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Corrosion and Surface Chemistry of Metals: Solution0DQXDO
Corrosion and Surface Chemistry of Metals: Solution0DQXDO
Solution0DQXDO
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CHAPTER 1
1.1
Fe + H 2 SO 4 --> FeSO 4 + H 2
Cu + H 2 SO 4 + ½ O 2 --> CuSO 4 + H 2 O
2 Cu + ½ O 2 + 4 HCl --> 2 CuCl- + 3 H+ + H 2 O
Zn + 2 HCl --> ZnCl 2 + H 2
1.2
v cor = 30Pm/year
i = nF v cor
table 1.3: 1 mm/year = 3.06 nU/M
iron: U = 7.86 g/cm3, M = 55.8 g/mol, n = 2 (in deaerated solution)
1 mm/year = 3.06 (2) (7.86)/55.8 = 0.862 A/m2
30 mm/year = (0.862) (30x10-3) = 2.59 x10-2 A/m2 = 2.6 PA/cm2
1.3
2 Al + 6 H+ --> 2Al3+ + 3 H 2
2 mol Al yield 3 mol H 2 ,
M Al = 27.0 g/mol, 1 g Al = 0.0370 mol Al
0.0379 mol Al --> 5.56x10-2 mol H 2
V H2 = N H2 RT/P = (5.56x10-2)(8.3)(298)/105 = 1.35x10-3 m3 = 1.375 liter
1.4
dV H2 /dt = 0.5 ml/h
dN H2 /dt = P (dV H2 /dt)/RT
= (105N/m2)(0.5cm3/h)(10-6m3/cm3)/(8.3Nm/molK)(298K) = 2.02x10-5 mol H 2 /h
= 5.62x10-9 mol H 2 /s
Ni + 2H+ --> Ni2+ + H 2
v cor = (5.62x10-9 mol Ni/s)/(20 cm2) = 2.81x10-10 mol Ni/ cm2s
table 1.3: 1 mol/cm2s = 3.5x108 (M/U) mm/year
1.5
Convert weight percent of Fe-13Cr into mol percent:
M Fe = 55.8 g/mol , M Cr = 52.0 g/mol
1 g alloy contains 0.87 g Fe = 0.87/55.8 = 1.559 x 10-2 mol Fe
0.13 g Cr = 0.13/52.0 = 0.250 x 10-2 mol Cr
---------------------------
Total 1.809 x 10-2 mol
%mol Cr: (0.250x10-2)(100)/1.809x10-2 ) = 13.8 mol %Cr ---> mol fraction Cr: X Cr = 0.138
mol% Fe: 86.2 mol% Fe ---> mol fraction Fe: X Fe = 0.862
1.6
Fe + 2 O 2 --> Fe 3 O 4
All the oxygen present reacts: (8mg/l) (10-3g/mg) (300 l) /(32g/mol) = 7.50x10-2 mol O 2
this corresponds to (3/2)(7.50x10-2 ) = 0.113 mol Fe
surface: 10 m2
Thickness corroded:
L = (0.133mol)(55.8g/mol)/10m2)(7.86g/cm3)(104cm2/m2) = 9.44x10-6 cm = 0.094Pm
CHAPTER 2
2.1
4 Cu + O 2 --> 2 Cu 2 O
2.2
Fe + CO 2 = FeO + CO T = 1373 K
'Go = - RT ln K = - RT ln (P co /P CO2 )
ǻG o ¦ Ȟ ǻG
i
o
i
'Go FeO = -264 + 64.7x10-3 T kJ/mol For T= 1373K: 'Go FeO = - 175 kJ/mol
'Go CO2 = -394 - 1.13x10-3 T kJ/mol 'Go CO2 = - 392 kJ/mol
'Go CO = -112 – 87.8 x10-3 T kJ/mol 'Go CO2 = + 8.55 kJ/mol
'Go = = -175 + 8.55 –(-392) –(0) = 225.5 kJ/mol
P CO /P CO2 = exp(-'Go/RT) = exp{(-225.5x103)/(8.3)(1373)}= 19.8
P CO + P CO2 = 1 bar
19.2 P CO2 + P CO2 = 1 bar ------> P CO2 = 4.8x10-2 bar
2.3
Co + H 2 O = CoO + H 2
'Go = 'Go CoO + 'Go H2 - 'Go Co - 'Go H2O
'Go H2 = 0, 'Go Co = 0
'Go CoO = -240 + 78.0 x10-3 T kJ/mol For 1223K : 'Go CoO = -144.6 kJ/mol
'Go H2O = -246 + 54.9 x10-3 T kJ/mol 'Go H2O = -178.9 kJ/mol
'Go = -144.6 –(-178.9) = 34.3 kJ/mol
K = exp(-'Go/RT) = exp{-(34.3x103)/(8.3)(1223)}= 3.38
K = P H2 /P H2O -------> P H2 = 3.38 P H2O
P H2 + P H2O = 1 bar ---> 3.38P H20 + P H2O = 4.38 P H2O
P H2 = 1/4.38 = 0.23 bar
P H2O = 1- 0.23 = 0.77 bar
2.4
A DB z z J 1 /2 1
Guntelberg equation: log fr
1 J 1/ 2
with J
2
¦ z 2i c i
2.5
E rev = 0 + (RT/nF) ln [a H+ 2 / P H2 ]
n = 2 for 2 H+ + 2 e = H 2 ; T = 60oC = 333K; P H2 = 0.5 bar; pH = 8
E rev = [(8.3)(333) / (2)(96485)] ln [10-8)2 / 0.5] = - 0.518 V
2.6
The corrosion reaction Cu + 2 H+ --> Cu2+ + H 2 occurs spontaneously provided E rev,Cu < E rev,H
T = 25oC, P H2 = 1 bar, c Cu2+ = 10-6 mol/l :
E rev,Cu = 0.34 + (0.059/2)log a Cu2+
= 0.34 + (0.059/2)log 10-6 = 0.163 V
E rev,H = 0.0 – 0.059 pH
= - 0.059 (0.5) = - 0.030 V
It follows that E rev,Cu > E rev,H -------> no corrosion
2.7
Fe3+ + H 2 O = FeOH2+ + H+ K 1 # c H+ c FeOH2+ / c Fe3+
FeOH2+ + H 2 O = Fe(OH) 2 + + H+ K 2 # c H+ c Fe(OH)2+ / c Fe3+
2.8
a Ag(CN)-
Ag+ + 2 CN- = Ag(CN) 2 - K= 2
2
a Ag + a CN -
Equilibrium if:
RT a Ag(CN)-2 RT
E rev = E o ´+ ln 2 = Eo + ln a Ag +
F a CN- F
2.9
Cell voltage at equilibrium: U = )’’ – )’ = 0.342 V
Cell reaction: 1/2 H 2 + AgCl = H+ + Ag + + Cl-
- The cell voltage U is equal to the reverible potentialof the cell reaction E rev .
