Corrosion Manual (2015) PDF

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
1.1 QUESTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2 ELECTROCHEMISTRY 5
2.1 PROBLEMS/QUESTIONS . . . . . . . . . . . . . . . . . . . . . 5
3 THERMODYNAMICS OF AN ELECTROCHEMICAL CELL 9

3.1 PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4 NANO ELECTROCHEMISTRY 25
4.1 PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
5 KINETICS OF ACTIVATION POLARIZATION 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

9 ELECTRODEPOSITION 125
9.1 PROBLEMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
10 HIGH-TEMPERATURE CORROSION 153
iii
iv CONTENTS
CHAPTERS:
v
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¡ (anode)

2H + + 2e¡ ! H2 (cathode)
F e + 2H + ! F e2+ + H2 (redox)
(b) Absorption of oxygen (O2 ) in neutral or basic medium.
1
2 CHAPTER 1. FORMS OF CORROSION
Fe ! F e2+ + 2e¡ (anode)

O2 + H2 O + 2e¡ ! 2OH ¡ (cathode)
F e + O2 + H2 O + 2e¡ ! 2+
F e + 2OH ¡
(redox)
F e2+ + 2OH ¡ ! F e(OH)2
1.5 Investigate the di¤erences between dry and wet corrosion Write down
at least three di¤erences 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 sur-

rounding 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 e¤ects or consequences of corrosion of structures?

Answer: To name a few
1.1. QUESTIONS 3
² Corrosion reduces the thickness of metal parts of a structure and as result,

loss of mechanical strength occurs, leading failure of the structure.
² E¢ciency of machines is reduced due to corrosion.
² Because of corrosion, pipes, boilers and pumps are blocked by the corrosion
compound and therefore, they are di¢cult to operate e¢ciently.
1.12 The principle constituent of wood is cellulose, which is a polysaccha-

ride. 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 sacri…cial 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 polysaccha-

ride. 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.
4 CHAPTER 1. FORMS OF CORROSION
Chapter 2
ELECTROCHEMISTRY
2.1 PROBLEMS/QUESTIONS
2.1 De…ne the galvanic electrode potential for the cell shown in Figure 2.4
using the interfacial potentials involved in the electrochemical process.
Solution:
£ ¤ £ ¤
E = ÁCu ¡ ÁCu SO4 Half ¡ cell + ÁZn SO4 ¡ ÁZn Half ¡ cell
£ ¤ £ ¤ £ ¤
+ ÁCu SO4 ¡ ÁZn SO4 + ÁZn ¡ Á0 0
0
Cu W ire + ÁCu ¡ ÁCu W ire
£ ¤
+ ÁCu SO4 ¡ ÁZn SO4 Bridge
E = ÁCu + ÁCu SO4 ¡ ÁCu SO4 + ÁZn SO4 ¡ ÁZn SO4 + ÁZn ¡ ÁZn ¡ Á0
Cu
+ÁCu ¡ Á00
Cu
E = ÁCu ¡ Á0
Cu
since ÁCu = Á0 0
Cu at the copper electrode and copper wire junction. In addi-
tion, let ÁCu and Á0
0 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
6 CHAPTER 2. ELECTROCHEMISTRY
2.3 Explain why an electrode potential di¤erence 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 po-
tential are
4F e + 12OH ¡ ! 4F e (OH)3 + 12e =) Eao = 0:771 V
3O2 + 6H2 O + 12e ! 12 (OH ¡ ) =) Eco = 0:401 V
4F e + 3O2 + 6H2 O ! 4F e (OH)3 =) 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 illus-
trated 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 simulta-

neous anodic and cathodic reactions on the metal surface.
2.1. PROBLEMS/QUESTIONS 7
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 (Áx ), 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¡ 12
mol
Q = 1:93x10¡ 7
C = 0:193 ¹C
But,
1 N: m2 J: m
¸ = = 9x109 = 9x109
4¼²o C2 C2
r = 0:09 m
Inserting these values into eq. (2.8) give the magnitude of the electric poten-
tial on a monopole system. Thus,
¡ ¢¡ ¢
¸Q 9 £ 109 J: m= C2 1:93x10¡ 7 C
Áx = =
r 0:09 m
Áx = 19; 300 J/C = 19; 300 N:m/C
Áx = 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,
¸Q Á 19; 300 N:m=C

Ex = = =
r2 r 0:09 m
Ex = 2:14 £ 105 N=C = 2:14 £ 105 V=m
Thus, the electric force acting on the particle becomes
¡ ¢¡ ¢
Fx = QEx = 1:93x10¡ 7
C 2:14 £ 105 N=C
Fx = 0:04 N
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:
8 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,
Q 38; 600 A:s

I = = = 2:68 A
t 4 £ 60 £ 60 s
P = 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
it is a standard reference. Thus, EH o
2 =H
+ = 0.
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 = EFo e3+ =F e2+ + ECd=Cd

o
2+ = 0:77 VSHE + 0:403 VSHE
Eo = 1:173 VSHE
F e+3 = Cathode because it reduces to F e+2
Cd = 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
ECd2+ =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 cal-
culate 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.
tentials (Table 2.2) are
Cu+2 + 2e ! Cu =) Eco = 0:337 V

H2 ! 2H + + 2e =) Eao = 0 V
Cu+2 + H2 ! Cu + 2H + =) E o = 0:337 V
Then,
µ ¶
o o J
¢G = ¡zF E = (2) 96; 500 (0:337 V )
mol:V
kJ
¢Go = ¡65
mol
Therefore, the reactions will occur as written since ¢Go < 0. The maxi-
mum 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
o RT [Cu]
ECu = ECu ¡ ln
zF [Cu+2 ]
2
o RT [H + ]
EH = EH ¡ ln = ¡0:059pH
zF [H2 ]
EH = ¡0:059 (2) = ¡0:118 V
Letting ECu = EH = ¡0:118 V yields
o RT [Cu]
EH = ECu ¡ ln = ¡0:118 V
zF [Cu+2 ]
µ ¶
[Cu] o zF
ln = (ECu ¡ EH )
[Cu+2 ] RT Cu
· ¸
¡ zF ¢ (2)(96500 m oJl . V )
o
(ECu ¡ EH ) = (0:337 V + 0:118 V)
RT Cu (8:314 m o lJ. o K )(298 o K)
µ ¶
o zF
(EH ¡ ECu ) = 35:44
RT Cu
and
[Cu]
ln = 35:44
[Cu+2 ]
[Cu]
= 2:46x1015
[Cu+2 ]
Thus,
£ ¤ [Cu] 1 mol=l
Cu+2 = 15
= 15
2:46x10
£ ¤ 2:46x10
aCu+2 = 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.
tential (Table 2.2) are
N i+2 + 2e ! N i =) o
ENi = ¡0:250 V
Zn ! Zn+2 + 2e =) o
EZn = +0:763 V
N i+2 + Zn ! Ni + Zn+2 =) 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
o RT [N i]
ENi = ENi ¡ ln = ¡0:280 V
zF [N i+2 ]
£ +2 ¤
o RT Zn
EZn = EZn ¡ ln = 0:793 V
zF [Zn]
E = ENi + EZn = 0:513 V
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 = Ag+ + OH ¡
[Ag+ ] [OH ¡ ]
Ke = = 1:10x10¡ 4
[AgOH]
(b) The free energy change is
µ ¶
J ¡ ¢
¢Go = ¡RT ln (Ke ) = ¡ 8:314 (298o K) ln 1:1x10¡ 4
mol:o K
¢Go ¼ ¡22:58 kJ=mol
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
[Ag + ] [OH ¡ ] [OH ¡ ]
Ke = =
[AgOH] [AgOH]
2 ¡ ¢2
[OH ¡ ] 4:03 ¤ 10¡ 3
[AgOH] = = = 0:15 mol=l
Ke 1:10 ¤ 10¡ 4
But,
CAgOH = [AgOH] Aw;AgOH

³ g´
CAgOH = (0:15 mol=l) 107:87 = 18:73 g=l
£ +¤ £ ¤ l
Ag = OH ¡ = 4:03x10¡ 3 mol=l
µ ¶
£ ¤ mol ³ g´
CAg+ = Ag+ Aw;Ag = 4:03x10¡ 3 107:87 = 0:43 g=l
l l
µ ¶
£ ¤ mol ³ g ´
COH ¡ = OH ¡ Aw;OH = 4:03x10¡ 3 17 = 6:85x10¡ 2
g=l
l mol
(b) The dissociation of water ant its rate constant are
H2 O = H + + OH ¡
[H + ] [OH ¡ ]
Kw = = 10¡ 14
[H2 O]
where [H2 O] = 1 mol=l and
£ ¤ Kw 10¡ 14
H+ = ¡
= = 2:48x10¡ 12 mol=l
[OH ] 4:03x10¡ 3 mol=l
£ ¤ ¡ ¢
pH = ¡ 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
µ ¶
J
¢Go = ¡zF E o = ¡ (2) 96; 500 (0:337 V )
mol:V
J
¢Go = ¡65; 041
mol
(b) The equilibrium constant is
¡ J
¢
¢Go ¡65; 041 mol
ln Ke = ¡ =¡ ¡ ¢ = 26:25
RT 8:314 mol:J o K (298 o K)
Ke = 2:52x1011
3.1. PROBLEMS 13
(c) The concentration of copper cations is
[Cu]
Ke =
[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)
CCu+2 = 2:52x10¡ 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 =) o
ECu = 0:337 V
Cd = Cd+2 + 2e =) o
ECd = 0:403 V
Cu+2 + Cd = Cu + Cd+2 =) E o = +0:740 V
RT
E = Eo ¡ ln (Ke )
£ zF +2 ¤
[Cu] Cd [1] [0:05]
Ke = +2
= = 0:2
[Cd] [Cu ] [1] [0:25]
zF (E ¡ E o )
T = ¡
R ln (Ke )
¡ J
¢
(2) 96; 500 mol:V (0:762 V ¡ 0:740 V )
T = ¡ ¡ J
¢
8:314 mol:o K ln (0:2)
T = 317:32o K = 44:32o C
b) Using eqs. (2.32) and (2.35) at constant pressure yields
RT
E = Eo ¡ ln (Ke )
zF
@E R
= ¡ ln (Ke )
@T zF
@E
¢S = zF = ¡R ln (Ke )
µ@T ¶
J J
¢S = ¡ 8:314 ln (0:2) = 13:38
mol:o K mol:o K
From eq. (2.26),

µ ¶
J
¢G = ¡zF E = (2) 96; 500 (0:762 V )
mol:V
¢G = ¡147 kJ=mol
From eq. (2.34),
¢H = ¢G + T ¢S
µ ¶
J
¢H = ¡147; 000 J=mol + (317:32o K) 13:38
mol:o K
¢H = 151:25 J=mol
From eq. (236),
µ ¶
J
Q = ¡T ¢S = ¡ (317:32o K) 13:38
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 =) o
ECu = 0:337 V
Co = Co+2 + 2e =) o
ECo = 0:227 V
Cu+2 + Co = Cu + Co+2 =) E o = +0:614 V
Using eq. (2.32) yields
RT
E = Eo ¡ ln (Ke )
zF
zF (E ¡ E o )
ln (Ke ) = ¡
¡ RT J
¢
(2) 96; 500 mol:V (0:65 V ¡ 0:614 V )
ln (Ke ) = ¡ ¡ J
¢ = ¡2:8044
8:314 mol:o K (298o K)
Ke = 0:0605
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
RT
E = Eo ¡ ln (Ke )
zF
@E R
= ¡ ln (Ke )
@T zF
@E
¢S = zF = ¡R ln (Ke )
µ@T ¶
J J
¢S = ¡ 8:314 o
ln (0:0605) = 23:32
mol: K mol:o K
From eq. (2.26),
µ ¶
J
¢G = ¡zF E = ¡ (2) 96; 500 (0:65 V )
mol:V
¢G = ¡125:45 kJ=mol
£ ¤ £ ¤
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 =) EMo
1
o
M2+2 + 2e = M2 =) EM 2
M1 + M2+2 = M1+2 + M2 =) o + Eo
E o = EM1 M2

RT
E = Eo ¡
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
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
RT
E = Eo ¡ ln (Ke )
zF
@E R
= ¡ ln (Ke )
@T 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-
+ V - + V -
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 =) o
ECu = 0:337 V
Zn = Zn+2 + 2e =) o
EZn = 0:763 V
Cu+2 + Zn = Cu + Zn+2 =) E o = +1:10 V
£ ¤
[Cu] Zn+2 [1] [1] 1
Ke = +2
= +2
=
[Cu ] [Zn] [Cu ] [1] [Cu+2 ]
RT
E = Eo ¡ ln (Ke ) = 0
zF
o
zF E
ln (Ke ) = =
RT
o
1 zF E
ln =
[Cu+2 ] RT
¡ J
¢
£ ¤ zF E o (2) 96; 500 mol:V (1:10 V )
ln Cu+2 = ¡ ¡ ¡ J
¢
RT 8:314 mol:o K T
£ ¤ 2:55x104
ln Cu+2 = ¡ =y (Solid curve)
T
b) Similarly, the Pb-Cu Cell gives
H2 = 2H + + 2e =) o
ECu =0V
Cu+2 + 2e = Cu =) EHo
= 0:337 V
Cu+2 + H2 = Cu + 2H + =) E o = +0:337 V
£ ¤
[Cu] P b+2 [1] [1] 1
Ke = = =
[Cu+2 ] [P b] [Cu+2 ] [1] [Cu+2 ]
RT
E = Eo ¡ ln (Ke ) = 0
zF
zF E o
ln (Ke ) =
RT
1 zF E o
ln =
[Cu+2 ] RT
¡ J
¢
£ ¤ zF E o (2) 96; 500 mol:V (0:337 V )
ln Cu+2 = ¡ ¡ ¡ J
¢
RT 8:314 mol:o K T
£ ¤ 7823: 1
ln Cu+2 = ¡ =y (Dash curve)
T
£ ¤
The required plots are y = ln Cu+2 = f (T )
y -25
-50
-75
-100
275 287.5 300 312.5 325 337.5
T
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
T
Besides the di¤erences in activity behavior, either trend means that the activ-
ity, solution conductivity and ionic di¤usivity increase with increasing tempera-
ture. 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 ®-² coupling are, respectively
3.1. PROBLEMS 19
dS = dS ® + dS ² (3.1a)
T dS ®
®
= dU ® + P ® dV ® ¡ [(¹® d´® )M + (¹® d´® )e ] (3.1b)
T ² dS ² = dU ² + P ² dV ² ¡ (¹² d´² )M z+ (3.1c)
dE = dU ® + dU ² + Á® dq ® + Á² dq ² (3.1d)
dq = dq ® + dq ² = ze F (d´® )e + zF (d´² )M z+ (3.1e)
where ¹ = Chemical potential P = Pressure E = Total energy

U = Internal energy V = Volume
S = Entropy T = Temperature
q = Electron charge ´ = Number of moles
Á = Electric potential F = Faraday’s constant
Figure 3.1 Galvanic cell and its phase components.
For an isolated ®-² thermodynamic system, the following constraints can be

used to develop the equilibrium conditions and the Gibbs free energy change
(¢G) [2]
(d´ ® )M z+ = ¡ (d´® )M (3.2a)

dV ² = ¡dV ® (3.2b)
dV = 0 (3.2c)
dE = 0 (3.2d)
dq = 0 (3.2e)
Hence, combining eq. (3.1e) and (3.2e) and the resultant expression with
eq. (3.2a) yields
(d´® )e = + (d´² )e since ze = ¡1 (3.3a)

(d´® )e = ¡z (d´® )M since z ¸ 1 (3.3b)
Adding (d´® )e and (d´² )M z+ moles to the ® phase and the ² phase, respec-
tively, the change in electron charges becomes [2]
dq ® = ¡F (d´ ® )e (3.4a)
dq ² = +zF (d´² )M z+ (3.4b)
Substituting eqs. (3.2a) and (3.3a) into (3.1e) and (3.1e) into (3.1d) yields
dU ® + dU ² + zF (Á® ¡ Á² ) (d´ ® )M = 0 (3.5a)
dU ² = ¡ [dU ® + zF (Á® ¡ Á² ) (d´ ® )M ] (3.5b)

Substituting eqs. (3.2a) through (3.5b) into (3.2b) and (3.2c) and the re-
sultant expressions into (3.2a), and subsequently, collecting terms yields the
entropy change of the ®-² system
· ¸ · ® ¸
1 1 ® P P²
dS = ¡ dU + ¡ dV ® (3.6)
T® T² T® T²
· ¸
(¹® )M z (¹® )e (¹² )M z+ (zF ) (Á² ¡ Á® )
+ ¡ + ¡ + (d´® )M
T® T® T² T²
At equilibrium, dS = 0 and the following is deduced from eq. (3.6) [2]
1) For thermal equilibrium,

· ¸
1 1
¡ = 0 since T ® = T ² (3.7)
T® T²
2) For mechanical equilibrium,
· ® ¸
P P²
¡ = 0 since P ® = P ² (3.8)
T® T²
3) For electrochemical equilibrium, T ® = T ² and
(¹® )M ¡ [z (¹® )e ¡ (¹² )M z+ ] + zF (Á® ¡ Á² ) = 0 (3.9a)
(¹® )M ¡ [z (¹® )e ¡ (¹² )M z+ ] = ¡zF (Á® ¡ Á² ) (3.9b)

3.1. PROBLEMS 21
and
¢G® = (¹® )M ¡ [z (¹® )e ¡ (¹² )M z+ ] (3.9c)

¢G® = ¡zF (Á® ¡ Á² ) (3.9d)
² ²
Thus, (¹® )M ¡ [z (¹® )e ¡ (¹² )M z+ ] is the a¢nity for M ® = (M z+ ) + (ze¡ )
and ¢G® is the Gibbs free energy change for the ®-² subsystem.
In addition, the potential di¤erence (Á® ¡ Á² ) between two phases in a half-
cell at equilibrium cannot be measured. Instead, two electrodes are connected
as shown in Figure 3.1 to measure the electric potential di¤erence between the
electrodes. This can be done by connecting, say, ¯-± system to the previous ®-²
system using a salt bridge or porous membrane. Thus, ³ the electrical
´ potential
di¤erence between the ¯ and ® electrodes is E = Á® ¡ Á¯ . 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 schemati-
cally shown in Figure 3.1 are given next.
® ¯
Case 1: The electron balance in the reactions is (z1 e¡ ) = (z2 e¡ ) = ze¡
® ¯ ®
and Á² = Á± . Case 2: If (z1 e¡ ) 6= (z2 e¡ ) and Á² = Á± , then z = x (z1 e¡ ) =
¯
y (z2 e¡ ) , where x and y are integer numbers. Hence, the reactions are
¡ z+ ¢² ¡ ¡ ¢®
M1® = M1 + z1 e ¢G® = ¡zF E® (3.10)
¡ z+ ¢± ¡ ¡ ¢¯
M2 + z2 e = M2¯ ¢G¯ = ¡zF E¯ (3.11)
¡ ¢± ¡ ¢²
M1 + M2z+
®
= M1z+ + M2¯ ¢G = ¡zF E (3.12)
¡ ¢
where E® = Á® ¡ Á² , E¯ = Á± ¡ Á¯ , E = Á® ¡ Á¯ , ¹¯ e = (¹® )e and
¢G = ¢G® + ¢G¯ . In general, the standard and non-standard Gibbs free
energy change expressions are, respectively
¢Go = ¡zF E o (standard) (3.13)

¢G = ¡zF E (non-standard) (3.14)
EX2. From thermodynamics,

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

Combining eqs. (1) and (2) yields
dQ = dU + dW (3)
dQ = dU + P dV + zF dE (4)
From the second law of thermodynamics,
dQ = T dS (5)
Then, eq. (4) becomes
T dS = dU + P dV + zF dE (6)
T dS = dH + zF dE (7)
where dH is the di¤erential enthalpy.
By de…nition, the di¤erential Gibbs free energy is
dG = dH ¡ T dS (8)
Combining eqs. (7) and (8) gives
dG = ¡zF dE (9)
Integrating
¢Go = ¡zF E o (standard) (10)

¢G = ¡zF E (non-standard) (11)
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 (º¹o )Cu ¡ (º¹o )Cu2+

