $=kW:h) (2:49 kW:h=Kg) (694 Kg)

$241:93 (Total)
Cte =NT = ($241:93) =100 = $2:4193 (Per tank)
Cte = (Nc ) = ($518:45) =29 = $8:34 (Per Cathode)
Thus, the cost of production is

Cprod
Cprod
Cte
$241:93
=
WT
694 Kg
= $0:35=Kg
=
9.1. PROBLEMS
151
If the market price is Cmarket = $3:193=lb = $7:041=Kg, then the gross

income in 24 hours is
GI
GI
= (Cmarket Cprod ) (WT ) = ($7:041=Kg $0:35=Kg) (694 Kg)

= $4; 643:60 (For a 24-hour run)
This result is rather low. What can be improved for a higher GI ?
152
Chapter 10
HIGH-TEMPERATURE
CORROSION
10.1 A silicon oxide crucible is used to melt pure aluminum in the presence
of oxygen at 1300o C. a) Will the silicon oxide (Si O2 ) corrode? b) Whats the
oxygen pressure? [Hint: Use Figure 10.1].
Solution:
From Figure 10.1 @ 1300o C,
4
3 Al
+ O2 = 23 Al2 O3
GoAl2 O3 = 774 kJ=mol
SiO2 = Si + O2
GoSiO2 = +586 kJ=mol
4
2
Go = 188 kJ=mol
3 Al + SiO2 = 3 Al2 O3 + Si
o
o
G = GAl2 O3 + GoSiO2
or
4Al + 3O2 = 2Al2 O3
3SiO2 = 3Si + 3O2
4Al + 3SiO2 = 2Al2 O3 + 3Si
GoAl2 O3 = 774 kJ=mol

GoSiO2 = +586 kJ=mol
Go = 188 kJ=mol
The SiO2 crucible will corrode at 1300o C since molten aluminum is reduced
Al2 O3 (alumina) because Go < 0.
b) From eq. (10.5b) and Po = 1 atm (standard pressure),
Go
o
Go
= RT ln [K]
= RT ln
[Al2 O3 ]2=3
= RT ln
[Si] [O2 ]
PO2
= RT ln [O2 ] = RT ln
Po
4=3
[Al]
153
1
[O2 ]
154
CHAPTER 10. HIGH-TEMPERATURE CORROSION
Thus,
PO2
= Po exp
PO2
= 5:71x10
Go
RT
7
188x103 J=mol
= (1 atm) exp
(8:314 J=mol:o K) (1573o K)
atm
10.2 An Alumina (Al2 O3 ) crucible contains molten copper and oxygen (O2 )
at 1300o C. Determine a) if the crucible will corrode, if so, calculate the oxygen
pressure.
Solution:
From Figure 10.1 @ 1300o C,
4Cu + O2 = 2Cu2 O
2Al2 O3 = 43 Al + O2
GoCu2 O = 130 kJ=mol

GoAl2 O3 = +774 kJ=mol
or
4Cu + O2 = 2Cu2 O
2Al2 O3 = 43 Al + O2
4Cu + 2Al2 O3 = 2Cu2 O + 43 Al
GoCu2 O = 130 kJ=mol