- The standard potential for the cell reaction is equal to that of the halfcell
2.10
Pt’¦ O 2 (0.002bar) ¦ KOH(0.01M) ¦ O 2 (0.2bar) ¦ Pt’’
U = )’’ – )’ = E rev ’’ – E rev ’
= (RT/nF) ln P O2 ’’ / P O2 ’ = (8.3)(353)/(4(96485)) ln (0.2/0.002)
= 3.50x10-2 V Æ U = 0.035 V
In this cell Pt’’ is the positive electrode (cathode) and Pt’ is the anode.
2.11
E prot = Eo + (RT/nF) ln 10-6 (mol/l)
Ni2+ + 2e = Ni Eo = - 0.257 V
E prot,Ni = -0.257 + (RT/nF) ln 10-6
25oC : E prot,Ni = -0.257 + (0.059/2) log 10-6 = - 0.434 V
E calomel = 0.241V
Protection potential versus saturated calomel electrode :
E prot,Ni = - 0.434 V – 0.241 V = - 0.675 V vs SCE
2.12
maximum corrosion rate : v cor = k L c s (mol/m2 s)
surface concentration of Cu2+ ions : c s = c Cu2+,s
Cu2+ + 2 e = Cu Eo = 0.340 V
E = Eo + (0.059/2) log c Cu2+,s (25oC)
0.160 = 0.340 + (0.059/2) log c Cu2+,s
log c Cu2+,s = - 6.10 --> c s = 7.91x10-7 mol/l
v cor = (10-5 m/s)(7.91x10-7 mol/dm3)(103 dm3/m3) = 7.91x10-9 mol/cm2 s
2.14
a) Calculation of standard potential::
Cu(NH 3 ) 4 2+ + 2e = Cu + 4 NH 3 Eo 3 (3)
c) From table 2:
Cu+ + e = Cu Eo = 0.520 V = Eo 4 (4)
Cu2+ + 2 e = Cu Eo = 0.340 V = Eo 5 (5)
Complexation reactions:
Monovalent copper:
(6) = (4) - (1) Æ 'Go 6 = 'Go 4 -'Go 1 = - F (Eo 4 -Eo 1 ) = - RT ln K 6
where K 6 = a Cu(NH3)2+ / a Cu+ a NH3 2
(RT/F) ln K 6 = 0.520 – (-0.1) = 0.420 V
25oC: log K 6 = 0.420/0.059 = 7.119 Æ K = 1.3x107
Divalent copper:
(7) = (5) – (3) Æ 'Go 7 = 'Go 5 -'Go 3 = - F (Eo 5 -Eo 3 ) = - RT ln K 7
where K 6 = a Cu(NH3)42+ / a Cu2+ a NH3 4
(RT/2F) lnK 7 = 0.340 – (0.0) = 0.340 V
25oC: log K 7 = 0.34/0.0295 = 11.5 Æ K = 3.3x1011
2.15
Cr2+ + 2e = Cr E° = –0.90 V (1)
Cr3+ + 3e = Cr E° = –0.74 V (2)
CHAPTER 3
3.1
Kelvin: RT ln (P'/P o ) = 2JM /rU
P o = 0.023 bar, T = 25oC
J= 0.072 Nm-1 (table 3.4)
U +2 = 1g/cm3, M H2O = 18 g/mol
ln (P'/P o ) = 2JM / RT r U (2) (0.072) (18) / (88.3) (298) (1x10-6 (1)) = 1.048x10-3
P'/P o = 1.001 --> P' = 0.023 bar
The small drop size has a negligible effect
3.2
Pressure difference to be applied : 'P = 2 J / r pore
J= 0.0720 , r pore = 3x10-6 m
'P = 2 (0.072)/ (3x10-6) = 4.80x104 N/m2
1 bar = 105 N/m2 ---> 'P = 0.48 bar
3.3
(111) plane, r = atom radius, h = (4 r) sin 60o = 3.464 r
a
surface of square: A = a2 = 7.952 r2
number of atoms per square: (4) (1/4) + 1 = 2
For copper: r = 0.1278x10-9 m
number of atoms per m2: N = 2 / 7.952 r2 = 1.54 x1019 atoms Cu / m2
3.4
v ads = s CO P CO / (2S M CO RT)1/2
P CO = 10-5 Pa
s CO = 0.5
M CO = 28 g/lmol = 28x10 -3 kg/mol
T = 298 K
One gets: (2S M CO RT)1/2 = 20.85 Ns/mol
v ads = (0.5)(10-5)/20.85 = 2.40 x 10-7 mol/m2s
The number of moles forming a monolayer is obtained by dividing the number of adsorption
divided by the Avogadro number: N mono = 10-19 / 6x1023 = 1.67x10-5 mol/m2
Time to form a monolayer: t mono = N mono / v ads
t = (1.67x10 mol m ) / (2.40x10-7 mol m-2s) = 70 s
-5 -2
3.5
Q ads /R = - d lnP/ d(1/T) for T = const, here: T = 0.5
from Figure:
T (K) 425 448 453 493
-3
10 /T (K-1) 2.35 2.23 2.21 2.03
108 P CO (Torr) 1.2 9 11 25
ln pCO -18.2 -16.2 -16 -15.2
-16
Log PCO
-17
-18
From this: Q ads /R = 8.57x103 (J mol-1/J mol-1 K) ---> Q ads = 7.1x104 J/mol = 71 kJ/mol
3.6
z0
carbon Lc z1
oxide
Lox
z2
metal
integration yields:
I c = - N c Cr3+ / [exp(-z 2 //) - exp(-z 1 //)] with z 1 = L c and z 2 = L c + L ox
From this:
I c /I o = [exp(-z 1 //) - exp(-z 2 //)] / [1 - exp(- L ox //) ]
= [exp(-L c //) - exp((-L c +L ox )//)] / [1 - exp(- L ox //) ]
= exp(-L c //) [ 1 - exp((L ox )//)] / [1 - exp(- L ox //) ] = exp(-L c //)