ECu2+ =Cu = ¡
· zF ¸
o (1)(0) ¡ (1)(+64:98 kJ=mol)
ECu2+ =Cu = ¡ = +0:337 V
(2)(96:50 kJ=mol ¢ V )
3.1. PROBLEMS 23
o (º¹o )Zn2+ ¡ (º¹o )Zn

EZn=Zn2+ = ¡
· zF ¸
o (1)(¡147:21 kJ=mol) ¡ (1)(0)
EZn=Zn2+ = ¡ = +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
E o = ECu
o o
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 in-
homogeneous 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 (¡¾z)
25
26 CHAPTER 4. NANO ELECTROCHEMISTRY
where Io and ¾ 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 Ã (x) within the barrier
of width w, the tunneling current It through the barrier and the decay length
are related as shown below:
Ã (x) = Ão exp (¡k2 x)

2
It / jÃo j exp (¡k2 x)
2¼ p 2¼ p
k2 = 2m (Uo ¡ E) = 2mÂ
h h
If the work function and the barrier width are Â = 4:32 eV and w = 0:151
nm in a ST M experiment, then determine It for a barrier of width 2w. Explain.
Solution:
³ ´
1=2
k2 = 5:1268 nm¡ 1 :eV ¡ 1=2
(Uo ¡ E)
³ ´ ³ ´
k2 = 5:1268 nm¡ 1 :eV ¡ 1=2
Â1=2 = 5:1268 nm¡ 1 :eV ¡ 1=2
(4:32 eV )1=2
k2 = 10:656 nm¡ 1
Then,
2
It;w jÃo j exp (¡k2 w)
=
It;2w jÃo j2 exp (¡2k2 w)
It;w £¡ ¢ ¤
= exp (k2 w) = exp 10:656 nm¡ 1 (0:20 nm)
It;2w
It;w
= 5 or It;w = 5It;2w or It;2w = 0:2It;w
It;2w
Denote the signi…cant 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 27
½e;Cu = [ne ½NA =Aw ]Cu

µ ¶µ ¶
8:94 £ 103 Kg=m3 6:02 £ 1023 atom
½e;Cu = (2)
63:55 Kg=Kmol 10¡ 3 Kmol
½e;Cu = 1:6937 £ 1029 1=m3
and
µ ¶2=3
h2 3
UF;Cu = ½e
2me 8¼
¡ ¢2 ·µ ¶ ¸
6:63 £ 10¡ 34 J:s 3 ¡ 28 3
¢ 2=3
UF;Cu = 7:6514 £ 10 1=m
2 ¤ 9:11 £ 10¡ 31 Kg 8¼
J .s
2 2
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
½e;W = [ne ½NA =Aw ]W

µ ¶µ ¶
19:3 £ 103 6:02 £ 1023
½e;W = (4) = 2:5278 £ 1029 1=m¡ 3
183:85 10¡ 3
¡ ¢2 µ ¶2=3
6:63 £ 10¡ 34 J:s 3 ¤ 1:694 £ 1029 1
UF;W = = 2:3383 £ 10¡ 18
J
2 ¤ 9:11 £ 10¡ 31 Kg 8¼ m3
2:3383 £ 10¡ 18 J
UF;W = = 14:61 eV
1:60 £ 10¡ 19 J=eV
Obviously, UF;W > UF;Cu due to the di¤erences in the amount of free elec-
trons and the electron densities between gold and tungsten metals.
(b) The velocity of electrons: Using eq. (4.12) yields
r
2UF
ve =
me
s s
2 (1:0541 £ 10¡ 18 J) 6 N:m
ve;Cu = = 1:52 £ 10
9:11 £ 10¡ 31 Kg Kg
s
Kg:m m
ve;Cu = 1:52 £ 106 = 1:52 £ 106 m=s
s2 Kg
and for tungsten
s
(2) (2:3383 £ 10¡ 18 J)
ve;W =
9:11 £ 10¡ 31 Kg
ve;W = 2:27 £ 106 m=s = 2; 270 Km=s
Therefore, an electron travels very fast in the vacuum gap. Let’s determine
the atom density using eq. (4.9)
¡ ¢µ ¶
½NA 8:94 £ 103 Kg=m3 6:02 £ 1023 atoms
na;Cu = =
Aw 63:55 Kg=Kmol 10¡ 3 Kmol
na;Cu = 8:4687 £ 1028 atoms=m3
¡ ¢µ ¶
½NA 19:30 ¤ 103 Kg=m3 6:02 ¤ 1023 atoms
na;W = =
Aw 183:85 Kg=Kmol 10¡ 3 Kmol
na;W = 6:3196 £ 1028 atoms=m3
Verify the number of free electrons being used. Thus,
µ ¶
½e 1:6937 £ 1029 1=m3
ne;Cu = = =2
na 1:8302 £ 1029 atoms=m3
µ ¶Cu
½e 2:5278 £ 1029
ne;W = = =4
na W 6:3196 £ 1028
According to the above calculations, the amount of energy (o¤set) being given
to the electrons during tunneling is
S T
Â = EF;Cu ¡ EF;W = 6:59 eV ¡ 14:61 eV = ¡8:02 eV
This is the energy that causes the electrons to acquire a speci…c velocity in
the tunneling gap (electrical conduction region).
4.6 For the reaction O + e¡ À R in an electrochemical cell, the cyclic

voltammetry method provided the formal potential (standard potential) Áo =
133 mV against a reference electrode. If the activity ratio is [O] = [R] = 0:2,
then calculate (a) the applied potential Á 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]
Á = Áo ¡ ln
zF [O]
RT [O] (8:314 J=mol:K) (298 K)
Á = Áo + ln = 0:133 V + ln (0:2)
zF [R] (1) (96; 500 J=mol:V )
Á = 0:09168 V = 91:68 mV
(b) The reaction energy:
¡ ¢
U = qe Á = 1:602 £ 10¡ 19
J=V (0:09168 V ) = 1:4687 £ 10¡ 20
J
U = 0:092 eV
4.7 Show that PT = exp (¡2k2 x), eq. (4.48), using the following equations
Ã = A exp (iµ)
p
2
d Ã 2m [U ¡ E] P2
= ¡ Ã = ¡ Ã
dx2 }2 }2
where P is the moment, x = w and } = h=2¼. Hint: extract the resultant
real and imaginary parts for solving this problem.
Solution:
Derivatives:
Ã = A exp (iµ) (a)

· ¸
dÃ dA dµ
= + iA exp (iµ)
dx dx dx
" µ ¶2 #
d2 Ã d2 A d2 µ dA dµ dµ
= + iA 2 + 2i ¡A exp (iµ) (b)
dx2 dx2 dx dx dx dx
" µ ¶2 #
d2 Ã d2 A d2 µ dA dµ dµ Ã
= + iA 2 + 2i ¡A
dx2 dx2 dx dx dx dx A
Equate d2 Ã=dx2 terms:
" µ ¶2 #
P2 d2 A d2 µ dA dµ dµ Ã
¡ 2Ã = + iA 2 + 2i ¡A
} dx 2 dx dx dx dx A
" µ ¶2 #
AP 2 d2 A d2 µ dA dµ dµ
¡ 2 = + iA + 2i ¡A (c)
} dx2 dx2 dx dx dx
Imaginary parts:of eq. (c) and multiply by A and eliminate i:
d2 µ dA dµ
0 = iA + 2i
dx2 dx dx
2
d µ dA dµ
0 = A2 2 + 2A (d)
dx dx dx
Eq. (d) becomes
· ¸
d2 µ
A2 2 =dx = 0 (e)
dx
Integrating eq. (e) yields the wave amplitude A as
dµ
A2 = C1
dx p
C1 C
A = p =p (f)
dµ=dx dµ=dx
Real Parts of eq. (c):
µ ¶2
AP 2 d2 A dµ
¡ = ¡A
}2 dx2 dx
µ ¶2
P2 1 d2 A dµ
¡ 2 = ¡
} A dx2 dx
and
µ ¶2
1 d2 A dµ P2
= ¡
A dx2 dx }2
If
µ ¶2
1 d2 A dµ P2
< < ¡
A dx2 dx }2
· ¸
1 d2 A
! 0
A dx2
then
µ ¶2
dµ P2
=
dx }2
dµ P
=
dx }Z
1
µ = P dx (g)
}
4.1. PROBLEMS 31
and
p
C C }C
A = p 1 =p =p
dµ=dx dµ=dx P
D
A = p
P
Thus,
Ã = A exp (iµ)
· Z ¸
D i
Ã = p exp P dx (h)
P }
But,
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
· 2Z ¸
D i p
Ã = p exp 2m (U ¡ E)dx
P }
" Z p #
D 2m (U ¡ E)
Ã = p exp ¡ dx
P }
· Z ¸
D 2¼ p
Ã = p exp ¡ 2m [U (x) ¡ E] dx
P h
· Z ¸
D
Ã = p exp ¡ k2 dx
P
· Z x ¸
D D
Ã = p exp ¡ k2 dx = p exp (¡k2 x)
P 0 P
p
Ã P
= exp (¡k2 x)
D
where
2¼ p
k2 = 2m [U (x) ¡ E]
h
Then,
Ã p !2
Ã P
PT =
D
PT = exp (¡2k2 x)
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 (Â) 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:
³ ´ ³ ´
1=2 1=2
k2 = 5:1268 nm¡ 1 :eV ¡ 1=2
(Uo ¡ E) = 5:1268 nm¡ 1 :eV ¡ 1=2
(4 eV )
k2 = 10:254nm¡ 1
and
£ ¡ ¢ ¤
PT = exp (¡2k2 z) = exp ¡2 10:254 nm¡ 1 (0:3 nm) = 2:13 £ 10¡ 3
PT ' 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 = exp (¡2k2 w)
k2 = ¡ ln (PT ) =2w = ¡ ln (0:106) = (2x0:4) = 2:81 nm¡ 1
Then,
³ ´
1=2
k2 = 5:1268 nm¡ 1 :eV ¡ 1=2
(Uo ¡ E)
2 2
E = Uo ¡ (2:81=5:1268) = 4:5 eV ¡ (2:81=5:1268) eV
E = 4:2 eV
4.1. PROBLEMS 33
4.10 Assuming that there is no wave re‡ection, 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),
Ã 1 (x) = A exp (ik1 x) + B exp (¡ik1 x)

dÃ1 (x)
= ik1 A exp (ik1 x) ¡ ik1 B exp (¡ik1 x)
dx
Ã2 (x) = C exp (ik2 x) + D exp (¡ik2 x)

Ã2 (x) = C exp (ik2 x) since D = 0
dÃ2 (x)
= ik2 C exp (ik2 x) ¡ ik2 D exp (¡ik2 x)
dx
dÃ2 (x)
= ik2 C exp (ik2 x) since D = 0
dx
At x = 0;
Ã (0)1 = Ã (0)2
A+B = C (1)
dÃ1 (0) dÃ2 (0)
=
dx dx
ik2
A¡B = C (2)
ik1
or
B C
1+ =
A A
B k2 C
1+ =
A k1 A
Combining eqs. (1) and (2) gives
µ ¶
B k2 B k2 k2 B
1+ = 1+ = +
A k1 A k1 k1 A
µ ¶
k2 B k2
1¡ = 1+
k1 A k1
B 1 + k2 =k1
=
A 1 ¡ k2 =k1
Then,
¯ ¯2 ¯ ¯
¯B ¯ ¯ 1 + k2 =k1 ¯2
PR = ¯¯ ¯¯ = ¯¯ ¯
A 1 ¡ k2 =k1 ¯
and
PT + PR = 1
PT = 1 ¡ PR
¯ ¯
¯ 1 + k2 =k1 ¯2
PT = 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 = C +D (4.31)
ik1 (A + B) = k2 (C + D) (4.32)
C exp (k2 w) + D exp (¡k2 w) = F exp (ik1 w) (4.33)
k2 [C exp (k2 w) ¡ D exp (¡k2 w)] = ik1 F exp (ik1 w) (4.34)
Divide these eqs. by A so that
A+B = C +D (a)
ik1 (A + B) = k2 (C + D) (b)
C exp (k2 w) + D exp (¡k2 w) = F exp (ik1 w) (c)
k2 [C exp (k2 w) ¡ D exp (¡k2 w)] = ik1 F exp (ik1 w) (d)
and
Ã1 (x) = A exp (ik1 x) + B exp (¡ik1 x)

dÃ1 (x)
= ik1 A exp (ik1 x) ¡ ik1 B exp (¡ik1 x)
dx
Ã2 (x) = C exp (ik2 x) + D exp (¡ik2 x)

Ã2 (x) = D exp (¡ik2 x) since C = 0
dÃ2 (x)
= ¡ik2 D exp (¡ik2 x)
dx
4.1. PROBLEMS 35
At x = 0;
Ã (0)1 = Ã (0)2
A+B = D (1)
dÃ1 (0) dÃ2 (0)
=
dx dx
ik2
A¡B = ¡ D (2)
ik1
Divide eqs. (1) and (2) by A so that
B D
1+ = (3)
A A
B k2 D
1¡ = ¡ (4)
A k1 A
Eliminate D=A
µ ¶
B k2 B ik2 k2 B
1+ = ¡ 1+ =¡ ¡
A k1 A ik1 k1 A
µ ¶
B k2 k2
1+ = ¡ ¡1
A k1 k1
B 1 + k2 =k1
= ¡
A 1 + k2 =k1
Then,
¯ ¯2 ¯ ¯
¯B ¯ ¯ 1 + k2 =k1 ¯2
PR ¯ ¯ ¯
= ¯ ¯ = ¯¡ ¯ =1
A 1 + k2 =k1 ¯
PT + PR = 1
PT = 1¡1=0
The particle will always be re‡ected 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 4ik1 k2 exp (¡ik1 w)

= 2 2
A (k2 + ik1 ) exp (¡k2 w) ¡ (k2 ¡ ik1 ) exp (k2 w)
16k12 k22
PT = h i
2 2
(k1 + k2 ) e¡ 2k2 w + (k1 + k2 ) e2k2 w + [12k12 k22 ¡ 2 (k24 + k14 )]
Solution:
Ã (w)2 = Ã (w)3
C exp (k2 w) + D exp (¡k2 w) = F exp (k1 w) (3)
dÃ2 (w) dÃ 3 (w)
=
dx dx
k2 C exp (k2 w) ¡ k2 D exp (¡k2 w) = ik1 F exp (ik1 w) (4)
Divide eqs. (a) through (d) by A and group them to be algebraically manip-
ulated.
A+B = C +D (5)
k2 k2
A¡B = C¡ D (6)
ik1 ik1
C exp (k2 w) + D exp (¡k2 w) = F exp (k1 w) (7)
ik1
C exp (k2 w) ¡ D exp (¡k2 w) = F exp (ik1 w) (8)
k2
The tedious work: Divide by A
B C D
1+ = + (9)
A A A
ik1 ik1 B C D
¡ = ¡ (10)
k2 k2 A A A
C D F
exp (k2 w) + exp (¡k2 w) = exp (k1 w) (11)
A A A
C D ik1 F
exp (k2 w) ¡ exp (¡k2 w) = exp (ik1 w) (12)
A A k2 A
Add eqs. (11) and (12) to get
µ ¶
C ik1 F
2 exp (k2 w) = +1 exp (ik1 w)
A k2 A
µ ¶
C F k2 + ik1
= exp (ik1 w) exp (¡k2 w) (13)
A A 2k2
Next, subtract eqs. (11) ¡ (12)
µ ¶
D ik1 F
2 exp (¡k2 w) = 1¡ exp (ik1 w)
A k2 A
µ ¶
D F k2 ¡ ik1
= exp (ik1 w) exp (k2 w) (14)
A A 2k2
4.1. PROBLEMS 37
Add eqs. (10) + (9) to get
C ik1 ik1 B B
2 = ¡ +1+
A k2 k2 A A
µ ¶
C k2 + ik1 k2 ¡ ik1 B
= + (15)
A 2k2 2k2 A
Subtract eqs. (9) ¡ (10) so that
µ ¶ µ ¶
D ik1 ik1
2 = 1¡ + 1+
A k2 k2
µ ¶
D k2 ¡ ik1 k2 + ik1 B
= + (16)
A 2k2 2k2 A
Now, equate eqs. (13) = (15)
µ ¶ µ ¶
F k2 + ik1 k2 + ik1 k2 ¡ ik1
B
exp (ik1 w) exp (¡k2 w) = +
A 2k2 2k2 2k2
A
F B
(k2 + ik1 ) exp (ik1 w) exp (¡k2 w) = (k2 + ik1 ) + (k2 ¡ ik1 ) (17)
A A
Equate eqs. (14) = (16)
µ ¶ µ ¶
F k2 ¡ ik1 k2 ¡ ik1 k2 + ik1
B
exp (ik1 w) exp (k2 w) = +
A 2k2 2k2 2k2
A
F B
(k2 ¡ ik1 ) exp (ik1 w) exp (k2 w) = (k2 ¡ ik1 ) + (k2 + ik1 ) (18)
A A
Rearrange eqs. (17) and (18) so that
F B
(k2 + ik1 ) exp (ik1 w) exp (¡k2 w) ¡ (k2 + ik1 ) = (k2 ¡ ik1 ) (19)
A A
F B
(k2 + ik1 ) exp (ik1 w) exp (¡k2 w) ¡ (k2 ¡ ik1 ) = (k2 + ik1 ) (20)
A A
Now divide eqs. (19)=(20) to eliminate B=A
F
A (k2 + ik1 ) exp (ik1 w) exp (¡k2 w) ¡ (k2 + ik1 ) k2 ¡ ik1
F
= (21)
A (k2 + ik1 ) exp (ik1 w) exp (¡k2 w) ¡ (k2 ¡ ik1 ) k2 + ik1
Solve for F=A

¯ ¯2
¯F ¯ F¤ F
PT = ¯¯ ¯¯ = ¤
A A A
F 4k1 k2 eik1 w
= 2 ¡ k2 w
A (k2 + ik1 ) e ¡ (k2 ¡ ik1 )2 ek2 w
F¤ ¡4k1 k2 e¡ ik1 w
= 2 ¡ k2 w 2 (Conjugate)
A¤ (k2 ¡ ik1 ) e ¡ (k2 + ik1 ) ek2 w
F¤ F ¡4k1 k2 e¡ ik1 w
= h i
A¤ A 2 ¡ k2 w
(k2 ¡ ik1 ) e
2
¡ (k2 + ik1 ) ek2 w
4k1 k2 eik1 w
xh i
2 ¡ k2 w
(k2 + ik1 ) e ¡ (k2 ¡ ik1 )2 ek2 w
Algebiaic work for the denominator:

2 ¡ ¢2
[(k2 ¡ ik1 ) (k2 + ik1 )] e¡ k2 w ¡ k2 w
e = k12 + k22 e¡ 2k2 w
¡ [(k2 ¡ ik1 ) (k2 ¡ ik1 )]2 e¡ k2 w k2 w

e = 4ik1 k23 ¡ k24 ¡ k14 ¡ 4ik13 k2 + 6k12 k22
2 22
¡ (k2 + ik1 ) (k2 + ik1 ) ek2 w2 e¡ k2 w
= 4ik13 k2 ¡ k24 ¡ 4ik1 k23 ¡ k14 + 6k12 k22
¡ ¢2
[(k2 + ik1 ) (k2 ¡ ik1 )]2 = k12 + k22 e2k2 w
X = 4ik1 k23 ¡ k24 ¡ k14 ¡ 4ik13 k2 + 6k12 k22 + 4ik13 k2 ¡ k24 ¡ 4ik1 k23 ¡ k14 + 6k12 k22
Y = 12k12 k22 ¡ 2k24 ¡ 2k14
X = Y
Then, the full-blown tunneling probability equation becomes
¯ ¯2
¯F ¯ F¤ F
PT = ¯¯ ¯¯ = ¤
A A A
16k12 k22
PT = 2 2
(k1 + k2 ) e¡ + (k1 + k2 ) e2k2 w + 12k12 k22 ¡ 2k24 ¡ 2k14
2k2 w
16k12 k22
PT = h i
2 2
(k1 + k2 ) e¡ 2k2 w + (k1 + k2 ) e2k2 w + [12k12 k22 ¡ 2 (k24 + k14 )]
4.1. PROBLEMS 39
Test:
If k1 = 14; k2 = 7 and w = 1:2, then
16k12 k22
PT = 2 2
(k1 + k2 ) e¡ 2k2 w + (k1 + k2 ) e2k2 w + 12k12 k22 ¡ 2 (k24 + k14 )
PT = 1:761 9 £ 10¡ 5
2 2
(k1 + k2 ) e¡ 2k2 w
+ (k1 + k2 ) e2k2 w = 8:721 4 £ 109
¡ ¢
12k12 k22 ¡ 2 k24 + k14 = 33; 614
h i £ ¡ ¢¤
2 2
(k1 + k2 ) e¡ 2k2 w
+ (k1 + k2 ) e2k2 w > > 12k12 k22 ¡ 2 k24 + k14
8:721 4 £ 109 > > 33; 614
According to these results, the full-blown equation can be simpli…ed as
16k12 k22
PT = 2 2 = 1:761 9 £ 10¡ 5
(k1 + k2 ) e¡ 2k2 w + (k1 + k2 ) e2k2 w
If e2k2 w >> e¡ 2k2 w
, then a further simpli…cation of the PT equations on-
tained as
16k12 k22
PT = = 1:761 9 £ 10¡ 5
(k1 + k2 ) e2k2 w
Thus,
¯ ¯2
¯F ¯ F¤ F 16k12 k22
PT = ¯¯ ¯¯ = ¤ = 2 exp (¡k2 w)
A A A (k22 ¡ k12 )
Chapter 5
KINETICS OF
ACTIVATION
POLARIZATION
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 ¼ ic = 10¡ 3 A=cm2
b) The cathodic overpotential is given by
ix
ć = ¡¯ c log
icorr
ć 0:20
¯c = ¡ =
log (ix =icorr ) log (10¡ 3 =105 )
¯c = 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 ¯ c = ¡0:10 VSHE

io;F e = 10¡ 8 A=cm2 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 ) EF e = ¡0:50 V
The possible reactions are 2H + + 2e ! H2 ) EH =?
F e + 2H + ! F e+2 + H2 ) E = EF e + EH
a) From Table 2.7 and Nernst equation,
Ecorr = ¡0:70 + 0:241 ¼ ¡0:46 VSHE

o RT [H2 ] o 4:606RT £ ¤
EH = EH ¡ ln 2 = EH + log H +
zF +
[H ] zF
o 4:606RT
EH = EH ¡ (pH)
zF
(4:606) (8:314 J=mol:K) (298K)
EH = 0¡ (pH)
(2) (96; 500 J=mol:V )
EH = ¡ (0:0591) (4:4) = ¡0:26 V
Thus, the cell potential and the overpotentials becomes
E = EF e + EH = ¡0:50 V ¡ 0:26 V = ¡0:76 V

á = EF e ¡ Ecorr = ¡0:46 V + 0:50 V = ¡0:04 V
ć = EH ¡ Ecorr = ¡0:26 V + 0:46 V = ¡0:20 V
Using eq. (5.35) yields the corrosion current density

µ ¶
io;H
ć = ¡¯ c log
icorr
icorr = io;H 10ć =¯ c
¡ ¢
icorr = 10¡ 6 A=cm2 100:2=0:10
¡ ¢
icorr = 10¡ 6 A=cm2 102
icorr = 10¡ 4
A=cm2
Using eq. (5.48) gives the iron corrosion rate

¡ ¡4 ¢
icorr Aw 10 A=cm2 (55:85 g=mol)
CR = =
zF ½ (2) (96; 500 A:s=mol) (7:86 g=cm3 )
¡ 9
CR = 3:68x10 cm=s = 1:16 mm=y
b) From eq. (5.32),

µ ¶
icorr
á = ¯ a log
io;F e
µ ¶
icorr
¯a = á = log
io;F e
¡ ¢
¯a = (0:04 V ) = log 10¡ 4 A=cm2 =10¡ 8 A=cm2
¯a = 0:01 V
c) The required diagram is
-0.20 (io,E)H
-0.30
E (V) ηc
-0.40 (io,E)Fe βc
ηa (i,E)coorr
-0.50
βa
-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 ¹A=cm2
+ ¡
2H + 2e = H2 EH = ¡0:200 VSHE io;H = 0:10 ¹A=cm2
where icorr = 102 ¹A=cm2 and Ecorr = ¡0:741 VSCE . a) Construct the cor-
responding kinetic diagram and b) determine both ¯ a and ¯ c from the diagram
and from the de…nition of overpotential equations.
Solutions:
From Table 2.7,
EM = ¡0:941 + 0:241 = ¡0:70 V

Ecorr = ¡0:741 + 0:241 = ¡0:50 V
Thus, the required diagram is

0
(io,E)H
-0.20
E (V) ηc
-0.40 βc
(i,E)coorr
-0.60 (io,E)M
ηa βa
-0.70
10-4 10-2 100 102 104
i (μA/cm2)
From the diagram,
Ecorr ¡ EM (¡0:50 V ) ¡ (¡0:70 V )

¯a = =
4 decades 4
¯a = 0:05 V
Ecorr ¡ EH (¡0:20 V ) ¡ (¡0:50 V )
¯c = =
3 decades 3
¯c = 0:10 V
From the overpotential eq. (5.32),
á = Ecorr ¡ EM = 0:20 V
ć = Ecorr ¡ EH = ¡0:30 V
µ ¶
icorr
á = ¯ a log
io;M
µ ¶
icorr
ć = ¡¯ c log
io;H
Then,
µ ¶
icorr
¯a = á = log
io;M
£¡ 2 ¢ ¤
¯a = (0:20 V ) = log 10 ¹A=cm2 =10¡ 2 ¹A=cm2
¯a = 0:05 V
and
µ ¶
icorr
¯c = ¡´ c = log
io;H
£¡ 2 ¢ ¡ ¢¤
¯c = (¡0:30 V ) = log 10 ¹A=cm2 = 0:10¹A=cm2
¯c = 0:10 V
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 de-
posited on the steel surface. This process produces a galvanized steel tank. Cal-
culate the time it takes for the zinc coating to corrode completely at a pH = 4:
Data: EZn = ¡0:8 V; io;Zn = 10 ¹A=cm2 , io;H = 10¡ 3 ¹A=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 =) EZn = ¡0:80 V

2H + + 2e ! H2 =) EH =?
Zn + 2H + ! Zn+2 + H2 =) E = EZn + EH
The activity of hydrogen ions and the hydrogen potential are, respectivily
£ ¤
pH = ¡ log H +
£ +¤
H = 10¡ pH = 10¡ 4
mol/l
EH = 0:059pH = 0:059 (4) = 0:24 V

Using the de…nition of overpotential along with the condition á = ć yields
µ ¶
icorr
á = E ¡ EZn = ¯ a log
io;Zn
µ ¶
icorr
ć = E ¡ EH ¡ ¯ c log
io;H
µ ¶ µ ¶
icorr icorr
EZn + ¯ a log = EH ¡ ¯ c log
io;Zn io;H
which leads to
1
log (icorr ) = [¡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 ) = 1:40

icorr = 101:40 ¹A=cm2 = 25:12 ¹A=cm2
From eq. (5.48),
¡ ¢
icorr Aw 25:12x10¡ 6 A=cm2 (65:37 g=mol)
CR = =
zF ½ (2) (96; 500 A:s=mol) (7:14 g=cm3 )
CR = 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
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 ¹A=cm2 Ecorr = ¡0:30 V ¯ a = 0:10 V

Aw;F e = 55:85 g=mol ½F e = 7:86 g=cm3
Solution:
The possible half-cell reactions and standard potentials are
F e = F e+2 + 2e =) EFo e = 0:440 V

1 ¡ o
2 O2 + H2 O + 4e = 2OH =) EH 2O
= ¡0:401 V
1
F e + 2 O2 + H2 O = F e+2 + 2OH ¡ =) E o = EFo e + EHo
2O
= 0:039 V
F e+2 + 2OH ¡ = F e (OH)2 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¡ 14

= 10¡ 5
mol=l so that the activity of
ferrous iron becomes
£ +2 ¤ 2
Fe [OH ¡ ]
KF e(OH)2 =
[F e (OH)2 ]
¡ ¢
£ +2
¤ [F e (OH)2 ] KF e(OH)2 [1] 1:64x10¡ 14
Fe = 2 = 2
[OH ¡ ] [10¡ 5 ]
£ ¤
F e+2 = 1:64x10¡ 4 mol=l
Using eq. (5.32) gives the corrosion density
á = Ecorr ¡ EFo e(OH)2 = ¡0:30 V ¡ 0:039 V

á = ¡0:339 V
µ ¶
icorr
á = ¯ a log
io;F e
µ ¶
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
icorr = 4:07x10¡ 12
A=cm2
From eq. (5.48), the corrosion rate is
¡ ¢
icorr Aw 4:07x10¡ 12 A=cm2 (55:85 g=mol)
CR = =
zF ½ (2) (96; 500 A:s=mol) (7:86 g=cm3 )
CR = 1:50x10¡ 16 cm=s = 4:73x10¡ 8 mm=y = 0:0473 ¹m=y
5.7 Plot the anodic data given below and determine the polarization re-
sistance (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¡ i ¹A=cm2 E (VSHE )
2H + + 2e¡ = H2 0:08 ¡ 0:32
0:10 ¡ 0:30
0:15 ¡ 0:25
0:18 ¡ 0:22
0:20 ¡ 0:20
Solution:
¡ ¢
Linear least squares on the given data gives E = ¡0:4 V + 1:0V:cm2 =A i
-0.1
-0.15
-0.2
E (V)
-0.25
-0.3
Slope = 1.0 V.cm2/A
-0.35
-0.4
0 0.05 0.1 0.15 0.2 0.25
i (A/cm2)
The polarization resistance and the anodic Tafel slope are
Rp = slope = 1:0 ohm:cm2

¯
Rp =
icorr
¯a¯c
¯ = = 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 e¤ects between the body-centered cubic

ferrite (BCC ®-F e) and tetragonal cementite (F e3 C) crystal structures. In
fact, this type of corrosion is bene…cial 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 crys-
talline 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
the other hand, impurities also change properties due to segregation along grain
boundaries. Therefore, E o must change and it is di¤erent at grain boundaries
(atomic mismatch) due to the straining e¤ects 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 di¤erence 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 e¤ects of other
ions that might react with silver.
Solution:
The possible half-cell reactions and standard potentials are
2Ag + + 2e = 2Ag =) o
EAg = 0:799 V
Cu = Cu+2 + 2e =) o
ECu = ¡0:337 V
2Ag + + Cu = 2Ag + Cu+2 =) o o + E o = 0:462 V
E = EAg Cu
The free energy change is
¢Go = ¡zF E o = ¡ (2) (96; 500 J=mol:V ) (0:462 V )

¢Go = ¡89; 166 J=mol
Therefore, silver (Ag) will be reduced since ¢Go < 0: Using the Nernst
equation yields the copper ion concentration
RT
E = Eo ¡ ln (K)
zF ¡ ¢
J
zF (E o ¡ E) (2) 96; 500 mol:V (0:462 V + 0:04 V )
ln (K) = = ¡ J
¢
RT 8:314 mol:o K (313o K)
ln (K) = 37:23
K = 1:48x1016
Then,
2£ ¤
[Ag] Cu+2
K = 2
[Ag + ] [Cu]
2
£ ¤ K [Ag + ] [Cu]
Cu+2 = 2
[Ag]
¡ ¢£ ¤2
£ ¤ 1:48x1016 8x10¡ 9
mol=l [1 mol=l]
Cu+2 = 2
[1 mol=l]
£ ¤
Cu+2 = 0:95 mol=l
£ ¤
CCu+2 = Cu+2 Aw;Cu = (0:95 mol=l) (63:55 g=mol)
CCu+2 ' 60 g=l
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
o
E = ¡0:042 V > ECu
á = E ¡ E o = ¡0:042 V ¡ 0:337V
á ' ¡0:38 V
5.13 What is the signi…cant di¤erences between the overpotential (´) and
the Ohmic potential (E)?
Answer: Mathematically, both potentials have di¤erent 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,
Ohm’s law, E = IR is linear and it may include other terms, such as overpo-
tential and solution (electrolyte) potential, Ás = IRs . Equation (3.25) describes
the Ohm’s potential in details.
E = Ecorr ¡ á ¡ ć ¡ Ás = IR
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 =) o
EZn = 0:763 V
2H + + 2e = H2 =) EHo
=0
Zn + 2H + = Zn+2 + H2 =) 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 = ¡zF E o = ¡ (2) (96; 500 J=mol:V ) (0:763 V )

¢Go = ¡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 de…ned by the Nernst equation.
Solution:
Using eqs. (3.31) and (2.24) yields
RT
E = Eo ¡ ln (K)
zF
o
zF (E ¡ E)
ln (K) =
RT
But,
¢G = ¡RT ln (K)
zF (E o ¡ E)
¢G = ¡RT:
RT
¢G = zF (E ¡ E o ) = zF ´ a
But,
µ ¶
ia
á = ¯ a log
icorr
µ ¶
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),

It (10 A) (1; 800 s)
N= = = 0:093moles
zF (2) (96; 500 A:s=mol)
From eq. (5.12c),
ItAw
W = = N Aw = (0:093mol) (63:55 g=mol)
zF
W = 5:93 grams
5.18 (a) Derive the Arrhenius equation from the general de…nition 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 coe¢cients 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) Dissociation Constant Ksp
200 0:02x1011
250 0:22x1011
280 0:50x1011
300 1:00x1011
330 1:95x1011
350 3:00x1011
360 3:65x1011
Solution:
(a) From eq. (5.20),
d (ln Ksp )
¢G¤ = RT 2
dT
dT Rd (ln Ksp )
=
T2 ¢G¤
Z T Z
R
T ¡ 2 dT = d (ln Ksp )
o ¢G¤
R
¡T ¡ 1
= (ln Ksp ¡ ln B)
¢G¤
Ksp ¢G¤
ln = ¡
B RT µ ¶
¢G¤
Ksp = B exp ¡
RT
(b) Using the derived expression for two di¤erent rates yields
µ ¶
¢G¤
Ksp@300 = B exp ¡
RT300
µ ¶
¢G¤
Ksp@350 = B exp ¡
RT350
· µ ¶¸
Ksp@300 ¢G¤ 1 1
= exp ¡
Ksp@350 RT T350 T300
Thus,
R ln (Ksp@300 =Ksp@350 )
¢G¤ =
1=T350 ¡ 1=T300
(8:314) ln (1=3)
¢G¤ = = 19; 181 J/mol
1=350 ¡ 1=300
and
µ ¶
¢G¤
B = Ksp@300 exp
RT300
½ ¾
¡ 11 ¢ 19181 J/mol
B = 10 exp ¡
[8:314 J/(mol.K)] (300 K)
B = 2:1869 £ 1014
Check:
µ ¶
¢G¤
Ksp@300 = B exp ¡
RT300
µ ¶
¡ ¢ 19181
Ksp@300 = 2:1869 £ 1014 exp ¡ = 1 £ 1011
(8:314) (300)
µ ¶
¡ ¢ 19181
Ksp@350 = 2:1869 £ 103 exp ¡ = 3 £ 1011
(8:314) (350)
Ksp@350 3 £ 1011
= =3
Ksp@300 1 £ 1011
¡ ¢ ¡ 19181 ¢ ¡ ¢
(c) Plot Ksp = 2:1869 £ 103 exp ¡ 8:314T = 2186:9 exp ¡ 2307:1
T
Ksp 3
0
200 250 300 350 400
T (Degree Kelvin)
5.19 Plot the given conductivity data vs: the aqueous Cu+2 SO4¡ concen-
tration 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 ¢ ¡ Kc ¢
mol=cm3 ohm¡ 1 ¢ cm¡ 1
x10¡ 6 x10¡ 3
0 0
25:00 3:00
50:00 5:10
75:00 7:40
100:00 8:50
102:50 10:00
200:00 15:00
202:50 16:00
Linear least squares on the given data yields
¡ ¢ ¡ ¢
Kc = 1:1922x10¡ 3 ohm¡ 1 ¢ cm¡ 1 + 73:46 mol=cm3 C
25
Kc (x10-3 ohm-1.cm-1)
20
15
10
0
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 cor-

roding metal is exposed to a H + ion-containing electrolyte. Use the given data
´ = 0:005 V T = 25o C
i = 3:895 £ 10¡ 8 A=cm2 ½ = 7:14 g=cm3
io = 10¡ 7 A=cm2 D = 10¡ 5 cm2 =s
CR = 5:8277x10¡ 4 mm=y
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 relation-
ship 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),

µ ¶
zF ´
i = io (3.16c)
RT
¡ ¢
iRT 3:895x10¡ 8 A=cm2 (8:314 J=mol:o K) (298o K)
z = =
io F ´ (10¡ 7 A=cm2 ) (96; 500 J=mol:V ) (0:005 V )
z = 2
iAw
CR = = 5:8277x10¡ 4 mm=y = 1:848x10¡ 12 cm=s (3.48)
zF ½
¡ ¢¡ ¢
zF ½CR (2) (96; 500 A:s=mol) 7:139 g=cm3 1:848x10¡ 12
cm=s
Aw = =
i (3:895 £ 10¡ 8 A=cm2 )
Aw = 65:38 g=mol
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 =) o
EZn = 0:763 V
2H + + 2e = H2 =) EHo
=0
Zn + 2H + = Zn+2 + H2 =) 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
RT
E = Eo ¡ ln (K) (2.32)
zF£ ¤
RT Zn+2 [H2 ]
´ = ¡ 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
c) From eq. (2.24),
¢G = ¡zF E (2.24)
E = ´ + E o = 0:005 V + 0:763V = 0:768 V
¢G = ¡ (2) (96; 500 J=mol:V ) (0:768 V )
¢G = ¡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 (3.95)
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
cm=s
e) Using eq. (5.97) yields the zinc ionic mobility
DZn+2 = kT BZn+2 (3.97)

DZn+2 10¡ 5 cm2 =s
BZn+2 = = ¡ 23
kT (1:38x10 J=mol:o K) (298o K)
cm2 :mol cm2
BZn+2 = 2:43x1015 = 2:43x1015
J:s V:s
f) Using eq. (5.93) gives the zinc ionic conductivity
Kc;Zn+2 = zF BZn+2 CZn+2
µ ¶
15 cm
2 ¡ ¢
Kc;Zn+2 = (2) (96; 500 A:s=mol) 2:43x10 6:77x10¡ 4
mol=cm3
V:s
Kc;Zn+2 = 3:18x1017 ohm¡ 1 :cm¡ 1
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) Faraday’s 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 =) o
ECu = 0:337 V
2H + + 2e = H2 =) EHo
=0
Cu + 2H + = Cu+2 + H2 =) 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 = (6; 000 C) 6:24x1018 electron=C
Ne ' 4x1022 electrons
c) From eq. (5.12b),
Q 6; 000 C
N= = = 0:0311 moles
zF (2) (96; 500 C=mol)
d) From eq. (5.12c),
W = N Aw = (0:0311 moles) (63:55 g=mol)

W = 1:98 grams
e)
W 1:98 g
PR = = = 1:65x10¡ 3
g=s = 5:94 g=h
t 1; 200 s
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 ¹A=cm2 and 100 ¹A=cm2 ,
respectively. Assume a symmetry factor of 0:50 at room temperature (25o C).
Solution:
2H + + 2e = H2 =) o
EH =0
From eq. (5.20b),
µ ¶
RT ic
ć = ¡ ln
zF ® io
¡ ¢ µ ¶
8:314 mol:J o K (298o K) 6; 000
ć = ¡ ln
(1) (96; 500 J=mol:V ) (0:5) 100
ć = ¡0:21V
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 ć < 0.
Solution:
From eq. (5.20b),

µ ¶
RT ic
ć = ¡ ln
zF ® io
µ ¶
2:303RT ic
ć = ¡ log
zF ® io
dć 2:303RT
= ¡
d log (ic ) zF ®
Thus,
¡ ¢
d´ c (2:303) 8:314 mol:J o K (298o K)
¯c = =¡
d log (ic ) (2) (96; 500 J=mol:V ) (0:5)
¯c = ¡0:06 V =decade
5.24 Plot the normalized current pro…le as a function of both symmetry

factor (®) and overpotential; that is, i=io = f (®; ´) when the oxidation state
is de…ned is z = 2 and ® = 0:35; 0:50 and 0:75 at room temperature (25o C).
Explain the polarization behavior very succinctly.
Solution:

· ¸ · ¸
i ®zF ´ (1 ¡ ®) zF ´
= exp ¡ exp ¡
io RT RT
i
= exp [77:90®´] ¡ exp [¡ (1 ¡ ®) 77:90´]
io
15
Cathodic α = 0.75 0.50
10 Region
i/io
5 0.35
-5 Tafel Region
-10 Anodic
Region
-15
-0.06 -0.04 -0.02 0 0.02 0.04 0.06 0.08
η (V)
The normalized current density (i=io ) shows the expected linearized Tafel re-
gion 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 signi…cantly. Therefore, variations of the current density (i) strongly
depend on the overpotential (´) and the shape of the curves depend on the sym-
metry 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 2 mm
60 mm
MnO2
( ) Carbon
15 mm
Solution:
Q = 36 kJ=V = 36; 000 A:s = 36; 000 Coulombs
2
As = 2¼Lr = (2¼) (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 = V ½ = 5:65 cm3 7:14 g=cm3 = 40:34 g
MZn 40:34 g
XZn = = = 0:62 mol
Aw;Zn 65:37 g=mol
b) The mass and moles of M nO2 are
Q 36; 000 A:s

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

Q 36; 000 A:s
t = = = 5 hours
I 2A
E = P=I = (3 V:A) = (2 A) = 1:5 V
5.26 A plate of pure nickel (N i) oxidizes in an electrochemical cell contain-

ing 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:
N i = N i+2 + 2e z=2 ½ = 8:90 g=cm3

r = 2x1016 e=s Aw = 58:71 g=mol
qe = 1:6022x10¡ 19 A:s=e As = 100 cm2
a) From eq. (5.50),

¡ ¢¡ ¢
I = rqe = 2x1016 e=s 1:6022x10¡ 19
A:s=e
I = 3:20x10¡ 3 A
I 3:20x10¡ 3 A
i = = = 32 ¹A=cm2
As 100cm2
Then,
¡ ¢
iAw 32x10¡ 6 A=cm2 (58:71g=mol)
CR = =
zF ½ (z) (96; 500 A:s=mol) (8:90g=cm3 )
CR = 1:10x¡ 9
cm=s = 0:35 mm=y
b)
I zF m
i = =
As As tAw
zF m zF ½CR
=
As tAw Aw
¡ ¢ ¡ ¢
m = ½CR As t = 8:90 g=cm3 (0:035 cm=s) 100 cm2 (1 y)
m = 31:15 grams
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 ½ = 7:85 g=cm3 , respectively.
Solution:
Curve …tting:
µ ¶
¡ 2 2 ohm:cm3 1
Rp = 3:8502 £ 10 ohm:cm + 30:147
y CR
140
120
Rp (ohm.cm2)
100
80
60
40 S = 30.147 ohm.cm3/y
20
0
1 2 3 4
1/CR (y/cm)
Combining eqs. (3.25a) and (3.48) yields

µ ¶
¯Aw 1
Rp =
zF ½ CR
µ ¶
¯Aw
S =
zF ½
¡ ¢¡ ¢¡ ¢
zF ½S (2) 3:06x10¡ 3
A:y=mol 7:85 g=cm3 30:147 ohm:cm3 =y
¯ = =
Aw 55:85 g=mol
¯ = 0:03 V
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 CNi+2 = 10¡ 5 mol=cm3

vSO¡2 = 0:1 cm=s CSO¡2 = 10¡ 5 mol=cm3
4
CCu+2 = 10¡ 5 mol=cm3
¡ If+2the
¢ current density is 1 A=cm , calculate the velocity of the nickel ions
2
Ni .
Solution:
From eq. (5.86),

X X¯ ¯
i = zj+ F vj+ Cj+ + ¯z ¡ ¯ F v ¡ C ¡
j j j
h i
i = F (zvC)Cu+2 + (zvC)Ni+2 + (jzj vC)SO¡2
4
h i
i = 2F (vC)Cu+2 + (vC)Ni+2 + (vC)SO¡2
4
¯ ¯
¯ ¯
If zCu+2 = zNi+2 = ¯zSO¡2 ¯ = 2 and C = CCu+2 = CNi+2 = CSO¡2 = 10¡ 5
4 4
mol=cm3 , then h i
i = 2F C vCu+2 + vNi+2 + vSO¡2
4
Solving for vNi+2 yields

i
vNi+2 = ¡ vCu+2 ¡ vSO¡2
2CF 4
1 cm cm
vNi+2 = ¡ mol
¢¡ A:s
¢ ¡ 0:22 ¡ 0:1
(2) 10¡ 5 cm3 96; 500 mol
s s
vNi+2 = 0:20 cm=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 e¤ective electrode surface is A = 8; 000 cm2 :
Solution:
a) From eq. (5.103),
s
µ ¶2
1
Z (w)x = Rx2 +
!Cx
s · ¸2
2 1
Z (w)x = (0:25 ohm) +
(50 s¡ 1 ) (20A:s=V )
Z (w)x = 0:25 ohm
Therefore, Rs = Z (w)x = 0:25 ohm:
b) From eq. (5.104),
Ex = Ix Z (w)x
Ex = (10 A) (0:25 ohm) = 2:5 V
c) From eq. (5.99),
¡ ¢
¸ = L=A = (15 cm) = 8; 000 cm2
¸ = 1:88x10¡ 3 cm¡ 1
¸ ¸
Kc = =
Rs Z (w)x
1:88x10¡ 3 cm¡ 1
Kc = = 7:50x10¡ 3
ohm¡ 1 :cm¡ 1
0:25 ohm
5.30 Determine and analyze the impedance pro…le 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
2 1
Z (w)x = (0:25) +
20!
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 (½c ). [Solution:
(a) v = 0:0055 cm=s, (b) Kc = 0:0106 ohm¡ 1 :cm¡ 1 and (c) ½c = 94:21 ohm:cm].
Solution:
a) From eq. (5.92),

µ ¶µ ¶
cm2 V
v = BFx = 55x10¡ 5
10 = 0:0055 cm=s
V:s cm
b) Using eq. (5.93) yields
Kc = zF BC
µ ¶µ ¶µ ¶
A:s cm2 mol
Kc = (2) 96; 500 55x10¡ 5
10¡ 4
mol V:s cm3
Kc = 0:0106 ohm¡ 1 :cm¡ 1
and from eq. (5.89)
½c = 1=Kc = 94:21 ohm:cm
5.32 It is known that current ‡ows when there exists a gradient of electric
potential (dÁ=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
de…nition 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
dÁ
Ex = ¡ (a)
dx
dÁ
i = Kc Ex = ¡Kc (b)
dx
I dÁ
= ¡Kc (c)
Ac dx
dÁ
I = ¡Ac Kc (d)
dx
This expression agrees with the above statement because I = f (dÁ=dx). For
a homogeneous conductor, eq. (d) becomes
¢Á
I = ¡Ac Kc
¢x
where ¢x becomes the length of the conductor.
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 = 2 & Aw;Mg = 24:31 g=mol

zAl = 3 & Aw;Al = 26:98 g=mol
zZn = 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
X fj Aw;j fMg Aw;Mg + fAl Aw;Al + fZn Aw;Zn

Aw;alloy = =
zj zMg + zAl + zZn
Aw;alloy = 13:48 g=mol
5.EX2 An electrochemical ionic concentration cell shown below was used

as a concentration cell in order to measure the current due to the di¤erence in
ionic concentration between the anodic half-cell and the cathodic-half cell. Deter-
mine the corrosion rate in terms of electrons/second and the number of anodic
reactions/second if the measured current is 3:23x10¡ 7 ¹A = 3:23x10¡ 7 C=s.
Solution:
The oxidation of copper (corrosion) and the reduction of copper (electroplat-

ing) are, respectively
Cu ¡! Cu2+ + 2e¡
Cu2+
+ 2e¡ ¡! Cu
Clearly, the oxidation state is z = 2: Thus, the corrosion rate is
I 3:23x10¡ 7 C=s
r= = ¼ 2x1012 electrons=s
qe (1:6022x10¡ 19 C=electrons)
Also,
I 3:23x10¡ 7 C=s
r = =¡ electrons
¢
zqe 2 reactions (1:6022x10¡ 19 C=electrons)
r = 1012 reactions=s
5.EX3 Use the Evans diagram given below to determine (a) the linear cor-
rosion rate pro…le, 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.
Solutions:
(a) From eq. (5.48),
ia Aw
CR = = ¸ix (a)
zF ½
Aw 55:85 V:cm3
¸ = = = 3:6770 £ 10¡ 5
zF ½ 2 ¤ 96500 ¤ 7:87 A:s
µ 3
¶
V:cm
CR = 3:6770 £ 10¡ 5 (60 ¤ 60 ¤ 24 ¤ 365) (10) ix
A:s
CR = 11; 596ix (inmm=yr)
The slope of this plot represents the volume of F e2+ ions per electric charge.
Hence,
dCR cm3
= ¸ = 3:6770 £ 10¡ 5
(slope)
dix A:s
dCR mm3
' 0:038
dix A:s
The upper and lower CR values are
CR = 11:60 mm=yr @Ecorr (upper limit )

CR = 1:16 £ 10¡ 4 mm=yr @EF e (lower limit)
Therefore, corrosion can be minimized signi…cantly 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
ia Aw
CR = = ¸ia
zF ½
µ ¶
2:303 (Ea ¡ Ecorr )
ia = icorr exp
¯a
µ ¶
2:303 (Ea ¡ Ecorr )
CR = ¸icorr exp (b)
¯a
CR = (11:60 mm=yr) exp (57:58Ea + 14:39) (c)
The non-linear corrosion rate pro…le is given by eq. (c) and it is depicted in
the …gure below.
The upper and lower CR values in this case are
CR = 11:54 mm=yr @Ecorr (upper limit )

CR = 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,
µ ¶
@C Co x2
= ¡p exp ¡
@x 4¼Dt 4Dt
µ ¶
@2C xCo x2
= p exp ¡
@x2 4Dt ¼Dt 4Dt
71
72 CHAPTER 6. MASS TRANSPORT BY DIFFUSION AND MIGRATION
Thus, Fick’s second law becomes
@C @2 C
= D
@t @x2 µ ¶
@C xCo x2
= p exp ¡
@t 4t ¼Dt 4Dt
¡ ¡4 ¢ " #
2
@C (0:1 cm) 10 mol=cm3 (0:1 cm)
= p exp ¡
@t (4) (10 s) (¼) (10¡ 5 cm2 =s) (10 s) (4) (10¡ 5 cm2 =s) (10 s)
@C mol
= 1:96x10¡ 16
@t cm3 :s
6.3 What’s the action of hydrogen on a steel blade exposed to an aqueous

solution of hydrogen sul…de 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 ¡ 2
+ 2H + + 2e ! F eS + 2H
Atomic hydrogen readily di¤uses 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 (¾ys ) of the steel blade. If P > ¾ 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 ¹A=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 ¡ (Cathode)
DO2 = 10¡ 5
cm2 =s T = 25o C F = 96; 500 A:s=mol
6.1. PROBLEMS 73
Solutions:
a) From eq. (6.1) along with Cb = 10¡ 2

mol=l = 10¡ 5
mol=cm3 , the molar
‡uxes are
¡ ¢¡ ¢
J (x; t)c = Cb v (x; t) = 10¡ 5 mol=cm3 2x10¡ 4
cm=s
mol
J (x; t)c = 2x10¡ 9
cm2 :s
mol @C DCb
J (x; t)d = 2x10¡ 9 =D =
cm2 :s @x ±
mol zF DC b dÁ
J (x; t)m = 2x10¡ 9 =
cm2 :s RT dx
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)
µ ¶µ ¶
A:s ¡ 9 mol
i = (4) 96; 500 6x10
mol cm2 :s
A ¹A
i = iL = 2:32x10¡ 3 = 2:32x103
cm2 cm2
c) Corrosion will not occur because iL = 2:32x103 ¹A=cm2 > icrit = 103
¹A=cm2 .
6.5 a) Determine the oxygen concentration for Problem 6.4 that will pro-
mote corrosion of the stainless steel pipe. b) How long will it take for corrosion
to occur?
Solutions:
a) For a di¤usional process only, From eq. (6.9a) yields along with @C=@x '
DCb =± and i = ic ,
¡ ¡3 ¢
ic ± 10 A=cm2 (0:05 cm)
Cb = =
zF D (4) (96; 500 A:s=mol) (10¡ 5 cm2 =s)
Cb = 1:30x10¡ 2
mol=l = 1:30x10¡ 5
mol=cm3
¡ ¢
This result indicates that approximately 100% 1:30x10¡ 2
¡ 10¡ 2
=1:30x10¡ 2
=
23% increase in oxygen content will cause corrosion.
b) From eq. (6.52),
zF C
ic p b
=
¼Dt
· ¸2
D zF Cb
t =
¼ ic
µ ¡5 ¶" ¡ ¢ #2
10 cm2 =s (4) (96; 500 A:s=mol) 1:30x10¡ 5
mol=cm3
t =
¼ 10¡ 3 A=cm2
t = 80:15 s = 1:34 min:
6.6 Use the given data to calculate a) the di¤usivity 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 ¡ i 2¢ ¡ @C=@x4 ¢
(sec) A=cm mol=cm
0 0 0
5 0:1455 0:07532
10 0:1029 0:05326
15 0:0840 0:04349
20 0:0728 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),
µ ¶
@C mol mol:s1=2 ¡
= 1:801 5 £ 10¡ 6
+ 0:16842 t 1=2
@x cm4 cm4
6.1. PROBLEMS 75
0.08
Eq. (4.48)
dC/dx (mol/cm4) 0.07
0.06
0.05
0.04 Slope = 0.1684 mol.s1/2.cm-4
0.03
0.2 0.25 0.3 0.35 0.4 0.45
-1/2 -1/2
t (sec )
From eq. (6.48),
µ ¶
@C Cb Cb
= p = p t¡ 1=2
@x ¼Dt ¼D
C mol:s1=2
S = p b = 0:16842
¼D cm4
µ ¶2 µ ¶2
1 Cb 1 9:443x10¡ 4 mol=cm3
D = =
¼ S ¼ 0:16842 mol:s1=2 =cm4
D = 10¡ 5
cm2 =s
b) Polynomial …t:
³ ´
i = 4:8903 £ 10¡ 3
A=cm2 + 0:30648 A:s1=2 =cm2 t¡ 1=2
0.14 Eq. (4.52)
i (A/cm2)
0.12
0.1
S = 0.30648 A.s1/2/cm2
0.08
0.06
0.2 0.25 0.3 0.35 0.4 0.45
-1/2 -1/2
t (sec )
From eq. (6.52),
zF DCb
i = p
¼Dt
µ ¶
zF DCb ¡ 1=2
i = p t
¼D
zF DCb
S = p = 0:30648 A:s1=2 =cm2
¼D
p ¡ ¢p
S ¼=D 0:30648 A:s1=2 =cm2 ¼=10¡ 5 cm2 =s
z = =
F Cb (96; 500 A:s=mol) (9:443x10¡ 4 mol=cm3 )
z = 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 di¤usion and migration mass transfer under steady-
state conditions, b) the gradients dc=dx; dÁ=dx; and d¹=dx, and c) approximate
the thickness of the di¤usion layer at the cathode electrode surface. Operate
the electrowinning cell for 10 minutes and let the di¤usivity for Cu+2 ions be
10¡ 5 cm2 =s:
Solutions:
Cb = 60 g=l = (60 g=l) (63:55 g=nol) t = 10 min = 600 sec

Cb = 0:944 mol=l z=2
Cb = 9:44x10¡ 4 mol=cm3 F = 96; 500 A:s=mol
D = 10¡ 5 cm2 =s k = 1:38x10¡ 23 J=o K
6.1. PROBLEMS 77
a) From eq. (6.52),

r
zF DCb D
i = p = zF Cb
¼Dt ¼t
s
¡ ¡ 4 3
¢ (10¡ 5 cm2 =s)
i = (2) (96; 500A:s=mol) 9:44x10 mol=cm
(¼) (600 sec)
i = 1:33x10¡ 2
A=cm2
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 di¤usion and migration ‡uxes are equal. Thus,
J = Jd + Jm
mol
Jd = Jm = J=2 = 3:44x10¡ 8
cm2 :s
From eq. (6.48),
¯
@C ¯¯ C 9:44x10¡ 4 mol=cm3
= p b =p
@x ¯x=0 ¼Dt (¼) (10¡ 5 cm2 =s) (600 sec)
¯
@C ¯¯ moil
= 3:88x10¡ 3
@x ¯ x=0 cm4
From eq. (6.15), the ionic mobility is
D 10¡ 5 cm2 =s
B = =
kT (1:38x10¡ 23 J=o K) (308o K)
cm2 V:cm2
B = 2:35x1015 = 2:35x1015
J:s C:s
Now, using eq. (6.12) yields
dÁ Jm
= ¡
dx zqe Cb B
mol
dÁ 3:44x10¡ 8 cm 2 :s
= ¡ ¡ mol
¢¡ V:cm2
¢
dx (2) (1:602x10¡ 19 ¡
C) 9:44x10 cm3 2:35x1015
4
C:s
dÁ
= ¡4:83x10¡ 2
V =cm
dx
From eq. (6.11),

d¹ dÁ
= zqe
dx dx
d¹ ¡ ¢¡ ¢
= (2) 1:602x10¡ 19
J=V ¡4:83x10¡ 2
V =cm
dx
d¹
= ¡1:55x10¡ 20
J=cm
dx
c) From eq. (6.53),
p
± = ¼Dt
p
± = (¼) (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

Cx = Co ¡ (Co ¡ Cb ) erf (y) (4.40)
x dx
y = p dy = p (a)
4Dt 2 Dt
2
x
y2 = (b)
4DtZ
y ¡ ¢
2
erf (y) = p exp ¡y 2 dy (c)
¼ o
Rearranging eq. (6.40) along with C = Cx and Co > Cb = C1 gives
· Z y ¸
2 ¡ ¢
C = Co ¡ Co p exp ¡y2 dy
¼ o
· Z y µ ¶ ¸
2 x2 dx
C = Co ¡ Co p exp ¡ p
¼ o 4Dt 2 Dt
·Z y µ ¶ ¸
Co x2
C = Co ¡ p exp ¡ dx (d)
¼Dt o 4Dt
Thus,
·Z y µ ¶ ¸
@C Co @ x2
= ¡p exp ¡ dx
@x ¼Dt @x o 4Dt
µ ¶
@C Co x2
= ¡p exp ¡
@x ¼Dt 4Dt
¯
@C ¯¯ Co
= ¡p (e)
@x ¯x=o ¼Dt
6.1. PROBLEMS 79
Combining eqs. (6.3) and (e) yields

¯
@C ¯¯
Jx=o = ¡D
@x ¯x=o
DCo DCo
Jx=o = p = ((4.51))
¼Dt ±
p
6.9 Show that dC=dx = Cb = ¼Dt:
Solution:
Using eq. (6.38) for activation polarization (Cb = C1 >> Co ) yields
Cx = Co + (Cb ¡ Co ) erf (y) (4.38)

Cx = Co + Cb erf (y) (a)
x dx
y = p dy = p (b)
4Dt 2 Dt
2 x2
y = (c)
4DtZ
y ¡ ¢
2
erf (y) = p exp ¡y 2 dy (d)
¼ o
Rearranging eq. (6.40) along with C = Cx gives