GoAl2 O3 = +774 kJ=mol
Go = +644 kJ=mol
The Al2 O3 crucible will not corrode at 1300o C because Go > 0. Therefore,
there is no need to calculate the oxygen pressure.
10.3 In the case of thick oxide formation at high temperature, the PillingBedworth theory may have a limited applicability. Explain why this may be the
case.
Solution: Basically, the Pilling-Bedworth theory fails when strains develop
during the formation and growth of the oxide scale. Consequently, the scale may
rupture or become nonprotective.
10.4 If the protective nature of an oxide lm at room temperature is lost
at relatively high temperatures, explain the sequence of the oxide thickening
process.
Explanation: This is the case of oxide lm growth in which the mechanical
properties and the thermal coecient of expansion are dierent from the base
metal. Therefore, the scale cracks and spalls. If the nature of the thick oxide
is volatile, such as tungsten oxide (W O3 ) at T > 550o C, the oxide vaporizes at
high pressure.
10.5 Determine the values of Kw from Figure 10.10 and plot Kw vs. T .
What can you conclude from this plot?
Solution:
From Figure 10.10,
155
T (o C)
900
950
1050
1100
1150
1200
1350
Kw mg:cm 4 h 1
10:40
25:00
56:00
83:00
125:0
250:0
750:0
2According
to these data, the trend is described by the curve tting equation
R = 0:99
Kw = 7 10 30 mg:cm 4 h 1 T 10:234
800
600
400
200
0
875
1000
1125
1250
1375
10.6 Use the data given below to plot Kp vs. Aw;oxide (oxide molecular
weight) at T = 1000o C and PO2 = 1 atm. What can you conclude from the
plot?
Element
Co
Cu
Fe
Si
Atomic Weight
(g=mol)
58:93
63:54
55:85
28:10
Molecular Weight
(g=mol)
CoO ! 74:93
Cu2 O ! 143
F eO ! 71:85
Si O2 ! 60:10
2 K
p
g O2 =cm4 :s
2:10x10 10
6:30x10 9
4:80x10 10
1:20x10 12
Solution:
Polynomial t with R2 = 0:98
Kp x10
10
mol
= 52:69 6 + 0:8:022 7
Aw;oxide
g
156
Figure 10.1:
One can conclude that Kp increases linearly with molecular weight of the
oxide, but more data is needed to be certain of this linear relationship.
10.7 Calculate a) the equilibrium constant K and b) the dissociation oxygen
pressure PO2 for the oxidation of aluminum at 1100O C:
Solution:
a) From Figure 10.1 @ 1100o C,
4
3 Al
Go
K
K
+ O2 = 23 Al2 O3
GoAl2 O3 = 820 kJ=mol of O2
= RT ln [K]
Go
820x103 J=mol
= exp
= exp
RT
(8:314 J=mol:o K) (1373o K)
= 1:58x1031
b) Dissociation oxygen pressure and Po = 1 atm (standard pressure):

2=3
PO2
[Al2 O3 ]
4=3
Po
PO2
[Al] [O2 ]
Po
1 atm
=
= 6:35x10
K
1:58x1031
32
atm
157
10.8 If 100 grams of pure aluminum (Al) oxidizes according to the reaction
4Al + 3O2 = 2Al2 O3 , calculate the P B ratio dened by
P B = VAl2 O3 =VAl
whereV 0s are volumes. Data: Al = 2:70 g=cm3 and Al2 O3 = 2:70 g=cm3 .
Solution:
Aw;Al = 26:98 g=mol

Aw;Al2 O3 = 101:96 g=mol
Al = 2:70 g=cm3
Al2 O3 = 3:80 g=cm3
If WAl = 100 g, then

WAl2 O3
WAl2 O3
WAl2 O3
2Aw;Al2 O3
= WAl
4Aw;Al
(2) (101:96 g=mol)

= (100 g)
(4) (26:98 g=mol)
= 188:95 g
Thus,
VAl
VAl2 O3
WAl
100 g
=
= 37:04 cm3
Al
2:70 g=cm3
WAl2 O3
188:95g
=
= 49:72 cm3
Al2 O3
3:80 g=cm3
and
PB
PB
VAl2 O3
49:72 cm3
=
VAl
37:04 cm3
= 1:34
=
10.9 A chromium bar is exposed to oxygen gas at 900o C. Calculate a) the

oxygen partial pressure and b) the oxygen activity.
Solution:
a) Using Figure 10.1 yields
4Cr + 3O2 = 2Cr2 O3
G = 550 kJ=mol @ T = 900o C
158
and
G = RT ln (K)
G
550x103 J=mol
K = exp
= exp
RT
(8:314 J=mol.o K) (1173o K)
K
is
= 3:11x1024
The equilibrium constant with the standard pressure Po = 1 atm = 101 kP a
K
PO2
PO2
3
a2 (Cr2 O3 )
1
1
=
= 3
=
a4 (Cr) a3 (O2 )
a (O2 )
PO2 =Po
1=3
24
= Po K
= (1atm) 3:11x10
= 6:85x10
atm = 6:92x10
kP a
b) The activity of oxygen is
= 3:11x1024
aO2
= K
aO2
= 6:85x10
1=3
1=3
mol=l = 6:85x10
12
mol=cm3

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ELECTROCHEMISTRY

University of Puerto Rico

3 THERMODYNAMICS OF AN ELECTROCHEMICAL CELL

(b) Absorption of oxygen (O2 ) in neutral or basic medium.