3.7
Energy of ISS signals (E P = energy of primary beam) :
Fe: E Fe /E P = (M Fe –M He )/(M Fe + M He )
Ni: E Ni /E P = (M Ni –M He )/(M Ni + M He )
M He = 4 g/mol
M Fe = 55.8 g/mol
M Ni = 58.7 g/mol
Relative energy resolution:
'E /E P = [(M Ni –M He )/(M Ni + M He )] – [(M Fe –M He )/(M Fe + M He )]
= [(58.7–4)/(58.7+ 4)] – [(55.8 –4)/(55.8 + 4)] = 0.8724 – 0.8662 = 0.0062
Absolute energy resolution for E P = 1KeV:
'E 'E /E P ) E P = (1000 eV) (0.0062) = 6.2 eV
3.8
1/ 2
§ 2z 2 F2HH o c b · § zF') GC ·
C ¨¨ ¸¸ cosh¨ ¸
© RT ¹ © 2RT ¹
§ zF') GC ·
cosh¨ ¸ = 1.51
© 2RT ¹
Double layer capacity: C = (7.15x10-2 )(1.51) c1/2 = 0.110 c1/2
For c = 0.001 mol/l: C = 0.110 As/Vm2= 0.110 F/m2 = 11.0 PF/cm2
3.9
2 2 2
1 § 2lc · § F')SC · 1 § 2lc · F § 2lc ·
Mott-Schottky: 2 ¨¨ ¸¸ ¨ 1¸ or ¨¨ HH ¸¸ RT ') SC ¨¨ HH ¸¸
C © HH o ¹ © RT ¹ C2 © o¹ © o¹
Flatband potential, E (')sc=0) : from the potential of intersect of (1/C2) vs E with x-axis:
1/C2 = 0 : E = E intersect
CHAPTER 4
4.1
BV equation: i = i o [ exp(K/E a ) – exp(- K/E c ) ]
Applied potential: E = - 0.6V vs SCE = - 0.359 V (NHE)
equilibrium potential: E rev = 0 – 0.059 pH = - 0.177 V
overvoltage: K= E – E rev = - 0.359 – (- 0.177) = -0.182 V
cathodic Tafel region: i = - i o exp(- K/E c ) = - 10-4 exp(- (-0.182)/0.055) = - 2.74x10-3 A/cm2
4.3
Equilibrium potential for pH = 1 : E rev = 0 – 0.059 = - 0.059 V
Saturated calomel electrode (SCE): E rev = 0.241 V
equilibrium potential versus SCE : E rev (SCE) = -0.059 +0.241 = - 0.300 V
Surface area: 6 cm2 : i = I/A = I/6 A/cm2
Experimental data:
E(SCE) K(V) I (A) i (A/cm2) log «i «
-0.360 -0.060 -0.0003 -5.0x10-5 -4.30
-4
-0-480 -0.180 -0.0029 -4.83x10 -3.32
-0.600 -0.300 -0.0310 -5.17x10-3 -2.29
0.720 -0.420 -0.3010 -5.02x10-2 -1.30
-1
-1.5
-2
-2.5
-3
-3.5
-4
-4.5
-5
-0.5 -0.4 -0.3 -0.2 -0.1 0
4.4
10
-5
-10
-20 -15 -10 -5 0 5 10 15 20
slope: di/dE = 1/r c # 0.58 mA/cm2mV = 0.58 :-1cm-2 ---> r c = 1.72 :cm2
i cor = (1/r c )[(1/b a ) + (1/b c ) ]-1
= 0.58 [ (1/0.03)+(1/0.05)]-1 = 0.58/53.3 = 0.011 Acm-2
i cor = 11 mA/cm2
4.5
100
10
0.1
0.01
-0.8 -0.75 -0.7 -0.65 -0.6 -0.55 -0.5
E (V vs SCE)
4.6
i cor = i o,Fe exp[(E-E rev,Fe )/E a,Fe ] (1)
i cor = i o,H exp[- (E-E rev,H )/E c,H ] (2)
(2 equations with 2 unknowns: E cor , i cor )
E rev,H = 0 – 0.059 pH = -0.059 V
E rev,Fe = -0.44 + (0.059/2) log 10-2 = - 0.499 V
E a,Fe = 0.0174 V, E c,H = 0.052 V
Corrosion potential:
i o,Fe exp[(E-E rev,Fe )/E a,Fe ] = i o,H exp[- (E-E rev,H )/E c,H ]
ln i o,Fe + (E cor /E a,Fe ) – (E rev,Fe /E a,Fe ) = ln i o,H - (E cor /E c,H ) + (E rev,H /E c,H )
ln 10-8 + (E cor /) – (-0.499 / ) = ln 10-7 - (E cor /) + (-0.059 /)
--> E cor = - 0.359 V
Corrosion current density:
i cor = i o,Fe exp[(E-E rev,Fe )/E a,Fe ]
ln i cor = ln i o,Fe + (E cor /E a,Fe ) – (E rev,Fe /E a,Fe ) = - 18.42 +(-20.61)+28.68 = - 10.36
--> i cor = 3.2 x 10-5 A/cm2
Note: The same result for i cor ccould also be obtained from equation (2)
4.7
i cor = i o,H exp[- (E-E rev,H )/E c,H ] Unknowns: i cor , i o,H
E cor = - 0.520 V (SCE) = - 0.279 V (NHE)
b c,H = 0.12 V ---> E c,H = 0.052 V
pH 4 : E rev,H = 0 – 0.059 pH = - 0.236 V
Calculation of i o,H from cathodic polarization:
For 1 mA/cm2 E = - 0.90 v (SCE) = - 0.659 V (NHE)
i = i o,H exp[- (E-E rev,H )/E c,H ]
10-3 = i o,H exp[- (-0.659 +0.236)/] = i o,H exp[8.135] = i o,H (3.41x103)
---> i o,H = 2.9x10-7 A/cm2
4.8
pH 3 : E cor = -0.50 V, i cor = 10-6 A/cm2 E rev = 0 – 0.059 (3) = - 0.177 V