· Z y ¸
2 ¡ 2¢
C = Co + Cb p exp ¡y dy
¼ o
· Z y µ ¶ ¸
2 x2 dx
C = Co + Cb p exp ¡ p
¼ o 4Dt 2 Dt
·Z y µ ¶ ¸
Cb x2
C = Co + p exp ¡ dx (e)
¼Dt o 4Dt
Thus,
·Z y µ ¶ ¸
@C C @ x2
= p b exp ¡ dx
@x ¼Dt @x o 4Dt
µ ¶
@C C x2
= p b exp ¡
@x ¼Dt 4Dt
¯
@C ¯¯ Cb
= p (e)
@x ¯x=o ¼Dt
6.10 Prove that the di¤usivity D is constant in the Fick’s second law, eq.
(6.17).
Solution:
From eq. (6.39),
Cx ¡ Co
= erf (y)
Cb ¡ Co
µ ¶
Cx ¡ Co x
= erf p
Cb ¡ Co 4Dt
For …xed values of distance x, time t, temperature T and concentration Cx ;
µ ¶
Cx ¡ Co x
= Constant = erf p
Cb ¡ Co 4Dt
Therefore, the di¤usivity is
µ ¶
E¤
D = Do exp ¡ = Constant
RT
D 6= f (Cx )
6.11 Assume that the total molar ‡ux of a specie j is due to di¤usion and
convection. The convective force acting on the specie is Fx = ¡ (1=NA ) (d¢G=dx),
where NA is Avogadro’s number and d¢G=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 = Cv = CBFx
CB d¢G
Jc = ¡
NA dx
Thermodynamically, the free energy change is de…ned by eq. (2.31a)
¢G = ¢Go + RT ln (K)
¢G = ¢Go + RT ln (C=Co )
d¢G d [ln (K)]
= RT
dx dx
6.1. PROBLEMS 81
where K is the rate constant. Thus,

CBRT d [ln (C=Co )]
Jc = ¡
NA dx
· ¸
d [ln (C=Co )]
Jc = ¡CkBT
dx
since k = R=NA = Boltzmann constant. Fick’s …rst law gives

@C
Jd = ¡D
@x
If Jd = Jc , then
· ¸
@C d [ln (C=Co )]
¡D = ¡CkBT
@x dx
· ¸
@C d [ln (C=Co )]
kBT = CkBT
@x dx
· ¸
@C d [ln (C=Co )]
= C
@x 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

d¢G RT dC
=
dx C C
Solution:
d¢G d ln (C=Co )
= RT
dx dx
But,
1 dC d ln (C=Co )
=
C dx dx
Then,
d¢G RT dC
=
dx C dx
6.13 Use the information given in Problem 6.12 to show that
D dC
vx = ¡
C dx
Solution:
From eqs. (6.13) and Problem 6.11,
v = BFx (4.13)
1 d¢G
Fx = ¡
NA dx
d¢G d ln (C=Co )
= RT
dx dx
But,
1 dC d ln (C=Co )
=
C dx dx
Then,
d¢G RT dC
=
dx C dx
Thus, eq. (6.13) yields the drift velocity as
BkT dC
v = ¡
C dx
D dC
v = ¡
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:
dC
J = ¡D + Cv
dx
Co ¡ C
J = ¡D + Cv
x
If C >> Co , then
DC
J =¡ + Cv
x
6.1. PROBLEMS 83
In addition, µ ¶
E¤
D = Do exp ¡
RT
and µ ¶
CDo E¤
J =¡ exp ¡ + Cv
x RT
Mathematically,
² @ If T ! 0, then D ! 0 andJ = Jc ' Cv

² @ If T ! 1, then D ! Do and
CDo
J '¡ + Cv
x
This analysis indicates that the di¤usivity 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 Fick’s
second law, @C=@t = D@ 2 C=@x2 ; based on this information
Solution:
Following the analytical procedure in Appendix A yields

x a¡x b¡x
y= p y1 = p y2 = p
2 Dt 2 Dt 2 Dt
Start with eq. (A6) and (A8):
Z Cb Z 1
¡ ¢ p
dC = B exp ¡y2 dy = ¼B
o ¡ 1
p
Cb = ¼B
Cb
B = p
¼
Then,
Z C Z y2
C ¡ ¢
dC = pb exp ¡y2 dy
o ¼ y1
Z C · Z y2 Z y2 ¸
Cb 2 ¡ 2¢ 2 ¡ 2¢
dC = p exp ¡y dy ¡ p exp ¡y dy
o 2 ¼ o ¼ o
C 1
= [erf (y2 ) ¡ erf (y1 )]
Cb 2
6.16 Derive Fick’s second law if the volume element in Figure 6.2 has a unit
cross-sectional area and a thickness x.
Solution:
µ ¶
@C
Jx;in = D
@x x
µ ¶ µ ¶ µ ¶
@C @C @C
Jx;out = ¡D = ¡D ¡D
@x x+dx @x x @x dx
The concentration rate is

@C @Jx @Jx;in @Jx;out
= ¡ =¡ ¡
@t @xµ ¶ @x µ @x¶ µ 2 ¶
@C @2 C @2C @ C
= ¡D + D + D
@t @x2 x @x2 x @x2 dx
µ 2 ¶
@C @ C
= D
@t @x2 dx
@C @2C
= D
@t @x2
6.17 What does Fick’s …rst law mean in terms of atoms or ions of a single
phase?
¡ @C ¢
Answer: Fick’s …rst law, Jx = D @x , means that atoms or ions di¤use
from high to low concentration regions.
6.18 What will Fick’s …rst law mean if D does not vary with x or C?
Answer: Fick’s …rst law will mean that Jx = D @C @x becomes a linear re-
¡ ¢
lationship under steady-state condition @C@t = 0 and hat atoms or ions di¤use
from high to low concentration regions.
6.1. PROBLEMS 85
6.19 Derive Fick’s second law if the volume element in Figure 6.2 has a unit
cross-sectional area and the di¤using 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 Fick’s …rst law and the continuity equation yields

@C @Jx
= ¡
@t @x
@C
Jx = ¡D
·@x ¸
@C 1 @C
= D
@t @x @x
@C @D @C @2C
= +D 2
@t @x @x @x
If D is constant, then Fick’s second law becomes
@C @2C
=D 2
@t @x
6.20 Find an expression for x when
µ ¶
Cx ¡ Cb x
= 0:5205 = erf p
Co ¡ Cb 4Dt
Solution:
µ ¶
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
y p
=
4Dt
1 x
= p
2 2 Dt
p
x = Dt
6.21 Derive eq. (6.85).
Solution:
Using eq. (6.82) for oxidation yields
· ¸
dCx Cx dÁ
i = zF D +
dx RT dx
· 2 ¸
di d C C d2 Á 1 dC dÁ
= zF D + + =0 (a)
dx dx2 RT dx2 RT dx dx
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 C
= p b (b)
dx ¼Dt
2
d C
= 0 (c)
dx2
Inserting eqs. (b) and (c) into (a) yields
d2 Á 1 dÁ
2
+p =0 (4.62)
dx ¼Dt dx
³ p ´
6.22 Show that dÁ=dx = ¡7Áo = 19 ¼Dt in a coupled di¤usion and
p
migration mass transfer. let x = ¼Dt:
Solution:

µ ¶
x
Á = Áo exp ¡ p
¼Dt
µ ¶
dÁ Áo x
= ¡p exp ¡ p
dx ¼Dt ¼Dt
Ã p !
dÁ Áo ¼Dt
= ¡p exp ¡ p
dx ¼Dt ¼Dt
dÁ Á
= ¡ p o exp (¡1)
dx ¼Dt
dÁ 0:368Áo
= ¡ p
dx ¼Dt
dÁ 7Áo
= ¡ p
dx 19 ¼Dt
6.23 For activation polarization, the concentration gradient is given by eq.

(6.50). If Co >> Cb , then show that
6.1. PROBLEMS 87
µ ¶
C 1 x3
=p ¡x
Co 4¼Dt 12Dt
Solution:
From eq. (6.49) along with Co >> Cb ,

µ ¶
dC Co x2
= ¡p exp ¡
dx 4¼Dt 4Dt
a) Taylor’s series: Letting y = x2 = (4Dt) and expanding the exponential
P
function, exp(¡y) = (¡y)k =k! ' 1 ¡ y, yields
dC Co
= ¡p (1 ¡ y)
dx 4¼Dt
µ ¶
dC Co x2
= ¡p 1¡
dx 4¼Dt 4Dt
µ 2 ¶
dC Co x
= p ¡1
dx 4¼Dt 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 + ::::
µ 1! ¶ 2! 3!
x2
f (x) = exp ¡
4Dt
µ ¶
x2
f (x = 0) = exp ¡ =1
4Dt x=0
µ ¶
0 2x x2
f (x = 0) = ¡ exp ¡ =0
4Dt 4Dt x=0
µ ¶ µ ¶
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
µ ¶
x2 x2
f (x) = exp ¡ =1¡
4Dt 4Dt
Then,
µ 2 ¶
dC 1 x
= p ¡ 1 dx
Co 4¼Dt 4Dt
Z C Z xµ 2 ¶
1 1 x
dC = p ¡ 1 dx
Co o 4¼Dt o 4Dt
µ 3 ¶
C 1 x
= p ¡x
Co 4¼Dt 12Dt
6.24 Derive eq. (5.122) by converting eq. (3.29) into chemical potential
(¹) if only one ion participates in a reaction. The reaction constant is de…ned
by Kr = °C, where ° is the activity coe¢cient and C is the concentration. Let
the molar di¤usion and migration be equal and Jc = 0 in eq. (6.10).
Solution:
¹ = ¹o + kT ln (Kr ) = ¹o + kT ln (°C)
¹ = ¹o + kT ln (°) + ln (C)
d¹ kT
=
dC C
Let
d¹ d¹ dC kT dC
= =
dx dC dx C dx
and
Jd = Jm
dC d¹ dC
¡D = ¡CB = ¡BkT
dx dx dx
D = 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 µ ¶
Cx ¡ C x
= erf p
Co;1 ¡ C ¼Dt
Average concentration:
Co;1 + Co;2 Co
C = =
2 2
Co
C =
2
6.1. PROBLEMS 89
Thus,
· µ ¶¸
Cx 1 x
= erf p
Co 2 ¼Dt
Cx 1
= @ x=0
Co 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 pro…les due to di¤usion, migration and convection for the reduc-
tion 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 di¤usivity 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
pro…les very succinctly and determine which molar ‡ux dominates in this hy-
pothetical 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 F = 96; 500 A:s=mol

Cb = 8 £ x10¡ 4 mol= cm3
vb = 20 cm= s
D = 1:44 £ 10¡ 5 cm2 = s
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 ) = ¼Dt = 1:712 8 £ 10¡ 3 = t
p ¡ ¢ p
Jd = (DCb ) = ¼Dt = 1:712 8 £ 10¡ 3 = t
Jx = Jd + Jm + Jc
¡ ¢
(2) 1:712 8 £ 10¡ 3
Jx = p + 0:002
t
3:4256 £ 10¡ 3
Jx = p + 0:002
t
where t is in seconds and Jx in mol:cm¡ 2 s¡ 1 . Thus, the Jx vs: t pro…le 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 pro…le 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 con…rmed 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 ³ p ´
¡ 1
Á = Áo exp (¡x=±) = RT (zF ) exp ¡x= ¼Dt
³ p ´¡ 1 ³ p ´
dÁ=dx = RT zF ¼Dt exp ¡x= ¼Dt
Jm = (DCb ) (RT )¡ 1 dÁ=dx
³p ´¡ 1 ³ p ´
Jm = (DCb ) ¼Dt exp ¡x= ¼Dt
Jm = 5:416 2 £ 10¡ 7 exp (¡47:016x)
³p ´¡ 1 ³ ´
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
0 1 2 3 4 5 6 7 8 9 10
This con…rms 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 ¼ Jc ¼ 0:002 mol=cm2 :s. Therefore, an e¤ective electrolyte ‡ow system is
important in electrodeposition. Similarly pro…les result for the current density.
¡ ¢
(2) 1:712 8 £ 10¡ 3 3:425 6 £ 10¡ 3
Jx = p + 0:002 = p + 0:002
t t
Using eq. (6.9) yield i in A=cm2 and time t in seconds
³ ´
6£ 10¡3
3: 425p
i = zF Jx = (2) (96500) t
+ 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 pro…le indicates that the current density in A=cm2 is su¢ciently 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 µ ¡ ¢ ¡ ¢ ¶
¡ 5:416 2 £ 10¡¢ 7 exp ¡1736:1x2
i = (2) (96500) ¡ 7
¡ + 5:416 22¢£ 10 exp (¡47:016x) + 0:002
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 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,
d¹=dx = ¡ (zF ) dÁ=dx with an electric potential decay, Áx = Áo exp (¡¸x) Let
6.1. PROBLEMS 93
the free energy change be de…ned as ¢G = ¢Gx @ x and ¢G = ¢G1 @ x = 1.

(b) Plot the concentration Cx pro…le at two di¤erent temperatures. Let
Á1 = 0 ¸ = 0:2 cm¡ 1
¡ 3
Áo = 8:314x10
¡ V¢ 0 · x · 3:8 cm
T = 298 K curve
o
C1 = 1:57x10¡ 3 mol=l = 0:1 g=l
T = 318o K (¢ ¢ ¢ curve) F = 96; 500 J=mol:V
Solution:
a) The oxidation reaction is Cu = Cu+2 + 2e. Combining eqs. (a) and (b)
yields
Z ¹x Z Á1
d¹ = ¡zF dÁ (c)
¹1 Áx
¹x ¡ ¹1 = ¡zF Áx (d)
¹x ¡ ¹1 = ¡zF Áo exp (¡¸x) (e)
From eq. (2.27),
¢Gx = ¹x;prod ¡ ¹x;react = ¹x;prod (f)

¢G1 = ¹1 ;prod ¡ ¹1 ;react = ¹1 ;prod (g)
since ¹x;prod = ¹1 ;react = 0 for the oxidation reaction. From eq. (2.31b),
the change
¢Gx = ¡RT ln (Kx ) = ¡RT ln (Cx ) (h)

¢G1 = ¡RT ln (K1 ) = ¡RT ln (C1 ) (i)
Combining eqs. (f) through (i) gives
¹x = ¡RT ln (Cx ) (j)

¹1 = ¡RT ln (C1 ) (k)
µ ¶
C1
¹x ¡ ¹1 = RT ln (l)
Cx
Finally, equating eqs. (e) and (l) yields

· ¸
zF Áo
Cx = f(x; T ) = C1 exp exp (¡¸x) (m)
RT
· ¸
193
Cx = (0:1 g=l) exp exp (¡0:2x) (n)
T
0.2
C x  0. 1 g/l exp 193

T
exp0. 2x
0.175
Cx
(g/liter)
0.15 T  298 o K
0.125 T  318 o K
0.1
0 1 2 3 4
x (cm)
6.28 Derive an expression for iL = f (Cx ; T; vx ) and explain its physical sig-
ni…cance with respect to concentration polarization and metal reduction. Plot
ć = f (i=iL ) when iL = 5 £ 10¡ 3 A and iL = 10¡ 2 A to support your explana-
tion. 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
zF ·Cx vx T
iL = p = f (Cx ; vx ; T ) (a)
Fx ¼Dt
µ ¶
2:303RT i
ć = log 1 ¡ (b)
zF iL
The schematic polarization diagram is shown below for two di¤erent cases.
6.1. PROBLEMS 95
Thus, iL = f (Cx ; vx ; T ) represents the maximum rate of reduction, and it is

the limiting di¤usion current density. In fact, iL = f (Cx ; vx ; T ) is signi…cant
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 ć ! 1 and ć ! 0 when iL ! 1. The
latter can be de…ned as
Ã p !
2:303RT iFx ¼Dt
ć = log 1 ¡ (c)
zF zF ·Cx vx T
It is also apparent that concentration polarization is possible when jć 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 ¹m=s for electroplating a 3-¹m 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 e¢ciency and at a passive current of 0:8 amperes.
Assume that the oxide passive …lm has a density of 7:19 g=cm3 .
Solution:
Cr+3 + 3e = Cr o
ECr = ¡0:744 V z=3 x = 3x10¡ 4 cm
½ = 7:19 g=cm3 Aw;Cr = 52 g=mol i = I=As = 0:08 A=cm2
As = 10 cm2 ² = 0:50 [Cr+3 ] = aCr+3 = 10¡ 4 mol=l
(a) Using Nernst equation yields
RT
E > Eo = E o + ln (aCr+3 )
zF
(8:314 J=mol:K) (298 K) ¡ ¡ 4 ¢
E > Eo = ¡0:744V + ln 10
(3) (96; 500 J=mol:V )
E > Eo = ¡0:823 V
(b) Integrating equation eq. (7.21) yields the time
Z xµ ¶
zF ½ zF ½x
t = dx =
0 ²iAw ²iAw
¡ ¢¡ ¢
(3) (96; 500 A:s=mol) 7:19 g=cm3 3x10¡ 4
cm
t =
(0:50) (0:08 A=cm2 ) (52 g=mol)
t = 300:22 sec ' 5 min
97
98 CHAPTER 7. CORROSIVITY AND PASSIVITY
(c) The …lm growth rate is
dx ¢x 3 ¹m
= =
dt ¢t 300:22 sec
dx ¹m
= 0:01
dt sec
7.2 (a) If chromiun oxide …lm frow rate is 0:03 ¹m= sec, how long will it
take to grow a 5 ¹m …lm on a Ni-substrate. Assume that the cell operates at
50% current e¢ciency. Calculate (b) the current density.
Solution:
(a) The time is
dx ¢x
=
dt t
¢x 5¹m
t = = = 100 sec
dx=dt 0:05 ¹m= sec
(b) From eq.(7.51), the current density is
¡ ¢
zF ½x (3) (96500) (7:19) 5 £ 10¡ 4
i = =
²tAw (0:8) (100) (52)
i = 0:25 A=cm2
7.3 Brie‡y, explain why the corrosion rate and the corrosion potential in-
crease on the surface of some metallic materials in contact with an oxygen-
containing 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 e¤ect 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 rea-

son why the corrosion rate increases in the presence of oxygen in an acid so-
lution. According to the …gure below, the corrosion rate in terms of current
density and the corrosion potential are
i0
corr = i0
H No oxygen
i0
net
0 0
= icorr ¡ iH = 0 at equilibrium
0 0
Ecorr = EH No oxygen
7.1. PROBLEMS 99
WITH OXYGEN: However, when oxygen is present as an oxidizer the cor-

rosion rate and corrosion potential become
icorr = (iH + iO2 ) > i0

corr
0
Ecorr > 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 insigni…cant e¤ect on the rate of metal dissolution.
Evans Diagram
EO2 Stern Diagram
i O2 iH iO2
ia = ir – if
E (V)
Eo,H
Ecorr io,H
Corrosion Point
E’corr
Eo,M i’corr
icorr
io,M 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
di¤usion coe¢cient of dissolved oxygen are 300 ¹A=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 ¹a=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:
F = 96; 500 A:s=mol Cx = 1:2x10¡ 6 mol=cm3

z=3 ±(static) = 0:07 cm
D = 10¡ 5 cm2 =s ±(flowing) = 0:008 cm
icrit = 300 ¹A=cm2 ½ = 7:8 g=cm3
The reduction reaction is
O2 + 2H2 O + 4e = 4OH ¡ with o

EO 2
= 0:401 VHSE
(a) From eq. (6.99), the limiting current density for both conditions is
¡ ¢¡ ¢
zF DCx 3 (96500 A:s=mol) 10¡ 5 cm2 =s 1:2x10¡ 6 mol=cm3
iL = =
± 0:07 cm
iL ' 49:63 ¹A=cm2 < icrit for corrosion under static solution
iL ' 43:43 ¹A=cm2 > icrit for passivation under ‡owing solution
(b) The limiting current density for passivation under ‡owing solution be-
comes the passive current density, then the passive …lm thickness can be esti-
mated 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
x =
zF ½
¡ ¢
50x10¡ 6 A=cm2 (55:85 g=mol) (300 s)
x =
(3) (96; 500 A:s=mol) (7:8 g=cm3 )
x = 0:371 ¹m = 371 nm
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 di¤usion and migration are equal and (b) the potential gradients.
[Solution: (a) x = 1:03 mm].
Solution:
(a) From eqs. (6.12) and (6.13),
µ ¶
dÁ RT
=
dx dif f usion xF
µ ¶
dÁ E
=
dx electric L
7.1. PROBLEMS 101
Equating these equation yields
RT L (8:314) (298) (8)

x= = = 1:03 mm
EF (2) (96500)
Then the potential gradients are
µ ¶ µ ¶
dÁ dÁ RT (8:314) (298)
= = =
dx electric dx dif fusion xF (0103) (96500)
µ ¶ µ ¶
dÁ dÁ
= = 2:49 £ 10¡ 4
V =cm
dx electric dx dif fusion
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 di¤usivity 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 pro…le 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 ¹A=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 ¹m 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,
i 1:5 ¹A=cm2 mol