CHAPTER 1. FORMS OF CORROSION

Corrosion reduces the thickness of metal parts of a structure and as result,

CHAPTER 1. FORMS OF CORROSION

Cu Cu SO4 Half cell + Zn SO4 Zn Half cell

+ Cu SO4 Zn SO4 Bridge

= Cu + Cu SO4 Cu SO4 + Zn SO4 Zn SO4 + Zn Zn 0

2.3 Explain why an electrode potential dierence occurs in Figure 2.4.

2.9 If a monopole contains a net charge (Q) due to 10 12 moles of a species

Q = zF X = (2)(96; 500 C=mol) 10

19; 300 N:m=C

Thus, the electric force acting on the particle becomes

2:14 105 N=C

= zF E = (2) 96; 500

10CHAPTER 3. THERMODYNAMICS OF AN ELECTROCHEMICAL CELL

Letting ECu = EH = 0:118 V yields

= Cu+2 = 4:06x10 16 mol=l

3.2 Consider a galvanic cell j Zn j0:10M ZnSO4 j j0:10 M N iSO4 j N i j.

3.3 The dissociation constant of silver hydroxide, AgOH, is 1:10x10 4 at

(b) The free energy change is

Therefore, the reaction will proceed as written since Go < 0.

12CHAPTER 3. THERMODYNAMICS OF AN ELECTROCHEMICAL CELL

(b) The dissociation of water ant its rate constant are

where [H2 O] = 1 mol=l and

= log H + = log 2:48x10 12 = 11:61

3.5 For an electrochemical copper reduction reaction at 25 C and 101 kP a,

(a) The reduction reaction and its standard potential are

= zF E o = (2) 96; 500

(b) The equilibrium constant is

(c) The concentration of copper cations is

CCu+2 = Cu+2 Aw;Cu = 3:97x10 12 mol=l (63:55 g=mol)

3.6 Use the electrochemical cell j Cd 0:05 M Cd+2 0:25 M Cu+2 Cu j to

b) Using eqs. (2.32) and (2.35) at constant pressure yields

From eq. (2.26),

14CHAPTER 3. THERMODYNAMICS OF AN ELECTROCHEMICAL CELL

G = zF E = (2) 96; 500

From eq. (2.34),

= 147; 000 J=mol + (317:32o K) 13:38

From eq. (236),

Using eq. (2.32) yields

b) Using eqs. (2.32) and (2.35) at constant pressure yields

From eq. (2.26),

G = zF E = (2) 96; 500

16CHAPTER 3. THERMODYNAMICS OF AN ELECTROCHEMICAL CELL

3.9 Show that S = R ln Ke in a galvanic cell at constant pressure.

b) Similarly, the Pb-Cu Cell gives

The required plots are y = ln Cu+2 = f (T )

18CHAPTER 3. THERMODYNAMICS OF AN ELECTROCHEMICAL CELL

where = Chemical potential

Figure 3.1 Galvanic cell and its phase components.

20CHAPTER 3. THERMODYNAMICS OF AN ELECTROCHEMICAL CELL

At equilibrium, dS = 0 and the following is deduced from eq. (3.6) [2]

2) For mechanical equilibrium,

3) For electrochemical equilibrium, T = T and

Thus, ( )M [z ( )e ( )M z+ ] is the anity for M = (M z+ ) + (ze )

dierence between the and electrodes is E = . Recall that the

Case 1: The electron balance in the reactions is (z1 e ) = (z2 e ) = ze

and = . Case 2: If (z1 e ) 6= (z2 e ) and = , then z = x (z1 e ) =

EX2. From thermodynamics,

22CHAPTER 3. THERMODYNAMICS OF AN ELECTROCHEMICAL CELL