pH 1 : E cor = ? , i cor = 10-5 A/cm2 E rev = 0 – 0.059 (1) = - 0.059 V
Corrosion current density: i cor = i o,H exp[- (E cor -E rev,H )/E c,H ] with E c,H = 0.053
pH 3 : 10-6 = i o,H(pH3) exp[- ((-0.50) –(-0.177))/]
Æ i o,H(pH3) = 10-6/(4.43x102) = 2.26x10-9 A/cm2
Exchange curent density: i o,H = n F k c c H+ exp[- E rev,H /E c,H ]
pH 3 : i o,H(pH3) = n F k c (10-3) exp[- (-0.177) /] = n F k c (28.2x10-3)
pH 1 : i o,H(pH1) = n F k c (10-1) exp[- (-0.059) /] = n F k c (3.04x10-1)
i o,H(pH1) / i o,H(pH3) = 0.304/(28.2x10-3) = 10.8
i o,H(pH1) = 2.44x10-8
Corrosion potential: E cor – E rev = - E c,H ln i cor /i o,H
E cor = E rev - E c,H ln i cor /i o,H
For pH 1: E cor = -0.059 – 0.053 ln (10-6/2.44x10-8) = - 0.059 – 0.197 = - 0.256 V
4.9
i l = 0.62 n F D2/3 Q-1/6 c b Z1/2
n=4
D = 2.51x10-5 cm2/s Æ D2/3 = 8.57x10-4 (cm2/s)2/3
Q = 10-2 cm2/s Æ Q = 2.15 (cm2/s)-1/6
c b = 8 mg/l = (8x10-3/32 )10-3 = 0.25x10-6 mol/cm3
Z= 1200 rpm = 2S (1200/60) = 126 rad/s Æ Z1/2 = 11.21 (rad/s)1/2
Limiting current density at 1200 RPM:
i l = (0.62)(4)(96585)( 8.57x10-4)( 2.15)( 0.25x10-6)( 11.21) = 1.23x10-3 A/cm2
Diffusion layer thickness:
i l = n F D c b /G Æ G = n F D cb / il
G = 4 (96585)( 2.51x10-5 )( 0.25x10-6) /(1.23x10-3) = 2.05x10-3 cm = 20.5 Pm
4.11
Table 4.27 : Sh = 0.079 Sc0.35 Re0.7
Re = Zr L /Q L = 2r = 0.04 m Z = 2S(4000/60) = 419 rad/s
Sc = Q/D H Q = 10-6 m2/s D H = 9.32x10-9 m2/s
Sh = i l L /n F D H c b c b = 0.001mol/l = 1 mol/m3 n = 1
Re = (419)(0.02)(0.04)/(10-6) = 3.35x105
Sc = (10-6)/9.32x10-9 = 1.072x102
Sh = (0.079)( 1.072x102)0.35(3.35x105)0.7 = 2.99x103
i l = Sh (n F D H c b )/L = (2.99x103)(1)(96485)( 9.32x10-9)(1)/(0.04) = 67.2 A/m2
Corrosion rate: 1 A/m2 = 0.327 (M/n U) mm/year (Table 1.1); M Mg = 24.3 g/mol, U Mg = 1.74
g/cm3 , n = 2 : --> v cor = (67.2)(0.327)(24.3)/(2)(1.74) = 1.53 mm/year
4.12
H2O, O2
O2
bentonite
copper
2 Cu + O 2 + 2 H 2 O Æ 2 Cu(OH) 2
4.13
c
O2
cs,OH OH- G
y O 2 + H 2 O + 4 e Æ 4 OH-
4.14
Limiting current density at RDE in a binary electrolyte:
i l = (1-(z + /z - )) 0.62 n F D + 2/3 Q-1/6 (c +s – c +b ) Z1/2
FeCl 2 : z + = 2, z - = 1 Æ 1-(z + /z - ) = 3
D + = 0.72x10-9 m2/s
c +s = 4.25 mol/l, c +b = 2.0 mol/l Æ c +s – c +b = 2.25 mol/l
Q = 10-6 m2s , Z = 200 RPM = (200)2S/60 = 20.9 rad/s
i l = (3)(0.62)(2)(96485)( 0.72x10-9)2/3(10-6)-1/6(2.25)(20.9)1/2 = 2.97x104 A/m2
i l = 2.97 A/cm2
4.16
steady motion: z i q i (d)/dy) = 6S r i K i v i
Definition of electric mobility: u e,i = v i /(d)/dy) [(m/s)/(V/m)]; u e,i = z i F u i with u i = D i /RT
Fe2+ : D Fe2+ = 0.72x10-9m2/s Æ u e,Fe2+ = (2)(96485)(0.72x10-9)/(8.3)(298) = 5.61x10-8 m2/Vs
Fe3+ : D Fe3+ = 0.61x10-9m2/s Æ u e,Fe2+ = (3)(96485)(0.61x10-9)/(8.3)(298) = 7.13x10-8 m2/Vs
ionic radius: r i = z i q i /6S K u e,i
Fe2+ : r Fe2+ = (2)(1.6x10-19) /(6S)(10-3)( 5.61x10-8) = 3.03x10-10 m
Fe3+ : r Fe3+ = (3)(1.6x10-19) /(6S)(10-3)( 7.13x10-8) = 3.57x10-10 m
r Fe3+ > r Fe2+ because the higher charge leads to stronger hydration
CHAPTER 5
5.1
Fe3+ + 2 e = Fe2+ Eo = 0.771 V
c Fe3+ = c Fe2+ = 0.001 mol/l
E rev = 0.771 + (RT/F) ln (a Fe3+ /a Fe2+ ) | 0.771 + (RT/F) ln (c Fe3+ /c Fe2+ ) = 0.771 V
Applied potential E = 0.595 V
5.2
I Fe + OH- Æ FeOH ads + e
II FeOH ads Æ FeOH ads + + e
III FeOH ads + + H+ Æ Fe2+ + H 2 O
5.3
5.4
For a charge transfer controlled reaction:
Rt / Z 2C 2 Rt2 / ZC
Z Re Z Im
Rt2 1/ Z 2C 2 Rt2 1/ Z 2C 2
A Nyquist plot of the tabulated data yields a hemi-circle:
0
0 2 4 6 8
ZRe
Z= Z=0
Charge transfer resistance from graph: R t = Z Re (Z=0) - Z Re (Z=) = 8 :