JCl¡ = = ' 1:5510¡ 11
zF (1) (96; 500 A:s=mol) cm2 : sec
(b) The time to initiate corrosion, eq. (7.63), is
· µ ¶¸¡ 2
x2 Cth
ti = erf ¡ 1 1 ¡
4D Cs
2 · µ ¶¸¡ 2
(50 mm) ¡ 1 0:6 Kg=m3
ti = erf 1¡
4 (31:61 mm2 =yr) 18 Kg=m3
ti ' 13:43 years
(c) The concentration pro…le of chloride ions, C (x; ti ) at the approximated

initiation time of 13:43 years can be determined using the solution of Fick’s
second law of di¤usion, eq. (7.59).
· µ ¶¸
x
C (x; t) = Cs 1 ¡ erf p (7.59)
2 Dt
" Ã !#
¡ ¢ 10x
C (x; t) = 19 Kg=m3 1 ¡ erf p
2
2 (32 mm =yr) (13:43 yr)
C (x; t) = y = 19:0 erfc (0:241 19x)
20
y 15
10
0
0 1.25 2.5 3.75 5
(d) From eq. (7.69) along with ia = icorr ,
icorr 1x10¡ 6 A=cm2

JF e(OH)2 = =
zF (2) (96500 A: sec =mol)
¡ ¢
JF e(OH)2 = 5:18 £ 10¡ 12 mol= cm2 : sec
Multiplying this result by the iron molar mass, 55:85 g=mol, yields
¡ ¢ ¡ ¢
JF e(OH)2 = 2:893 £ 10¡ 10 g= cm2 : sec = 9:123 £ 10¡ 3
g= cm2 :yr
¡ ¢ ¡ ¢
JF e(OH)2 ' 91:23 g= m2 :yr ' 0:091 Kg= m2 :yr
Thus, the rate of rust [F e(OH)3 ] production, eq. (7.68), is

7.1. PROBLEMS 103
· ¸
MF e(OH)3
JF e(OH)3 = JF e(OH)2 (Rust)
MF e(OH)2
µ ¶
106:85 g=ml £ ¡ ¢¤
JF e(OH)3 = 91:23 g= m2 :yr
89:85 g=mol
¡ ¢
JF e(OH)3 ' 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
¡ ¢
ia Aw 1:5 £ 10¡ 6 A=cm2 (55:85 g=mol)
CR = =
zF ½ (2) (96500 A:sec=mol) (7:86 g=cm3 )
CR = 5:5225 £ 10¡ 11
cm= sec ' 0:017 mm=yr
CR = 17 ¹m=yr
Therefore, the corrosion rate, 127 ¹m=yr, is rather low, but su¢cient 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 ¹m, then the
time for some rust formation that causes cracking and spalling, eq. (7.64), is
25 ¹m
tc = = 1:47 yr
17 ¹m=yr
(g) The repair time, eq. (7.65), is
tr = ti + tc = 13:43 yr + 1:47 yr
tr = 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 = Jrust :tc = 108:49 g= m2 :yr (1:47 yr)
mrust = 159:48 g=m2 = 0:159 g=cm2
7.7 Assume that all electrochemical reactions are governed by the Nernst
equation, which speci…es the relationship between the potential of an electrode
and the concentrations of the two species F e3+ and F e+2 involved in the re-
versible redox reaction at the working electrode. Assume a hydrogen-rich elec-
trolyte. (a) Write down the electrochemical reaction for F e3+ and F e2+ and
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 pro…les 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¡ = R
F e3+ + e¡ = F e2+ for z = 1
µ ¶
RT CF e2+
E = 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¡ = F e2+ for z = 1

µ ¶
RT CF e2+ (0; t)
E = Eo ¡ ln
zF CF e3+
µ ¶
RT 0:5C F e3+ (0; t)
E = Eo ¡ ln
zF CF e3+
RT
E = Eo ¡ ln (0:5)
zF
From Table 2.2, E o = 0:77 VSHE and the driving force is
¡ ¢
8:314510 J:mol¡ 1 K ¡ 1 (298 K)
E = 0:44 VSHE ¡ ln (0:5)
(1) [96; 500 J= (mol:VSHE )]
E = 0:46 VSHE
(d) The current equation at the working electrode surface (x = 0) is
µ ¶
@C
J = ¡D
@x x=0
Q = zF N
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
µ ¶
dQ @C
I= = ¡zF As J = zF As D
dt @x x=0
(e) The schematic concentration pro…les 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 di¤usion is the form of mass transport so that the
current in a voltammetric cell is
I = KO ([O]b ¡ [O]x=0 ) (a)

I = KR ([R]x=0 ¡ [R]b ) = KR [R]x=0 (b)
where KO = zF As DO =± and KR = zF As DR =±, [R]b = 0 in the bulk solution

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

I
[R]x=0 = (e)
KR
Substitute eq. (d) into (a) yields
I = IL ¡ KO [O]x=0
IL ¡ I
[O]x=0 = (f)
KO
Substitute eqs. (e) and (f) into (c) gives
RT [R]x=0
E = Eo ¡ ln
zF [O]
µ x=0 ¶
RT I KO
E = Eo ¡ ln
zF KR IL ¡ I
·µ ¶µ ¶¸
RT KO I
E = Eo ¡ ln
zF KR IL ¡ I
and
µ ¶ µ ¶
RT
o KO RT I
E=E ¡ ln ¡ ln
zF KR zF IL ¡ I
Use I = 0:5IL to get E = E1=2 and
µ ¶
RT KO
E1=2 = E o ¡ ln
zF KR
since ln [I= (IL ¡ I)] = ln [0:5IL = (IL ¡ 0:5IL )] ln [1] = 0. Hence,
Chapter 8
DESIGN AGAINST
CORROSION
CATHODIC PROTECTION
8.1 Why cathodic protection is not generally recommended for stress cor-
rosion 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, cathodi-
cally discharged atomic hydrogen readily di¤uses into the iron matrix, speci…cally
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 > ¾ys (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 sacri…cial 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 Faraday’s law, Eq. (3.12c) or (8.60), the total theoretical weight of
anodes is
ItAw
W =
zF ¡ ¢
(0:70 A) 31:536x106 s (65:37 g=mol)
W =
(2) (96; 500 A:s=mol)
W = 7:48 Kg
Using the anode life (Ld = t) equation given in Table 8.4 yields the theoretical
number of anodes. Hence,
7Ca Aw
N =
3¼zF
¡ ¢
(7) 2:772x106 A:s=Kg (65:37 g=mol)
N =
(3¼) (2) (96; 500 A:s=mol)
N ' 1
Then,
W
M> = 7:48 Kg
N
8.3 Cathodically protect a vertical pressurized steel tank (¾ys = 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 ¹A=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 ½x = 5; 000 ohm:cm for the soil.
Given data for the M g-alloy anode: ½ = 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 = ¼di ht = (¼) (15:24 cm) (25:40 cm)

At = 1; 216 cm2
Aa = N wL = (1) (3 cm) (6 cm) = 18 cm2
The initial current for polarizing the structure is

¡ ¢¡ ¢
Ii = Aa i = 18 cm2 0:43 ¹A=cm2 = 7:74 ¹A
From Table 8.4, the average initial weight of the anode is

3¼Ii Ld
Wi =
7Ca
¡ ¢
(3¼) 7:74x10¡ 6 A (219; 000 h)
Wi =
(7) (1; 230 A:h=Kg)
Wi = 1:86 grams
From Table, 8.5, the anode electrical resistance is

¼½x
Rf = p
10 Aa
¡ ¢
(¼) 5x103 ohm; cm
Rf = p = 370:24 ohm
10 18 cm2
Using Ohm’s law yields the initial potential (Ei ) using a recti…er 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 ¹A=cm2 so
that ¡ ¢¡ ¢
Ip = Aa ip = 18 cm2 0:5 ¹A=cm2 = 9 ¹A
The …nal current for maintaining the structure polarized and cathodically
protected is
If = (1 ¡ ¸i ¡ ¸c Ld ) (Aa i) (8.61)
· µ ¶ ¸
2%
If = 1 1¡0¡ (25) (Aa i)
100%
If = 0:5Aa i = 0:5Ii
¡ ¢¡ ¢
If = (0:5) 18 cm2 0:43 ¹A=cm2 = 3:87 ¹A
For maintenance, the current and the …nal current density are, respectively
Ip + If 9 ¹A + 3:87 ¹A
I = = = 6:44 ¹A
2 2
I 6:44 ¹A
if = = = 0:36 ¹A=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
a) There will be a potential drop and a current change of
¢E = Ei ¡ Ef = Ei = 2:87mV ¡ 2:38 mV = 0:49 mV

¢I = Ii ¡ I = 7:74 ¹A ¡ 6:44 ¹A = 1:30 ¹A
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 an-
ode in terms of current density are 0:43 ¹A=cm2 and 0:36 ¹A=cm2 , respectively.
The initial corrosion rate of the anode in mm=y is
¡ ¢
ii Aw 0:43x10¡ 6 ¹A=cm2 (24:31 g=mol)
CR;i = =
zF ½ (2) (96; 500 A:s=mol) (1:74 g=cm3 )
CR;i = 3:11x10¡ 11
cm=s = 0:0010 mm=y
and the …nal corrosion rate becomes

¡ ¢
if Aw 0:36x10¡ 6 ¹A=cm2 (24:31 g=mol)
CR;;f = =
zF ½ (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
Pd (12 MP a) (15:24 cm)

¾h = = = 50:8 M P a
2B 2 (1:8 cm)
¾h << ¾ ys
As a result, he steel tank will not deform neither explode because ¾h << ¾ 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, respec-
tively. If the measured corrosion rate is 0:051 mm=y, determine a) the tank life
and b) the developed current. Data: ½ = 7:86 g=cm3 and Aw = 55:86 g=mol.
Solutions:
F e ! F e+2 + 2e
P = 200 kP a d=2m
¾ = 420 M P a B = 2 cm
CR = 0:051 mm=y h=8m
a) From eq. (8.64),
iAw Pd
CR = = (8.64)
zF ½ 2¾t
¡ ¢
Pd (200 kP a) 2x103 mm
t = =
2¾CR (2) (420; 000 kP a) (0:051 mm=y)
t = 9:34 years = 2:94x108 sec
b) From eq. (8.61),
zF ½B
i = (8.63)
tAw
¡ ¢
(2) (96; 500 A:s=mol) 7:86 g=cm3 (2 cm)
i =
(2:94x108 s) (55:85 g=mol)
i = 1:84x10¡ 4
A=cm2 = 184 ¹A=cm2
For a lateral area As = ¼dh, the current becomes
I = As i = ¼dhi
¡ ¢¡ ¢¡ ¢
I = (¼) 2x102 cm 8x102 cm 1:84x10¡ 4
A=cm2
I = 92:49 A
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 ² = 1 and Table 8.4,
ItAw
m = eq. (5.30)
zF
3¼It
W = Table 8.4
7Ca
Let m = W since both represent mass. Thus, the anode capacity equations
is
ItAw 3¼It
=
zF 7Ca
3¼zF
Ca =
7Aw
(b) Anode capacity for M g and Zn:
Mg = M g+2 + 2e
3¼zF (3¼) (2) (96; 500 A:s=mol)
Ca;Mg = =
7Aw (7) (24:31 g=mol)
A:h
Ca;Mg = 2; 969
Kg
and
Zn = Zn+2 + 2e
3¼zF (3¼) (2) (96; 500 A:s=mol)
Ca;Zn = =
7Aw (7) (65:37 g=mol)
A:h
Ca;Zn = 1; 104
Kg
p
8.6 Show that ® = Rs =RL .
Solution:
From eq. (8.20),
´x = ó exp (¡®x) (8.20)

d´x
= ¡®ó exp (¡®x) (a)
dx
d2 ´x
= ®2 ´ o exp (¡®x) (b)
dx2
Substituting eqs. (a) and (b) into (8.18) yields
µ ¶
d2 ´ x Rs
= ´x (8.18)
dx2 RL
µ ¶
Rs
®2 ó exp (¡®x) = ó exp (¡®x) (c)
RL
r
Rs
® = (d)
RL
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
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 + Mg Anode Rod
H = 85 cm - L = 0.75H cm
Di = 40.64 cm L H d = 5.08 cm
+
-
Ρw = 900 ohm.cm Aw,Mg = 24.31 g/mol
Aw, s = 55.85 g/mol ΡMg = 1.74 g/cm3
Anode
PS = 7. 86 g/cm3
Di
Drain Valve
Solution:
(a) The design hoop stress (tangential stress) is given
¾ ys 355 MP a
¾= = = 177:50 M P a
SF 2
The hoop stress (average tangential stress) equation is used for determining
the average allowable pressure
P Di
¾ =
2B
2B¾ (2) (0:635cm) (177:50 M P a)
P = = = 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.
(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
P Di (1 M P a) (40:64 cm)
¾ = = = 32 M P a
2B (2) (0:635 cm)
¡ ¢
zF ½B (2) (96; 500 A: sec =mol) 7:86 g=cm3 (0:635 cm)
i = =
tAw;F e (6:312 £ 108 sec) (55:85 g=mol)
i = 27:33 ¹A=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 = Ao (1 ¡ ¸s )
As = ¼Di h (1 ¡ ¸s ) = (¼) (40:64 cm) (76:20 cm) (1 ¡ 0:98)
As = 194:58 cm2
¡ ¢¡ ¢
I = iAs = 27:33 ¹A=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
E 0:65 V
Rs = = = 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
²zF (0:50) (2) (96; 500 A:s=mol)

Ca = = = 1; 103 A:h=Kg
Aw 24:31 g=mol
Thus, anode e¤ective length is La = 0:75H = (0:75) (85 cm) = 63:75 cm so
that the anode mass becomes
¼d2 La (¼) (5:08 cm)2 (63:75 cm)

Va = = = 1; 292:10 cm3
4 ¡ 4 ¢ ¡ ¢
ma = ²½a Va = (0:50) 1:74 g=cm3 1; 292:10 cm3
ma = 1:12 Kg
From Table 8.4, the average anode lifetime is

7Ca ma (7) (1; 103 A:h=Kg) (1:12 Kg)

Ld = =
3¼Ia (3¼) (5:32x10¡ 3 A)
Ld = 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 = Ca ma
EE = (1; 103 A:h=Kg) (1:12 Kg) = 1; 235:36 A:h
EE = 4:45 MJ
Recall that 1 J = 1 A:s.
ANODIC PROTECTION
8.8 For anodic protection, the interface potential of the structure is in-
creased to passive domain, provided that the metal exhibits active-passive be-
havior. Thus, prevention of corrosion is through impressed anodic current.
Explain including the mathematical de…nition 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 solu-
tions?
Answer: The cathodic protection currents in acid solution can lead to hy-
drogen 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
in its passivated stated. The mechanism is quantum mechanical electron tunnel-

ing 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 be-
low. 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 iO2 ¢Go = ¡852:70 kJ=mol

T i + 2H2 O = T iO2 + 4H + + 4e¡ ¢Go = ¡346:94 kJ=mol
Solutions:
(a) The potential for T i + O2 = T iO2 ,
¢G (¡852:70 kJ=mol)
E=¡ =¡ = 4:42 mV
zF 2 (96500 J=mol:V )
Using the Nernst equation,
RT RT [T iO2 ]
E = Eo ¡ ln Ksp = E o ¡ ln
zF zF [T i] [O2 ]
E = E o since [T iO2 ] = [T i] = [O2 ] = 1
For T i + 2H2 O = T iO2 + 4H + + 4e¡ at E o = ¡0:860 V (Table 2.3 ),
¢G (¡346:94 kJ=mol)
E=¡ =¡ = 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
RT RT [T iO2 ] [H + ]
E = Eo ¡ ln Ksp = E o ¡ ln 2
zF zF [T i] [H2 O]
4RT £ + ¤
E = Eo ¡ ln H since [T iO2 ] = [T i] = [H2 O] = 1
zF
Thus,
· ¸
£ ¤ zF (E ¡ E o )
H+
= exp ¡
4RT
· ¸
£ +¤ 2 (96500) (0:0018 + 0:86)
H = exp ¡
4 (8:314) (298)
£ +¤ ¡ 8
H = 5:1417 £ 10
Then,
£ ¤ ¡ ¢
pH = ¡ log H + = ¡ log 5:1417 £ 10¡ 8
pH = 16:78
8.13 The e¤ect of sulfuric acid (H2 SO4 ) concentration on polarization be-
havior of a metal at 25o C can be assessed obtaining experimental potentiody-
namic polarization curves. Below is a data set for the critical current density
(ic ) of a hypothetical metal.
C (%) 0 20 30 40 50 60 70
ic (A=cm2 ) 46 30 23 17 12 8 5
Plot ic = f (C) and explain whether or not passivation is a¤ected 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
For anodic protection, ic must exist for passivation to take place by the for-
mation of an oxide …lm. The plotted data indicates that ic nonlinearly decrease
with increasing percent concentration. This trend means that passivation is read-
ily 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 de-
termining the e¤ect 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 ¢ 0 40 45 55 65 75
ic mA=cm2 4:7 1:6 1:4 1:0 0:7 0:4
CR:icorr (mm=y) 0 2:2 5:6 8:9 7:8 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 com-
pare 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 coe¢cient R2 = ¡0:97. The plot is

y 3.75
2.5
1.25
0
0 20 40 60 80
Actually, Aw has been used as the atomic weight of an element, but now Aw
becomes the molecular weight of the alloy.
Element Fe C Cr Mn Mo Ni Si P S
% 62 0.08 18 2 3 14 1 0.045 0.03
1 X 1
Aw = fi Aw;i = (62 ¤ 55:845 + 0:08 ¤ 12 + 18 ¤ 51:996 + ::::)
100 100
Aw = 75:684g=cm3
Oxidation of iron (Fe):

Aw;F e = 55:85 g=mol ½F e = 7:857 g=cm3 F e ! F e2+ + 2e¡ with
z=2
ic AwF e (55:85 g=mol) (ic )

CR;F e;ic = =
zF ½F e (2) (96500 A:s=mol) (7:857 g=cm3 )
ic AwF e (55:85)(0:4)(10¡3 )
CRF e = zF ½F e = (2)(96500 )(7:857) (10) (60 ¤ 60 ¤ 24 ¤ 365) = 4:6460
%C
¡ H2 SO4 ¢ 0 40 45 55 65 75
ic mA=cm2 4:7 1:6 1:4 1:0 0:7 0:4
CR;F e:ic (mm=y) 54.59 18.58 16.26 11.62 8.13 4.65
Polynomial …t: yF e = 6:4166 £ 10¡ 3 x2 ¡ 1:1395x + 54:501 with R2 = ¡0:97
Oxidation of chromium (Cr):

Aw;Cr = 52 g=mol ½Cr = 7:19 g=cm3 Cr ! Cr3+ + 3e¡ with z = 3
ic AwCr (52 g=mol) (ic )

CR;Cr;ic = =
zF ½Cr (3) (96500 A:s=mol) (7:19 g=cm3 )
(52)(0:4)(10¡3 )
CRF e = (3)(96500 )(7:19) (10) (60 ¤ 60 ¤ 24 ¤ 365) = 3:1513
%C
¡ H2 SO4 ¢ 0 40 45 55 65 75
ic mA=cm2 4:7 1:6 1:4 1:0 0:7 0:4
CR;Cr:ic (mm=y) 37.03 12.61 11.03 7.88 5.51 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 ½Mo = 10:22 g=cm3 M o ! M o3+ + 2e¡ with
z=3
ic AwMo (95:96 g=mol) (ic )

CR;Mo;ic = =
zF ½Mo (3) (96500 A:s=mol) (10:22 g=cm3 )
(95:96)(0:4)(10¡3 )
CRF e = (3)(96500 )(10:22) (10) (60 ¤ 60 ¤ 24 ¤ 365) = 4:0913
%C
¡ H2 SO4 ¢ 0 40 45 55 65 75
ic mA=cm2 4:7 1:6 1:4 1:0 0:7 0:4
CR;Mo:ic (mm=y) 48.07 16.37 14.32 10.23 7.16 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 ½Mn = 7:44 g=cm3 M n ! Mn2+ + 2e¡ with z = 2
ic AwMn (54:94 g=mol) (ic )