A = 2 cm2 Æ r t = R t A = (8)(2) = 16 :cm2
Rt / Z 2C 2 Rt2 / ZC
= 2 Æ 1/ZC = R t
Rt2 1/ Z 2C 2 Rt 1/ Z 2C 2
Z max = 1.25 kHz (see figure and table) ; R t = 8 : Æ C = 1/Z R t = 10-4 Farad
c dl = C/A = 0.5 x 10-4 F/cm2 = 50 PF/cm2
Exchange current density:
At the equilibrium potential : r t = RT/nFi o Æ i o = RT/nFr t
n = 2; RT/F = 0.026V ; r t = 16 :cm2 Æ i o = 0.013/16 = 8.1x10-4 A/cm2
5.5
6
ZI
m
4
0
0 2 4 6 8
Z Re
From graph: R : = 2 :,
R t = 8 – 2 = 6 :
5.6
(I) Ni + H 2 O = NiOH ads + H+ + e
(II) NiOH ads o NiOH+ + e
(III) NiOH+ + H+ = Ni2+ + H 2 O
d log i o / d log c Ni2+ = (d log i o / dE rev )(dE rev / d logc Ni2+ ) = ((1+Df /2.3)(2.3/2f) = (1+D
( setting E rev | Eo + (RT/2F) ln c Ni2+ = Eo + (2.3/2f) log c Ni2+ )
§ d log i0 ·
¨ ¸ = (1 + 0.5)/2 = 0.75
© d log cNi2+ ¹pH
5.7
I Cu = Cu+ + e
II Cu+ Æ Cu2+ + e
D I = D II = D f = F/RT K = E - E rev
(a)
reaction step I:
i I = F k a,I exp(Df E) – F k c,I c Cu+ exp(-(1-D)f E)
i o,I = F k a,I exp(Df E rev ) = F k c,I c Cu+(eq) exp(-(1-D)f E rev )
(b) For i o,I >> i o,II and K >> 0 (anodic Tafel region) :
from above equation it follows (setting i o,I = ) : i = i a = 2 i o,II exp ((1+D) f K)
E a = 1/(1+D)f
For i o,I >> i o,II and K << 0 (cathodic Tafel region) :
i = i c = - i o,II exp ( -(1-D) f K)
E c = 1/(1-D)f
CHAPTER 6
6.1
The standard potential of the halfcell reaction
Fe 2 O 3 + 6 H+ + 6 e = 2 Fe + 3 H 2 O
corresponds to the standard free energy change of the reaction (Chapter 2):
Fe 2 O 3 + 3H 2 = 2 Fe + 3 H 2 O
'Go = 3 'Go (H2O) - 'Go (Fe2O3) = 3 (-237.2) –(-742.2) = + 30.6 kJ/mol
Eo = -'Go/nF = (-30.6x103) /(6)(96485) = - 0.053 V
Equilibrium potential in 0.5M H 2 SO 4 of pH | 0 :
E rev = Eo + RT/6F ln (1/a H+ 6) = - 0.053 – 0.059 pH = - 0.053 V
6.2
3 Fe 2 O 3 + 2 H+ 2 e = 2 Fe 3 O 4 + H 2 O (1) E 1 o =?
One finds in Table 6.9 :
Fe 3 O 4 + 8 H+ + 8 e = 3 Fe + 4 H 2 O (2) E 2 o = - 0.087 V
Fe 2 O 3 + 6 H+ + 6 e = 2 Fe + 3 H 2 O (3) E 3 o = - 0.053 V
--------------------------------------------------------------------------------
reaction (1) = 3 x reaction (3) – 2 x reaction (2)
'Go 1 = 3 'Go 3 – 2 'Go 2
-n 1 F Eo 1 = - 3 n 3 F Eo 3 + 2 n 2 F Eo 2
Æ Eo 1 = 3 (n 3 /n 1 ) Eo 3 – 2 (n 2 /n 1 ) Eo 2
n 1 = 2, n 2 = 8, n 3 = 6 :
Eo 1 = 3 (3) (- 0.053) – 2 (4) (- 0.087) = 0.219 V
6.3
ln | i |
Ecor Ep E
6.4
ln | i |
6.5
From Fig. 6.16 we read:
pH log |i p |
1.8500 -1.6500
3.0200 -1.9500
4.5500 -3.7000
7.4500 -4.8000
8.4200 -5.3000
9.3700 -5.9000
11.500 -7.2000
-
0 2 4 6 8 1 1
p By regression analysis: log |i p | = -0.08 – 0.57 pH
6.6
From Fig. 6.15 :
Z(rad/s) Z1/2 i p (mA/cm2)
261.80 16.180 1550.0
167.60 12.940 1300.0
41.900 6.4700 600.00
1600
y = -28.182 + 99.313x R= 0.99702
1400
1200
1000
ip(mA/cm2)
800
600
400
200
0
0 5 10 15 20
Z1/2
6.8
Data points:
Z(rad/s) i(A/cm2) 1/i 1/Z1/2
600.00 0.26200 3.8170 0.041000
400.00 0.25000 4.0000 0.050000
200.00 0.22700 4.4050 0.071000
100.00 0.20000 5.0000 0.10000
50.000 0.17200 5.8140 0.14100
20.000 0.13400 7.4630 0.22400
10.000 0.10700 9.3460 0.31600
10
y = 2.9883 + 20.071x R= 0.99998
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
6.9
CHAPTER 7
7.1
E rev = Eo + (RT/F) ln a Cu2+ Eo = 0.340 V
0.1 ppm = (0.1x10-6g/g)(103g/l)/63.5g/mol = 1.57x10-6 mol/l
a Cu2+ # c Cu2+ = 1.57x10-6 mol/l
95oC = 368 K : E rev,95 = 0.340 + (8.3)(368)/896485)ln(1.57x10-6) = 0.128 V
55oC = 338 K : E rev,55 = 0.340 + (8.3)(338)/896485)ln(1.57x10-6) = 0.146 V
'E = E rev,95 - E rev,55 = 0.018 V
For corrosion cells: E anode < E cathode --> Metal at 95oC is anodic and corrodes preferentially.
7.3
Fe + ½ O 2 + 2H+ --> Fe2+ + H 2 O --> V cor = N Fe2+ = 2 N O2 (mol/cm2s)
A = A Fe + A Cu = 2500 = A Fe + 5(0.5) cm2 --> A Cu = 2.5 cm2
A Fe = 2497.5 cm2 | 2500 cm2
N O2 = 4x10-11 mol/cm2s
Number of moles O 2 reacting per second: J O2 = N O2 A = (4x10-11)(2500) = 1.0x10-7 mol O 2 /s
number of moles Fe reacting per second: J Fe = 2 J O2 = 2.0 x10-7 mol Fe/s
(a) Rivets made of iron: A Fe = 5x0.5 cm2
v cor = N Fe = 2.0 x10-7/2.5 = 8.0x10-8 molFe/cm2s
Table 1.3: 1 mol/cm2s = 3.15x108 (M/U) mm/year
M Fe = 55.8 g/mol ; U Fe = 7.86 g/cm3 --> v cor = 179 mm/year
(b) Rivets made of copper: A Fe = 2500 cm2
v cor = N Fe = 2.0 x10-7/2500 = 8.0x10-11 molFe/cm2s --> v cor = 0.179 mm/year
7.4
Anodic partial reaction: i a , Zn = i cor,Zn exp(E Zn -E cor,Zn )/E a,Zn
A Zn = A Cu =10cm2; i l,O2 = 0.05 A/cm2;
E cor,Zn = - 0.765 V ; E cor,Cu = 0.01 V ; R int = 1 : ; E a,Zn = 0.04V
For I a,Cu | 0 : I a,Zn = i l,O2 (A Cu + A Zn ) = (0.05)(20) = 1.0 A
7.5
(a) Noble electrode, equilibrium conditions for oxygen: O 2 + 4H+ + 4e = 2 H 2 O
E rev,I = Eo + (RT/4F) ln(P O2,I a H+ )
E rev,II = Eo + (RT/4F) ln(P O2,II a H+ )
E rev,I - E rev,II = (RT/4F) ln(P O2,I /P O2,II ) = 0.0064 ln(0.01/1.0) = - 0.0295 V
(b)
brass
ln |i| O2,II
O2,I
E
k H = 1.3 x10-3 mol/dm3 bar
P O2,I = 0.01 bar : c O2,I = k H (0.01) = 1.3x10-5 mol/l
P O2,II = 1.0 bar : c O2,II = k H (1.0) = 1.3x10-3 mol/l
i lO2 = - nFD O2 C O2 /G !i lO2,I / i lO2,II = c O2,I / c O2,II
Dissolution of brass: i a = i cor exp(E-E cor )/E a
It follows for electrodes I and II: E I – E cor = E a ln(i a,I /i cor ) and E II – E cor = E a ln(i a,II /i cor )
--> E I – E II = E a ln(i a,I /i a,II ) = E a ln(i lO2,I /i lO2,II )
= 0.017 ln(1.3x10-5/1.3x10-3) = - 0.078 V --> E II is more noble than E I
7.6
Steel pipe: E cor,I = 0.1 V
Rebar : E cor,II = 0.6 V
soil resistance: U e = 3000 :cm2 = 1/N
Ohmic resistance at coating defect: R int (1/2 d N ) = 3000 /(2)(1) = 1500 :
Ohmic control: E cor,II - E cor,I = I (R int + R ext ) # I R int
--> I = (0.6 – 0.1)/1500 = 3.33x10-4 A
7.7
Fe-18w%Cr-8w%Ni-0.4w%C: C dissolved --> C 23 Cr 6
initial concentrations of Cr and C :
18gCr/100g steel = (18/52.0)/100g steel = 0.346 molCr/100g steel M Cr = 53.0 g/mol
0.4gC/100g steel = (0.4/12.0)/100g steel = 0.0333 molC/100g steel M C = 12.0 g/mol
Reaction of 0.0333 mol C with 23 Cr/ 6C :
(0.033/6) 23 = 0.128 mol Cr/100g steel = 0.128(53.0) g Cr/100g steel = 6.64 g Cr/100g steel
Remaining Cr concentration : 18g/100g steel – 6.64 g/100 g steel = 11.36 g Cr/100g steel
Chromium concentration in w% : 11.4 w%
7.8
Pit growth rate: (dL/dt)= (i a /nF)(M/U) = [D (c sat -c b )/L] (M/r)
For c b = 0: L = (2 D Fe2+ c sat M/U)1/2 t1/2 L = pit depth
M Fe = 55.8 g/mol; U Fe = 7.86 g/cm3
c sat = 4.25 mol/l
D Fe2+ = 0.72x10-5 cm2/s (Table 4. )
--> L = [(2)(0.72x10-5)(4.25x10-3)(55.8)/(7.86)]1/2 t1/2 = 6.66x10-4 t1/2
Wall thickness 3 mm :
Time to perforation: tp1/2 = (0.3 cm) /(6.66x10-4 cm s1/2 )= 455 s-1/2
tp = 2.07x105 s = 2.07x105 / 3600 = 57.5 h
(b) Binary electrolyte , 0.1 M FeCl
(dL/dt)= (i a /nF)(M/U) = [(1 – z + /z - ) D Fe+ (c sat -c b )/L] (M/U)
with (1 – z + /z - ) = 1 – 2/(-1) = 3 ; (c sat -c b ) = 4.25 – 0.1 = 4.15 mol/l
--> L = [(2)(3)(0.72x10-5)(4.15x10-3)(55.8)/(7.86)]1/2 t1/2 = 1.13 x10-3 t1/2
tp = (0.3/(1.13x10-4)2 = 6.94x10-4 s = 19.2 h
CHAPTER 8
8.1
Plot L versus log t:
L (nm t (min) Log t
1.5 1.0 0
2.0 11.0 1.04
2.6 98 1.99
3.1 1050 3.02
3.6 9960 4.0
4
y = 1.493 + 0.53084x R= 0.99912
3.5
2.5
1.5
1
- 0 1 2 3 4 5
log t Regression line : 1.50 + 0.53 log t
8.3
T = 30oC ; relative humidity: RH = 53 %
From Fig. 8.10: absolute humidity for these conditions AH | 16 g /m3
for T = 20oC and AH = 16 g/m3 Æ RH | 95 %
Saturation in presence of ZnSO4 : (Table 8.11) : RH sat, ZnSO4 = 90%
Æ RH at 20oC > RH sat, ZnSO4 condensation is possible
8.4
months mass (mg) log t log m
2 20 0.301 1.30
12 69 1.08 1.84
22 101 1.38 2.00
36 148 1.56 2.17
1.8
1.6
1.4
1.2
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
log (months)
8.5
8.6
4Fe + 3O 2 + 2 H 2 O Æ 4 FeOOH
Maximum rate = limiting current density for O 2
Oxygen flus to surface: N O2 = D O2 c O2 /G
D O2 = 2.5x10-9 m2/s (Table 4. x )
c O2 = c O2, saturation = 2.5x10-4 mol/l = 2.5x10-1 mol/m3
G = 1 Pm = 10-6 m
N O2 = (2.5x10-9)(2.5x10-9)/(10-6) = 6.25x10-4 mol/m2s
N Fe = (4/3) N O2
Corrosion rate: N Fe = 8.33x10-4 mol/m2s
Table 1.1 : 1 mol/m2s = (3.15x10-4)(M/U) mm/year
Vcor = (3.15x10-4) (8.33x10-4)(55.8)/7.86 = 186.3 mm/year
The actual values are usually lower because of the precipitation of corrosion products on the
surface
CHAPTER 9
9.1
k p = k p ' P O2 1/n
k p ' = k o exp(-'G#/RT) --> ln k p ' = ln k o - 'G#/RT
Activation energy at P O2 = 1bar: d ln kp' / d(1/T) = -'G#/R
Estimated from Fig. 9.13 for 1 bar :
T (1/T)x104 k p ' ln k p '
1073 9.32 6.1E-13 -28.128
1173 8.53 4.5E-12 -26.135
1273 7.86 3.1E-11 -24.209
1373 7.28 1.5E-10 -22.649
1473 6.79 5.8E-10 -21.269
-23
-24
-25
-26
-27
-28
-29
6. 7 7.5 8 8. 9 9.5
Slope: 'G#/R = 2.72x104 K
4
10 /T
9.2
n-type oxide M 2 O :
M 2 O = ½ O 2 + 2M i x +2 e
K = P O2 1/2 c Mix 2 c e 2 where M i = interstitial cation
c Mix = c e --> K = P O2 1/2 c Mix 4
c Mix 4 = K P O2 -1/2 --> c Mix v P O2 -1/8
---------------------
p-type oxide M 2 O :
M 2 O + 2 V M ' + 2h = ½ O 2
K = P O2 1/2 c h -2 c VM' -2 = P O2 1/2 c VM' -4 (since c h = c VM' )
c VM' 4 = P O2 1/2 K-1 --> c VM' v P O2 1/8
----------------
9.3
Cu 2 O is a p-type semiconductor that conducts by movement of metal vacancies V M '
Ni2+ is an electron donor in a monovalent copper oxide:
c Dx = c VM'
Wagner Hauffe rules: oxidation rate of Cu 2 O should increase in presence of Ni
3
2
NiS
-8
-12
NiO
-16
Ni
-20
9.5
From Fig. 9.1 (Ellingham diagram) for 900oC:
'Go TiC > 'Go Cr23C6 > 'Go MoC > 'Go Fe3C
Æ all Ti will react with C to TiC, the rest forms Cr 23 C 6 . (If there were still C left it would form
MoC and Fe 3 C).