CR;Mn;ic = =
zF ½Mn (2) (96500 A:s=mol) (10:22 g=cm3 )
(54:94)(0:4)(10¡3 )
CRF e = (2)(96500 )(7:44) (10) (60 ¤ 60 ¤ 24 ¤ 365) = 4:8264
%C
¡ H2 SO4 ¢ 0 40 45 55 65 75
ic mA=cm2 4:7 1:6 1:4 1:0 0:7 0:4
CR;Mn:ic (mm=y) 56.71 19.31 16.89 12.07 8.45 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
50
y
37.5
25
12.5
0 20 40 60 80
The above …gure shows that the AISI 316 stainless steel is a corrosion resis-
tant 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 experi-
mental 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
ip Aw
CR =
zF ½
For Aw = 47:867 g=mol and ½ = 4:54 g=cm3 ,
Aw 47:867 g/mol cm3

= ³ ´ = 5:4629 £ 10¡ 5
zF ½ (2) (96500 A.s/mol) 4:54 g/cm3 A:s
Thus,
µ ¶
cm3
CR = 5:4629 £ 10¡ 5
ip
A:s
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
2.5
y
2
1.5
0.5
0
0 125 250 375 500 625
Curve …tting gives

µ ¶ µ ¶
mA mA s
ip = 0:09932 + 4:2327 £ 10¡ 3
v
cm2 cm2 mV
with a correlation coe¢cient R2 = 0:99.
Let y = CR and x = v. The plot for CR = f (v) is

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

being. For instance, the lowest and highest corrosion rates are
¡ ¢
CR;min = (0:23122 (10) + 5:4276) 10¡ 8 = 7:74 £ 10¡ 8 mm=y
¡ ¢
CR;max = (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 e¤ects in humans.
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
ItAw (10 A) (8x60x60 s) (63:55 g=mol)

W = =
zF (2) (96; 500 A:s=mol)
W = 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 e¢ciency

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, ½ = 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
²ItAw (0:85) (6 A) (8x60x60 s) (63:55 g=mol)

W = =
zF (2) (96; 500 A:s=mol)
W = 48:36 grams
b) Letting m = W = 48:36 grams yields

m
V = xAT =
½
m 48:36 g
x = =
½AT (8:96 g=cm3 ) (100 cm2 )
x = 0:54 mm
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 ¹m
thick. How long will it take to produce a 1:5 ¹m thick electroplated chromium
…lm on the bumper if the total surface area is 100 cm2 and ² = 60%?
Solution:
Cr+3 + 3e = Cr
a) Using eq. (9.9) with F = 96; 500 C = 96; 500 A:s=mol; ½ = 7:20 g=cm3
and Aw = 52 g=mol yields
²ItAw (0:85) (6 A) (8x60x60 s) (63:55 g=mol)

W = =
zF (2) (96; 500 A:s=mol)
¡ ¢¡ ¢¡ ¢
W = V ½ = As x½ = 100 cm2 1:5x10¡ 4 cm 7:20 g=cm3
W = 0:1080 g
zF W (2) (96; 500 A:s=mol) (0:1080 g)
t = =
²IAw (0:60) (6:68 A) (52 g=mol)
t = 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 di¤usivity
equals to 2:34x10¡ 5 cm2 =s. Calculate the current density due to di¤usion 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),

r
DC D
Jd = p o = Co
¼Dt ¼t
s
¡ ¢ (2:34x10¡ 5 cm2 =s)
Jd = 2x10¡ 4 mol=cm3
(¼) (600 s)
mol
Jd = 2:23x10¡ 8
cm2 :s
From eq. (9.71),
µ ¶
mol
id = zF Jd = (2) (96; 500 A:s=mol) 2:23x10¡ 8
cm2 :s
id = 4:30x10¡ 3
A=cm2 ' 43 A=m2
Obviously, the assume di¤usion 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
i 200x10¡ 4 A=cm2
Jx = =
zF (2) (96; 500 A:s=mol)
mol
Jx = 1:04x10¡ 7
cm2 :s
Thus, the migration and convection molar ‡ux becomes
mol
Jm + Jc = Jx ¡ Jd = 8:13x10¡ 8
cm2 :s
9.5 Calculate the amount of silver that can be electroplated in an electro-

chemical cell containing Ag+ ions and operates at 7 A, 25o C and 101 kP a for
10 minutes. Assume a current e¢ciency of 95%.
Solution:
Ag + + e = Ag
From eq. (9.9),
²ItAw (0:95) (7 A) (10x60 s) (107:87 g=mol)

W = =
zF (1) (96; 500 A:s=mol)
W = 4:46 grams
9.6 What are the di¤erences between galvanic and electrolytic cells? Recall
that both are electrochemical cells.
Answer: Figure 2.2 shows the di¤erences 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 electrore…ning metal M . Thus, the
rate of formation (reduction) and dissolution (oxidation) are treated as steady-
state 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 di¤usion mechanism. Derive expressions for
the weight gain at the cathode side and the weight loss at the anode side.
Solution:
x' x
Electrode
JM JM+2
Reduction Oxidation
0
JM =³¡D@C=@x ´ JM +2 = ¡D@C=@x
³ 0 ´
0
JM = ¡D0 Co ¡ Cx0 =x0 JM +2 = ¡D Cx ¡ Co =x
Co > Cx0 Cx > Co
W 0= V 0½0= x0A0½0 W = V ½ = xA½
Eliminating x0and x yields

³ 0 ´ ³ 0 ´
W 0= A0½0D0 Co ¡ Cx0 =JM W = A½D Cx ¡ Co =JM +2
According to the given conditions, W 0 = W since A0 = A, ½0 = ½ 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:
H+
Cr+6 + 6e¡ = Cr
(a) Thickness:
W 0:25 g
x = =
As ½ (100 cm ) (7:19 g=cm3 )
2
x = 3:48 ¹m
(b) Production rate:
W 0:25 g
PR = = = 2:78x10¡ 4
g=s
t 900 s
PR = 1 g=h
(c) From eq. (9.16),
zF W
² =
ItAw
¡ A:s
¢
(6) 96; 500 mol (0:25 g)
² = = 0:39
(8 A) (900 s) (52 g=mol)
² = 39%
This is a low, but typical current e¢ciency in Cr electroplating.
9.9 It is desired to produce a 20 ¹m 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 e¢ciency
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 ¹m thick …lm of chromium from a solution containing
Cr+6 cations at 30o C.
Solution:
Cr+6 + 6e¡ = Cr
a) Amount of Cr:
W = V ½ = ½xAs
¡ ¢¡ ¢¡ ¢
W = 7:19 g=cm3 20x10¡ 4
cm 65 cm2
W = 0:94 g
b) From eq. (9.16),
zF W
t =
²IAw
¡ 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
9.10 Predict (a) the electric potential E, (b) the time in minutes, and (c)
the …lm growth rate in ¹m= min for electroplating a 10 ¹m-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 e¢ciency and at a passive current density of 5:12x10¡ 3
A=cm2 .
Solution:
Cr+3 + 3e = Cr o
ECr = ¡0:744 V z=3
½ = 7:19 g=cm3 Aw;Cr = 52 g=mol
As = 10 cm2 ² = 0:50 aCr+3 = 10¡ 4 mol=l
(a) Using Nernst equation yields
RT
E > Eo = E o + ln (aCr+3 )
zF
(8:314 J=mol:K) (298 K) ¡ ¡ 4 ¢
E > Eo = ¡:0744V + ln 10
(3) (96; 500 J=mol:V )
E > Eo = ¡0:82 V
(b) Integrating eq. (7.21) yields the time
Z xµ ¶
zF ½ zF ½x
t = dx =
0 ²iAw ²iAw
¡ ¢¡ ¢
(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
(c) The …lm growth rate is
dx ¢x 10 ¹m
= =
dt ¢t 26 min
dx ¹m
= 0:38
dt 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 = Ag+ + OH ¡
[Ag+ ] [OH ¡ ]
Ke = = 1:10x10¡ 4
[AgOH ¡ ]
From eq. (2.67) with x = y = 1;
¡ ¢1=(x+y) ¡ 1+1=(x+y) ¡ 1=2

®1 = Ke x¡ x y ¡ y [CT ] = Ke1=2 [CT ]
¡ ¢ ¡ 1=2
®1 = 1:05x10¡ 2 [CT ]
0.25
0.2
0.15
1
0.1
0.05
0
0 0.125 0.25 0.375 0.5
C T (mol/liter )
b) The degree of dissociation:

¡ ¢ ¡ 1=2
®1 = 1:05x10¡ 2 [0:144] = 0:028
c) The free energy change is
µ ¶
J ¡ ¢
¢Go = ¡RT ln (Ke ) = ¡ 8:314 (298o K) ln 1:1x10¡ 4
mol:o K
¢Go ¼ ¡22:58 kJ=mol
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¡ 4

(From Example 2.11). Let
[Ag + ] = [OH ¡ ] for charge balance so that
2
[Ag+ ] [OH ¡ ] [OH ¡ ]
Ke = = (a)
[AgOH] [AgOH]
£ ¡
¤ p
OH = K [AgOH] (b)
The dissociation of water ant its rate constant are
H2 O = H + + OH ¡ (c)
[H + ] [OH ¡ ]
Kw = = 10¡ 14
(d)
[H2 O]
From eq. (2.64a) along with [H2 O] = 1 mol=l,
£ ¤
OH ¡ = x®1 [CT ] = (1) (0:028) [0:144 mol=l] = 4:03x10¡ 3 mol=l (e)
µ ¶
£ ¤ mol ³ g ´ g
COH ¡ = OH ¡ Aw;OH = 4:03x10¡ 3 17 = 6:85x10¡ 2
(f)
l mol l
£ +¤ £ ¤
Ag = OH ¡ = 4:03x10¡ 3 mol=l (g)
µ ¶
£ ¤ mol ³ g´ g
CAg+ = Ag+ Aw;Ag = 4:03x10¡ 3 107:87 = 0:43 (h)
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),

9.1. PROBLEMS 133
£ ¤ Kw 10¡ 14
H+ = ¡
= = 2:48x10¡ 12 mol=l
[OH ] 4:03x10¡ 3 mol=l
£ ¤ ¡ ¢
pH = ¡ log H + = ¡ log 2:48x10¡ 12 = 11:61
9.13 An electrochemical cell contains 75 g=l of Cu+2 ions at 35o C. Calcu-

late (a) the Reynold and Sherwood numbers,(b) the di¤usion ‡ux (Jx ), (c) the
current density (i) and (d) the the applied potential (E). Data:
d Characteristic distance = 12 cm .
L=x Cathode height = 100 cm .
w Cathode width = 80 cm .
N Number of cathodes = 50 .
Kv Kinematic viscosity = 0:80 cm2 =s .
D di¤usivity = 1:24x10¡ 5 cm2 =s
vx Flow velocity = 46:90 cm=s .
P Electrical Power = 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
² = 0:85 F = 96; 500 Aa:s=mol
(a) From eq. (9.4), (7.5) and (7.25), the Reynold and Sherwood numbers are
vx d (46:90 cm=s) (12 cm)

Re = = = 703:50
Kv (0:80 cm2 =s)
Kv 0:80 cm2 =s
Sc = = = 64; 516:13
D 1:24x10¡ 5 cm2 =s
2 1=3 1=2
Sh = (Sc ) (Re ) = 709:19
3
(b) The di¤usion ‡ux Jx :
@C DCCu+2
Jx = ¡D =¡ =
¡ @x x ¢¡ ¢
1:24x10¡ 5 cm2 =s 1:18x10¡ 3
mol=cm3
Jx =
100 cm
¡ 10 mol
Jx = 1:46x10
cm2 :s
(c) From (7.13), the current density is
i = zF Jx Sh
µ ¶µ ¶
A:s mol
i = (2) 96; 500 1:46x10¡ 10
(709:19)
mol cm2 :s
i = 2x10¡ 2
A=cm2 = 200 A=m2
(d) From elementary physics, the electrical power divided by the current is
the applied potential. Thus,
Ac = wL = (80 cm) (100 cm) = 8; 000 cm2

¡ ¢
As = 2N Ac = (2) (50) 8; 000 cm2
As = 800; 000 cm2 = 80 m2
¡ ¢¡ ¢
I = iAs = 200 A=m2 80 m2 = 16 kA
P 32 kW 32 kV=A
E = = =
I 16 kA 16 kA
E = 2 volts
9.14 An electrolyte containing P b+2 ions at 35o C is used in an electrowin-

ning cell. The electrolyte is under steady laminar force convection. Use the
data given below to determine (a) the the Sherwood number, (b) the di¤usion
‡ux and (c) the current.
Cb Bulk concentration = 75 g=l .

D di¤usivity = 1:24x10¡ 5 cm2 =s
L=x Cathode length = 100 cm
Sc Schmidt Number = 64; 516:13 .
Re Reynolds Number = 703:50 .
As Total cathode area = 800; 000 cm2
² Current e¢ciency = 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

2 1=3 1=2
Sh = (Sc ) (Re )
3
2 1=3 1=2
Sh = (64; 516:13) (703:50) = 709:19
3
9.1. PROBLEMS 135
(b) The di¤usion ‡ux is

@C DCb
Jx = ¡D =¡ =
¡ @x x ¢¡ ¢
1:24x10 cm =s 3:62x10¡
¡ 5 2 4
mol=cm3
Jx =
100 cm
¡ 11 mol
Jx = 4:49x10
cm2 :s
(c) The current is
i = zF Jx Sh
µ ¶µ ¶
A:s mol
i = (2) 96; 500 4:49x10¡ 11
(709:19)
mol cm2 :s
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 di¤usivity 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 e¢ciency range of 0:50 · ² · 1:
Theoretically, analyze the e¤ect of a) the angular velocity ! on the current

density and b) the angular velocity (!) and the current density (²) on the
production rate of metal powder, and c) the potential (E) and the current
density (²) on the energy consumption °.
Solution:
Data: Cu+2 + 2e = Cu @ T = 40o C

¡ ¢
Co = 65 g=l = 65x10¡ 3 g=l = (63:55 g=mol) Aw = 63:55 g=mol
Co = 1:02x10¡ 3 mol=cm3 r = 50 cm
D = 10¡ 5 cm2 =s Kv = 0:60 cm2 =s
µ = 160o w = 6 cm
Total e¤ective surface area:
h1 = r cos (µ=2) = 8:68 cm L = r sin (µ=2) = 49:24 cm

h2 = r = h1 = 41:32 cm S = ¼rµo =180o = 139:63 cm
2 ¡ ¢
¼µ o
Aseg = r2 180 o
µ ¶
r2 ¼µo
Aseg = ¡ sin (µ) = 3; 063:13 cm2
2 180o
Aarc = wL = 295:44 cm2
As = 4 (2Aseg + Aarc ) = 25; 686:80 cm2 ' 2:57 m2
a) From eq. (9.107),
p
0:62zF Co D2=3 !
i =
K 1=6
¡ ¢¡ ¡ ¢2=3 p
(0:62) (2) (96; 500 A:s=mol) 1:02x10¡ 3
mol=cm3 10 5
cm2 =s !
i = 1=6
(0:60 cm2 =s)
µ ¶
A:s1=2 p
i = 616:87 !
m2
8000
7000
i
6000
(A/m2)
5000
4000
3000
2000
1000
0
20 40 60 80 100
ω (Rad/sec)
9.1. PROBLEMS 137
12
10
8
PR
6
(g/s)
4
0
0.5 0.6 100 0
0.7 200
ε 0.8 0.9 400 300
ω (Hz)
Figure 9.1:
b) From 7.16,
³ ´ p
A:s1=2
²iAs Aw 616:87 m2 As Aw ² !
PR = =
³ zF ´¡ zF
¢ p
A:s1=2
616:87 m2 2:57 m2 (63:55 g=mol) ² !
PR =
(2) (96; 500 A:s=mol)
³ ´ p
1=2
PR = 0:52 g:s =s ² !
12
1
10
ε 0.9
0.8
PR 8
0.7
(g/s) 6
0
100 200 300 400 500
ω (Hz)
c) From eq. (9.18),
zF E
° =
Aw ²
(2) (96; 500 A:s=mol) E
° =
(63:55 g=mol) ²
µ ¶
A:s E
° = 3; 036:98
g ²
µ ¶
kW:h E
° = 0:84 where E is in volts
Kg ²
7 4
γ 6 E (V)
(kW.h/Kg) 5 3
4
3
2
2
0
0.5 0.6 0.7 0.8 0.9 1
ε
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 di¤usivity D of a metal cation M +2 in solution at
room temperature.
! (1=¡ sec)¢ 100 225 400 625 900 1; 225

!¡1=2 s1=2 ¢ 10 15 20 25 30 35
i mA=cm2 4:81 7:22 9:58 12:10 14:38 16:80
Co = 2:21x10¡ 6 mol=cm3
Kv = 0:056 cm2 =s
z=2
9.1. PROBLEMS 139
Solution:
Linear least squares on the given data, i vs: !1=2 , yields the Levich plot
³ ´
i = ¡0:488 57mA:cm¡ 2 + 0:49771 mA:s1=2 :cm¡ 2 !1=2
20
18
16
14
2 12
i (mA/cm )
10
8
6
4
2
0
10 20 30 40
1/2
ω (Hz)
From eq. (9.107),
³ ´p
i = 0:62zF Co D2=3 Kv¡ 1=6 !
³ ´
Slope = 0:62zF Co D2=3 Kv¡ 1=6
Ã !3=2
Slope
D = ¡ 1=6
0:62zF Co Kv
" #3=2
0:49771x10¡ 3 A:s1=2 :cm¡ 2
D = ¡ ¢¡ ¢ ¡ 1=6
A:s mol
(0:62) (2) 96; 500 mol 2:21x10¡ 6 cm3 (0:056 cm2 =s)
D = 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
(H2 SO4 ) solution at 35o C. The anodes operate at 100% current e¢ciency with
respect to oxygen evolution and that for the cathodes is ² = 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 speci…c 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) Aw = 63:54 g=mol

E = 2:4 V DCu+2 = 1:24x10¡ 5 cm2 =s
NT = 100 (Tanks) Kv = 0:80 cm2 =s
Na = 30 (Anodes per tank) vx = 0:312 cm=s (Velocity of Cu+2 )
Nc = 29 (Cathodes per tank) d = 6 cm (electrode distance)
Ae = 0:80 m2 (Electrode area) 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.
[Solutions: (a) EHalf
o
¡ cell ¼ ¡1:57 V , (b) ic = 0:001293 A=cm , (c) Sh ¼ 39
2
and Cb = 78:80 g=l].
Solution:
(a) The reactions, the standard half-cell potential and the applied potential
are
Anode: 2H2 O ) 4H + + O2 + 4e
Cathode: Cu+2 + 2e ) Cu
Cathode: 2H + + 2e ) H2
Overall : 2H2 O + Cu+2 + 2H + ) Cu + 4H + + O2 " +H2 "
o o o o
EHalf ¡ cell = EH 2O
+ ECu + EH 2
= ¡1:23 V ¡ 0:337 V + 0
o
EHalf ¡ cell ¼ ¡1:57 V
¯ o ¯
E ¸ ¯EHalf ¡ cell
¯
(b) The total current