Element w-% M (g/mol) Mol /g alloy
Fe 75 55.8 1.34x10-2
Cr 23.4 52.0 4.50x10-3
Ti 0.05 47.9 1.04x10-5
Mo 0.015 95.9 1.56x10-5
C 0.05 12.0 4.17x10-5
C available for reaction with Cr: 4.17x10-5 -1.04x10-5 mol = 3.13 x10-5 mol C
23 Cr + 6 C Æ Cr 23 C 6 3.13 x10-5 mol C / 6 = 0.522 x10-5 mol Cr 23 C 6
M Cr23C6 = (23)(52)+(6)(12) = 1268 g / mol
Æ 0.522 x10-5 mol Cr 23 C 6 = (0.522 x10-5)( 1268) = 6.62x10 -3 g Cr 23 C 6 / g alloy
Result: TiC: 0.062 w-% Cr 23 C 6 : 0.66 w-%
10.2
Adhesive wear rate : v w = K WA (F N l s / 3H)
wear resistance v (1/v W ) v (H/ K WA )
If K WA is independent of hardness H the adhesive wear should vary hardness in the same way as
abrasive wear.
10.3
Dimensionless force: F* = F N /A H
H = 250 kg/mm2 = 2450 MPa
F* = (50N)/(4x10-6m2)(2450x106 Ns/m2) = 5.10x10-3
Dimensionless sliding velocity: v* = v s r o /D T
v s = 2S f r o = 2S (3/60)(8) = 2.57 cm/s
Thermal conductivity D T = h T /c p U
with h T = 0.46 J/cm s K; c p = 490 J/kg K ; U Fe = 7.86 g/cm3
D T = (0.46 J/cm s K ) / (490 J/kg K ) (7.86 g/cm3) = 0.117 cm2/s
v* = (2.57 cm/s )(8 cm)/( 0.117 cm2/s)= 176
Zone III, Severe oxidation wear
10.4
Friction coefficient: f = (F f /A)/E k
where F f = friction force, A wall area, E k = kinetic energy of fluid
Wall area: A = 2S r L where L = 10 m (length of pipe)
Shear force acting on pipe wall: F f /A = 'P (4Sr2)/ 2S r L = 'P 2r / L
10.5
Critical flow velocity : v crit = (2 W crit / Uf)1/2
Friction coefficient: f = 0.32 Re-1/4 with Re = v L / Q
W crit = 9.6 N/m2; U= 103 kg/m3; Q = 10-6 m2/s ; (a) L = 0.05 m ; (b) L = 0.20 m
v crit = [2 W crit / (U0.32 Re-1/4)]1/2 = [2 W crit / (0.32 U v crit -1/4 L-1/4 Q )]1/2
[2 W crit 0.32-1 U v crit +1/4 L+1/4 Q )]1/2 = [2 W crit (3.125) UQ1/4]1/2 v crit 1/8 L1/8
= [2 (9.6) (3.125) (10-3)(106/4)]1/2 v crit 1/8 L1/8
= [2 (9.6) (3.125) (10-3)(31.62)]1/2 v crit 1/8 L1/8 = [1.90]1/2 v1/8 L1/8 = 1.377 v crit 1/8 L1/8
v crit 7/8 = 1.377 L1/8 Æ v crit = 1.44 L1/7
(a) L = 0.05 m : v crit = 1.44 (0.05)1/7 = 0.93 m/s
(b) L = 0.20 m : v crit = 1.44 (0.20)1/7 = 1.14 m/s
10.6
fȕ
Tinst -Ts = F*1/2 v*
2N1/2
5.5
y = 3.2 - 0.5x R= 1
4.5
3.5
3
- -4 - - - 0 1
log v* Wear map showing isotherm for f = 0.5 and 'T = 400
Discussion: v* = v sl r /D T
F* = F N /A H
For a given set up the heating increases with either sliding velocity or applied normal force.
CHAPTER 11
11.1
Cold worked copper: E rev,1 = E o,1 + (RT/2F) ln a Cu2+
Annealed copper: E rev,2 = E o,2 + (RT/2F) ln a Cu2+
Cu annealed --> Cu coldworked 'Go = 'Go 2 –'Go 1
'Go 2 = -nF E o,2
'Go 1 = -nF E o,1
'Go = - nF (E o,2 – E o,1 ) = - nF E cell
'Go = 12 J/g = (12) (63.5) = 762 J/mol
E cell = - 'Go/nF = E o,2 – E o,1 = -(762)/(2)(96485)= - 3.9 x10-3 V = - 3.9 mV
It follws :
E o,2 < E o,1 The cold worked electrode is anodic and corrodes preferentially
note: The effect of cold work on the equilibrium potential is small, however.