9.1. PROBLEMS 141
P 72 £ 103 A V
I= = = 3:0 £ 104 A
E 2:4 V
Electrode areas per tank :
¡ ¢
Aa = NT Na Ae = (100) (30) 8; 000 cm2 = 24:0x106 cm2
2
Ac = NT Nc Ae = (100) (29) (8; 000 cm) = 23:2x106 cm2
Current densities per tank :
I 3:0 £ 104 A A
ia = = = 0:001250 A=cm2 = 1:250
Aa 24:0x106 cm2 m2
I 3:0 £ 106 A A
ic = = = 0:001293 A=cm2 = 1:293
Ac 23:2x106 cm2 m2
(c) Assume force laminar ‡ow. The Schmidt ( Sc ), Reynolds ( Re ) number

and the anode length are
¡ ¢ ¡ ¢
Sc = Kv =D = 0:80 cm2 =s = 1:24x10¡ 5 cm2 =s = 64:52x103
¡ ¢
Re = 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 Sher-
wood number is
p p
L = Ae = 0:8 m2 = 0:8944 m2 = 89:44 cm2
µ ¶µ ¶1=3 µ ¶ " 2
#1=3
9 vx d2 9 (0:312 cm=s) (6 cm)
Sh = =
5 LD 5 (89:44 cm) (1:24x10¡ 5 cm2 =s)
Sh ¼ 39
or from eq. (9.97)
µ ¶· ¸1=3
9 d
Sh = (Sc Re )
5 L
µ ¶ ·µ ¶ ¸1=3
9 6 ¡ ¢
Sh = 64:52 ¤ 103 (2:34) ¼ 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.
µ ¶1=3
9zF Cb vx d2 D2
ic =
5 L4
µ ¶1=3
5ic L4
Cb =
9zF vx d2 D2
¡ ¢" 4
#1=3
(5) 0:001293 A=cm2 (89:44 cm)
Cb = ¡ ¢ ¡ ¢
A:s
(9) (2) 96; 500 mol cm 2¡ 5 cm2
¢2
0:312 s (6 cm) 1:24x10¡ s
Cb = 1:24 £ 10¡ 3 mol=cm3 = 1:24 mol=l
Cb = (1:24 mol=l) (63:55 g=mol) ' 78:80 g=l
Alternatively, using eqs. (9.94) and (7.87b) with ¢C = Cb gives per tank
µ ¶ µ ¶
2 1=3 1=2 2 ¡ ¢1=3 1=2
Sh = (Sc ) (Re ) = 64:52x103 (2:34) ¼ 41
3 3
¡ A
¢
ic L 0:001293 cm 2 (89:44 cm)
Cb = = ¡ ¢ ¡ 2¢
zF DSh (2) 96; 500 mol 1:24 £ 10¡ 5 cm
A:s
s (41)
Cb = 1:18x10¡ 3 mol=cm3 = 1:18 mol=l
Cb = (1:18 mol=l) (63:55 g=mol) = 75 g=l
Both equations give fairly similar results. Let’s use the results given by eq.
(4.94) in eq. (9.87b).
(d) Production rate ( PR ) and total weight produced ( WT ) in 24 hours:
¡ A
¢¡ ¢¡ g
¢
²ic Ac Aw (0:90) 0:001293 cm 2 23:2x106 cm2 63:55 mol
PR = =
zF (2) (96; 500 A:s=mol)
PR = 8:8897 g= sec = 32:003 Kg=h = 768:07 Kg=day (Total)
WT = (32:003 Kg=h) (24 h) = 768:07 Kg (Total)
wt = WT =NT = (768:07 Kg) =100 = 7:68 Kg (Per tank)
wc = (7:68 Kg) =29 = 0:26483 Kg = 264:83 grams (Per cathode)
The energy consumption is
P 72 kW
° = = = 2:25 kW:h=Kg (Total)
PR 32:003 Kg=h
° = 0:0225 kW:h=Kg (Per tank)
° = 7:76x10¡ 4 kW:h=Kg (Per cathode)
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 = Ce °WT = (0:30 $=kW:h) (2:25 kW:h=Kg) (768:07 Kg)

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

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

GI = $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 con-

taining 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 x-

direction. Using Newton’s 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 di¤erential equation.
½ ¾
d2 vx vx = 0 @ y = ±
´v = ¡½g cos (µ) with BC’s
dy 2 vx > 0 @ y > 0
where ´v = Fluid viscosity, vx = Fluid velocity and ½ = Density of the
‡uid: Solve this di¤erential equation and calculate the average a) value of the
boundary layer, b) velocity vx , c) molar ‡ux of hydrogen due to both di¤usion
and convection e¤ects, 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:
½ = ½Al = 2:5 g=cm3 w = 50 cm

´v = 40 g:cm¡ 1 s¡ 1 L = 100 cm
DH = 5x10¡ 3 cm2 =s µ = 2o
¢
CH;b = 30 mol=cm3 m = 100 g=s
CH = 0 @ y = 0 g = 981 cm=s2
Solution:
The solution of the above di¤erential equation is
dvx ½g cos (µ)

= ¡ y
dy ´v
Z vx Z
½g cos (µ) y
dvx = ¡ ydy
0 ´v ±
½g cos (µ) ¡ 2 ¢
vx = ± ¡ y2
2´v
½g± 2 cos (µ)
vx;max =
2´ v
The average ‡uid velocity is
Z ± Z
1 1 ± ½g cos (µ) ¡ 2 ¢
vx = vx dy = ± ¡ y 2 dy
± 0 ± 0 2´ v
· ¸· ¸±
1 ½g cos (µ) y3
vx = ±2 y ¡
± 2´v 3 o
½g± 2 cos (µ)
vx =
3´ v
2
vx = 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 ½A
¢ ½g± 3 w cos (µ)
m =
3´ v
a) Thus, the average boundary layer becomes
" ¢
#1=3
3´v m
±= = 0:46 cm
½gw cos (µ)
b) The average ‡uid velocity is
½g± 2 cos (µ)

vx = = 4:34 cm=s
3´ v
c) The average molar ‡ux mathematical model is de…ned in Chapter 4. Using
eq. (4.9a) along with dÁ=dx = 0 gives
@C
Jx = Jd + Jc = ¡DH + vx CH;b
@x
Cs ¡ Cx
Jx = ¡DH + vx CH;b
±
Using the boundary conditions Cs = 0 at y = 0 and Cx = CH;b at y = ±
yields
DH CH;b
Jx = + vx CH;b
±µ ¶
DH mol
Jx = CH;b + vx = 130:53
± cm2 s
d) The average time along the channel length is

L
t=
= 23:04 sec
vx
Then, the amount of hydrogen removed is
¢
m = tm = 2; 304 g ¼ 2:30 Kg
e) Using eq. (9.78) yields the Reynolds number along with d = ±
½vx ±
Re = = 0:13
´v
9.19 An electrowinning cell produces 10 Kg=h of nickel (Ni) at a current

e¢ciency (²) of 80%: The cell contains 20 cathodes and operates at a current of
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 = zF Pr = (²iAw ) = 53:10 m2
I = iAs = 11; 416:20 A
P = 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 simpli…ed energy consumption equation becomes
° = 1:83=² (in kW:h=Kg)
which is plotted in …gure given below indicating that the energy consumption
is strongly dependent on the current e¢ciency since ° is inversely proportional
to ²: However, this strong dependency begins to have a lesser e¤ect when ² ¸ 0:25
and when ² > 0:80 the energy consumption is signi…cantly reduced.
Let y = ° and x = ² 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 elec-
trowinning 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 e¢ciency with respect to oxygen evolution and that for the cathodes is
² = 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 speci…c submerged area Ae . Use the following relevant data to perform some
calculations given below. The average retail price of electricity (cost of electric-
ity) per kWh: Ce = 0:14 $=kW:h, Market price of copper: Cmarket = $0:17=Kg,
and
P = 72 kW (Power) Aw = 63:54 g=mol
E = 2:6 V DCu+2 = 1:24x10¡ 5 cm2 =s
NT = 100 (Tanks) Kv = 0:80 cm2 =s
Na = 30 (Anodes per tank) vx = 0:312 cm=s (Velocity of Cu+2 )
Nc = 29 (Cathodes per tank) d = 6 cm (electrode distance)
Ae = 0:80 m2 (Electrode area) Ce = 0:14 $=kW:h (Electricity)
(a) Write down all the reactions and the standard half-cell potential in-
volved in this electrowinning process. What should the applied potential be
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 num-
ber (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 eco-
nomics 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 indus-
trial 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)
¡ cell ¼ ¡1:57 V , (b) ic = 0:001194 A=cm , (c) Sh ¼ 39 and Cb = 73:08
o 2
EHalf
g=l].
Solution:
(a) The reactions, the standard half-cell potential and the applied potential
are
Anode: 2H2 O ) 4H + + O2 + 4e
Cathode: Cu+2 + 2e ) Cu
Cathode: 2H + + 2e ) H2
Overall : 2H2 O + Cu+2 + 2H + ) Cu + 4H + + O2 " +H2 "
o o o o
EHalf ¡ cell = EH 2O
+ ECu + EH 2
= ¡1:23 V ¡ 0:337 V + 0
o
EHalf ¡ cell ¼ ¡1:57 V
¯ o ¯
E ¸ ¯EHalf ¡ cell
¯
¯ ¯
¯ o ¯
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
P 72 £ 103 A V
I= = = 27; 692 A
E 2:6 V
Electrode areas per tank :
¡ ¢
Aa = NT Na Ae = (100) (30) 8; 000 cm2 = 24:0x106 cm2
2
Ac = NT Nc Ae = (100) (29) (8; 000 cm) = 23:2x106 cm2
Current densities per tank :

9.1. PROBLEMS 149
I 27; 692 A A
ia = = = 0:001154 A=cm2 = 1:250
Aa 24:0x106 cm2 m2
I 27; 692 A A
ic = = = 0:001194 A=cm2 = 1:293
Ac 23:2x106 cm2 m2
(c) Assume force laminar ‡ow. The Schmidt ( Sc ), Reynolds ( Re ) number
and the anode length (L) are
¡ ¢ ¡ ¢
Sc = Kv =D = 0:80 cm2 =s = 1:24x10¡ 5 cm2 =s = 64:52x103
¡ ¢
Re = 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 Sher-
wood number is
p p
L = Ae = 0:8 m2 = 0:8944 m2 = 89:44 cm2
µ ¶µ ¶1=3 µ ¶ " 2
#1=3
9 vx d2 9 (0:312 cm=s) (6 cm)
Sh = =
5 LD 5 (89:44 cm) (1:24x10¡ 5 cm2 =s)
Sh ¼ 39
or from eq. (9.97)
µ ¶· ¸1=3
9 d
Sh = (Sc Re )
5 L
µ ¶ ·µ ¶ ¸1=3
9 6 ¡ ¢
Sh = 64:52 ¤ 103 (2:34) ¼ 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,
µ ¶1=3
9zF Cb vx d2 D2
ic =
5 L4
µ ¶1=3
5ic L4
Cb =
9zF vx d2 D2
¡ ¢" 4
#1=3
(5) 0:001194 A=cm2 (89:44 cm)
Cb = ¡ ¢ ¡ ¢
A:s
(9) (2) 96; 500 mol cm 2¡ 5 cm2
¢2
0:312 s (6 cm) 1:24x10¡ s
Cb = 1:15 £ 10¡ 3 mol=cm3 = 1:24 mol=l
Cb = (1:15 mol=l) (63:55 g=mol) = 73:08 g=l
Alternatively, using eqs. (9.94) and (7.87b) with ¢C = Cb gives per tank
µ ¶ µ ¶
2 1=3 1=2 2 ¡ ¢1=3 1=2
Sh = (Sc ) (Re ) = 64:52x103 (2:34) ¼ 41
3 3
¡ A
¢
ic L 0:001194 cm 2 (89:44 cm)
Cb = = ¡ ¢ ¡ 2¢
zF DSh (2) 96; 500 mol 1:24 £ 10¡ 5 cm
A:s
s (41)
Cb = 1:189x10¡ 3 mol=cm3 = 1:19 mol=l
Cb = (1:19 mol=l) (63:55 g=mol) = 75:63 g=l
Both equations give fairly similar results. Let’s use the results given by eq.
(4.94) in eq. (9.87b).
(d) Production rate ( PR ) and total weight produced ( WT ) in 24 hours:
¡ A
¢¡ ¢¡ g
¢
²ic Ac Aw (0:88) 0:001194 cm 2 23:2x106 cm2 63:55 mol
PR = =
zF (2) (96; 500 A:s=mol)
PR = 8:0266 g= sec = 28:90 Kg=h ' 694 Kg=day (Total)
WT = (28:90 Kg=h) (24 h) = 694 Kg (Total)
wt = WT =NT = (694 Kg) =100 = 6:94 Kg (Per tank)
wc = (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 = Ce °WT = (0:14 $=kW:h) (2:49 kW:h=Kg) (694 Kg)

Cte = $241:93 (Total)
Ct = Cte =NT = ($241:93) =100 = $2:4193 (Per tank)
Cc = Cte = (Nc ) = ($518:45) =29 = $8:34 (Per Cathode)
Thus, the cost of production is
Cte $241:93
Cprod = =
WT 694 Kg
Cprod = $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 = (Cmarket ¡ Cprod ) (WT ) = ($7:041=Kg ¡ $0:35=Kg) (694 Kg)

GI = $4; 643:60 (For a 24-hour run)
This result is rather low. What can be improved for a higher GI ?

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) What’s 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
3 Al + SiO2 = 3 Al2 O3 + Si ¢Go = ¡188 kJ=mol
¢G = ¢GAl2 O3 + ¢GoSiO2
o o
or
4Al + 3O2 = 2Al2 O3 ¢GoAl2 O3 = ¡774 kJ=mol
3SiO2 = 3Si + 3O2 ¢GoSiO2 = +586 kJ=mol
4Al + 3SiO2 = 2Al2 O3 + 3Si ¢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 = ¡RT ln [K]

µ ¶
o [Al2 O3 ]2=3 1
¢G = ¡RT ln 4=3
= ¡RT ln
[Al] [Si] [O2 ] [O2 ]
· ¸
PO2
¢Go = RT ln [O2 ] = RT ln
Po
153
154 CHAPTER 10. HIGH-TEMPERATURE CORROSION
Thus,
µ ¶ · ¸
¢Go ¡188x103 J=mol
PO2 = Po exp = (1 atm) exp
RT (8:314 J=mol:o K) (1573o K)
PO2 = 5:71x10¡ 7
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 ¢GoCu2 O = ¡130 kJ=mol
2Al2 O3 = 43 Al + O2 ¢GoAl2 O3 = +774 kJ=mol
or
4Cu + O2 = 2Cu2 O ¢GoCu2 O = ¡130 kJ=mol
2Al2 O3 = 43 Al + O2 ¢GoAl2 O3 = +774 kJ=mol
4Cu + 2Al2 O3 = 2Cu2 O + 43 Al ¢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 Pilling-
Bedworth 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 coe¢cient of expansion are di¤erent 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) Kw mg:cm¡ 4 h¡ 1
900 10:40
950 25:00
1050 56:00
1100 83:00
1150 125:0
1200 250:0
1350 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
K 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 Atomic Weight Molecular Weight £¡ 2 K ¢p ¤

(g=mol) (g=mol) g O2 =cm4 :s
Co 58:93 CoO ! 74:93 2:10x10¡ 10
Cu 63:54 Cu2 O ! 143 6:30x10¡ 9
Fe 55:85 F eO ! 71:85 4:80x10¡ 10
Si 28:10 Si O2 ! 60:10 1:20x10¡ 12
Solution:
Polynomial …t with R2 = 0:98
µ ¶
¡ ¢ mol
Kp x10¡ 10
= ¡52:69 6 + 0:8:022 7 Aw;oxide
g
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 + O2 = 23 Al2 O3 ¢GoAl2 O3 = ¡820 kJ=mol of O2
¢Go = ¡RT ln [K]

µ ¶ µ ¶
¢Go 820x103 J=mol
K = exp ¡ = exp
RT (8:314 J=mol:o K) (1373o K)
K = 1:58x1031
b) Dissociation oxygen pressure and Po = 1 atm (standard pressure):
2=3
[Al2 O3 ] Po
K = 4=3
=
[Al] [O2 ] PO2
Po 1 atm
PO2 = = = 6:35x10¡ 32
atm
K 1:58x1031
157
10.8 If 100 grams of pure aluminum (Al) oxidizes according to the reaction
4Al + 3O2 = 2Al2 O3 , calculate the P B ratio de…ned by
P B = VAl2 O3 =VAl
whereV 0s are volumes. Data: ½Al = 2:70 g=cm3 and ½Al2 O3 = 2:70 g=cm3 .
Solution:
Aw;Al = 26:98 g=mol ½Al = 2:70 g=cm3

Aw;Al2 O3 = 101:96 g=mol ½Al2 O3 = 3:80 g=cm3
If WAl = 100 g, then

· ¸
2Aw;Al2 O3
WAl2 O3 = WAl
4Aw;Al
· ¸
(2) (101:96 g=mol)
WAl2 O3 = (100 g)
(4) (26:98 g=mol)
WAl2 O3 = 188:95 g
Thus,
WAl 100 g
VAl = = = 37:04 cm3
½Al 2:70 g=cm3
WAl2 O3 188:95g
VAl2 O3 = = = 49:72 cm3
½Al2 O3 3:80 g=cm3
and
VAl2 O3 49:72 cm3

PB = =
VAl 37:04 cm3
PB = 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
and
¢G = ¡RT ln (K)
µ ¶ · ¸
¢G 550x103 J=mol
K = exp ¡ = exp
RT (8:314 J=mol.o K) (1173o K)
K = 3:11x1024
The equilibrium constant with the standard pressure Po = 1 atm = 101 kP a

is
· ¸3
a2 (Cr2 O3 ) 1 1
K = = 3 =
a4 (Cr) a3 (O2 ) a (O2 ) PO2 =Po
¡ 1=3
¡ 24
¢
PO2 = Po K = (1atm) 3:11x10
PO2 = 6:85x10¡ 9
atm = 6:92x10¡ 7
kP a
b) The activity of oxygen is

¡ ¢¡ 1=3
aO2 = K¡ 1=3
= 3:11x1024
aO2 = 6:85x10¡ 9
mol=l = 6:85x10¡ 12
mol=cm3

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ELECTROCHEMISTRY

3 THERMODYNAMICS OF AN ELECTROCHEMICAL CELL 9

5 KINETICS OF ACTIVATION POLARIZATION 41

6 MASS TRANSPORT BY DIFFUSION AND MIGRATION 71

7 CORROSIVITY AND PASSIVITY 97

8 DESIGN AGAINST CORROSION 107

10 HIGH-TEMPERATURE CORROSION 153

1.2 Is copper corrosion an oxidation process?

1.3 It is known that corrosion on the surface of a metal is due to a direct

F e ! F e2+ + 2e¡ (anode)

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

Fe ! F e2+ + 2e¡ (anode)

1.6 What is bimetallic corrosion?

1.8 Why stress corrosion is not uniform?

1.9 What form of corrosion develops at rivets and bolts?

1.10 Corrosion is a process of destruction of a metal surface by the sur-

1.11 What are the main e¤ects or consequences of corrosion of structures?

² Corrosion reduces the thickness of metal parts of a structure and as result,

1.12 The principle constituent of wood is cellulose, which is a polysaccha-

1.13 What method is used to prevent corrosion of iron by zinc coating?

1.14 The principle constituent of wood is cellulose, which is a polysaccha-

Explanation: The Cu ¡ Zn interface is disturbed causing electrons to ‡ow

2.3 Explain why an electrode potential di¤erence occurs in Figure 2.4.

Explanation: The CuSO4 solution is depleted of Cu+2 cations and the

2.4 Why are Cu+2 cations electroplated on the Cu electrode surface in

Answer: During the operation of the galvanic cell both Zn ! Zn+2 + 2e

Explanation: The electrode anodic and cathodic reactions dissipate energy

Answer: Because Zn is more active than Cu and therefore, Zn is anodic

2.8 Is the cell potential a surface potential? If so, why?

Answer: Ecorr must be a surface potential because it arises due to simulta-

From eq. (2.4),

¸Q Á 19; 300 N:m=C

Thus, the electric force acting on the particle becomes

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

2F e3+ + Cd ! Cd2+ + 2F e2+

Eo = EFo e3+ =F e2+ + ECd=Cd

Cu+2 + 2e ! Cu =) Eco = 0:337 V

Letting ECu = EH = ¡0:118 V yields

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

(a) The dissociation chemical reaction is

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

(a) AgOH = Ag+ + OH ¡ and Ke = 1:10x10¡ 4 . Let [Ag + ] = [OH ¡ ] for

CAgOH = [AgOH] Aw;AgOH

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

where [H2 O] = 1 mol=l and

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

(a) The reduction reaction and its standard potential are

(c) The concentration of copper cations is

a) The reactions and the required temperature are

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

From eq. (2.26),

From eq. (2.34),

From eq. (236),

a) The reactions and the required cobalt activity are

Using eq. (2.32) yields

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

From eq. (2.26),

The reactions and the required activities are

Using eq. (2.32) yields