11.3
cross section: A = Sd2/4 = 0.0052 S/4 = 1.96x10-5 m2
applied stress: V appl = F/A = (1.5x104 N)/(1.96x10-5m2) = 7.64x108 N/m2
yield strength: V e = 1100 MPa = 1.1x109 N/m2
(a) inert environment: V e > V appl no rupture
(b) dissolved hydrogen:
in Fig. 11.27 we find for a steel with V e = 1100 MPa : V rupture = 30 – 80 N/mm2
or V rupture = 30 x107 – 80 x107 N/m2
In presence of dissolved H: V rupture << V appl rupture occurs due to hydrogen
embrittlement
11.4
½ H 2 = H (m) 'G = 'Go + RT ln (X H / P H2 1/2) (setting a H = X H )
at equilibrium: 'G = 0 --> ln X H = - 'Go/RT + ln P H2 1/2
P H2 = 20 bar --> lnP H2 1/2 = 1.5
ln X H = - 'Go/RT + 1.5
Table 11.20 for Fe D :
'Ho = 26.3 kJ/mol 'So = -50.3 J/mol K for 300- 900 oC; T = 200oC = 473 K
'Go = 'Ho - T 'So
= 26.3x103 – (473)(-50.3) = 5.01x104 J/mol H (m) = 50.1 kJ/mol mol H (m)
11.5
reaction at anode : H (m) --> H+ + e
diffusion controlled anodic current density: i a = 80PA/cm2 = F [D H(m) c Hsat(m) /L]
where L = thickness of Fe sheet; L = 20 Pm
c Hsat(m) = hydrogen concentration in Fe on cathode side
D H(m) = diffusion coefficient of H in Fe
hydrogen solubility:
c Hsat(m) = 1.62x10-3 cm3 H 2 /g Fe (25oC, 1 bar)
= 1.62x10-3 / 7.86 = 1.27x10-2 cm3 H 2 /cm3Fe ( U Fe = 7.86 g/cm3)
number of moles H 2 :
n H2 = PV/R T = (105)(1.27x10-8)/8.31)(298) = 5.13x10-7 mol H 2 /cm3 Fe
n H = 2 n H2 --> n H = 10.26x10-7 mol H / cm3 Fe
CHAPTER 12
12.1
overall reaction: Ni2+ + H 2 PO 2 – + H 2 O o Ni + H 2 PO 3 – + 2 H+
anodic partial reaction: H 2 PO 2 – + H 2 O o H 2 PO 3 – + 2 H+ + 2 e E = 0.085 + 0.065 ln
i a,HP
cathodic partial reaction: Ni2+ + 2 e o Ni E = –0.542 – 0.039 ln |i c,Ni |
12.2
French hardness = total concentration of Mg2+ and Ca2+ ions exprssed in mg CaCO3 /l :
10 mg CaCO 3 = 1oF
c Ca2+ = 10-4 mol/l
c Mg2+ = 4x10-5 mol/l
c tot = c Ca2+ + c Mg2+ = 14 x 10-5 mol/l
10 mg CaCO 3 = 10-3 g / M CaCO3 = 10-3/100.1 = 10-5 mol CaCO 3 (M CaCO3 = 100.1 g/mol)
Æ 10 mg CaCO 3 /l corresponds to c tot = 10-5 mol Ca2+/l
c tot = 14 x 10-5 mol/l Æ 14 oF
Although degree hardness is often used in practice this concentration unit should be avoided
whenever possible.
12.3
'G° ads = –RT ln b L
(a) From Fig. 12.32: c/T # 0.1 + c [mM/l]
Langmuir: c/T = 1/b L + c
By comparison: 1/b L = 0.1x10-3 mol/l = 104 mol/l
b L = 104 l/mol
'G° ads = –RT ln b L = - (8.3)(298) ln 104 = 2.28x104 J/mol
(b) ln b L = - 'G° ads /RT
'G° ads = 'H° ads – T 'S° ads
R (dln b L /dT) = - d('G° ads /T)/dT
= -[ (d'G° ads /dT) (1/T) -'G° ads /T2] = -[-'S° ads /T – ('H° ads -T'S° ads )/T2 ]
12.4
Fe + O 2 + H 2 O --> Fe2+ + 2OH-
log |i|
Eprot Ecor E
i cor = - i l,O2 = nF v cor
i prot = - i cor = i l,O2
2 2
v cor = 10 mg/cm day = 10x10 mdd = 1000 mdd
Table 1.3 : 1 mdd = 0.112 (n/M) A/m2 n = 2 ; M = 55.8 g/mol
v cor = (1000) (0.112)(2)/ (55.8) = 4.01 /Am2
A = 2 m2 --> I prot = 8.02 A
12.5
E prot = Eo + (RT/nF) ln 10-6 [mol/l] Eo = -0.44 V; T = 15oC = 288K
E prot = (-0.44) + [(8.31)(288)/(2)(96485)] ln10-6 = -0.44 – 0.171 = -0.611 V
E Cu/CuSO4 = 0.316 V
E prot (Cu/CuSO4) = -0.611- 0.316 = - 0.927 V
12.6
Protection current: I prot = i prot A = - i cor A = i l,O2 A
Estimation of corrosion current density from polarization resistance:
r p = (dE/di) E=Ecor or (1/ r p ) = (di/dE) E=Ecor
For charge transfer controlled anodic reaction and mass transport controlled cathodic reaction:
i = i cor exp(]/E a ) – i l,O2 where polarization ] = (E-E cor )
(1/ r p ) = (di/dE) E=Ecor = (di/d]) ]=0 = i cor (1/E a ) --> i cor = E a / r p
E a = 20 mV = 0.02 V ; r p = 4x104 :cm2 ; A = 9 m2
i cor = 0.02/4x104 = 5x10-7 A/cm2 = 5x10-3 A/m2
12.7
RE1 RE2
y
r1 = h
r2
The stray current creates a potential gradient in the soil. For cylindrical geometry in infinite
space :
d)/dr = - i/N = – U e i = – U e I / 2S r L
where N = conductivity; U e = resisitivity; L = length of pipe, r = radial coordinate
U e I r1 dr Ue I r1
2SL ro³ r
integration yields: )1 ) 0 ln
2SL r0
U e I r2
)2 )0 ln
2SL r0
Here r o is the pipe radius.
For a finite space we suppose a symetrical image field. The potential difference between
reference electrodes RE1 and RE2 is then obtained from the sum of the two potential fields:
) 2 ' – ) 1 ' = 2 () 2 – ) ) = - (U e I/SL) ln r 2 /r 1
set r 1 2 = h2 ; r 2 2 = h2 + y2 :
) 2 ' – ) 0 ' = - (U e I/SL) ln r 2 /r 1 = (1/2)(U e I/SL) ln r 2 2/r 1 2 = (1/2)(U e I/SL) ln[(h2+y2)/h2] q.e.d.
numerical values:
12.8
Fe + 2 H+ --Fe2+ + H 2
anodic partial reaction: E = 0.08 + 0.05 log i a,Fe
cathodic partial reaction: E = –0.36 – 0.12 log |i c,H |
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