Académique Documents
Professionnel Documents
Culture Documents
CONTENTS
1 INTRODUCTION 2 CORROSION THERMODYNAMICS 3 ELECTRODE KINETICS 4 CORROSION KINETICS 5 COMPLEX CORROSION SYSTEMS
1 INTRODUCTION
1.1 1.2 1.3 1.4 1.5 ECONOMIC SIGNIFICANCE DEFINITION OF CORROSION THERMODYNAMICS ELECTROCHEMISTRY KINETICS
1.3 THERMODYNAMICS
SYSTEM; SURROUNDINGS; EQUILIBRIUM STANDARD STATE LAWS OF THERMODYNAMICS CHEMICAL POTENTIAL EQUILIBRIUM CONSTANT REACTION ISOTHERM
1.4 ELECTROCHEMISTRY
ELECTROCHEMICAL POTENTIAL ELECTROCHEMICAL CELLS
OXIDATION REACTION (ANODE) REDUCTION REACTION (CATHODE)
ELECTROCHEMICAL SERIES
1.5 KINETICS
CHEMICAL REACTION RATE ARRHENIUS RATE EQUATION ACTIVATED COMPLEX ACTIVATION ENERGY REACTION MECHANISMS AT AN ELECTRODE-ELECTROLYTE INTERFACE
2 CORROSION THERMODYNAMICS
2.1 CHEMICAL SYSTEMS 2.2 ELECTROCHEMICAL SYSTEMS 2.3 DIAGRAMS POTENTIAL-pH 2.4 IMMUNITY, PASSIVITY AND CORROSION 2.5 EXAMPLES
G = H - TS
EQUILIBRIUM CRITERION
DG = 0
CHEMICAL POTENTIAL
mi = dG/dni = mio + RT ln ai
S ni Mi = 0
CRITERION FOR REACTION EQUILIBRIUM
S ni mio + RT S ni ln ai = 0
IN TERMS OF EQUILIBRIUM CONSTANT
-S ni mio = RT S ni ln ai = RT ln K
S ni Mi + ne = 0
CRITERION FOR ELECTROCHEMICAL EQUILIBRIUM
Eo = Eoo + (2.3RT/nF)S ni log ai = 0.0 + 0.059 log aH+ - 0.0295 log PH2 AND FOR PH2 = 1 atm
Eo = 0.0 - 0.059 pH
(E - Eo) i = 0 OR
(E - Eo) i > 0
E = 0.0 - 0.059 pH
OXYGEN REDUCTION (LINE b) O2 + 2 H2O + 4 e = 4 OH-
E = 1.228 - 0.059 pH
2.5 EXAMPLES I
Fe/Fe2+/Fe3+/Fe3O4/Fe2O3 SYSTEM
2.5 EXAMPLES II
Fe/Fe2+/Fe3+/Fe3O4/Fe2O3 SYSTEM
EQUILIBRIUM POTENTIALS/EQNS E4 = 0.771 + 0.0591 log( Fe3+/Fe2+) E13 = -0.085 - 0.0591 pH E17 = 0.221 - 0.0591 pH log(Fe3+)20 = -0.72 - 3 pH E23 = -0.44 + 0.0295 log( Fe2+) E26 = 0.98 - 0.2364 pH - 0.0886 log( Fe2+) E28 = 0.728 - 0.1773 pH - 0.0591 log( Fe2+)
INTERSECTION 1: 20-28 INTERSECTION 2: 17-26-28 INTERSECTION 3: 13-23-26 VERTICAL LINES: 20 HORIZONTAL LINES: 23
2.5 EXAMPLES IV
EXERCISE: CONSTRUCT POURBAIX DIAGRAMS Mg/Mg2+/Mg(OH)2 SYSTEM Mg2+ + 2e = Mg E3 = -2.363 + 0.0295 log(Mg2+) OTHER SYSTEM OF YOUR CHOICE
3 ELECTRODE KINETICS
3.1 MECHANISMS OF ELECTRODE REACTIONS 3.2 EXCHANGE CURRENT 3.3 POLARIZATION AND OVERVOLTAGE 3.4 TYPES OF OVERVOLTAGE 3.5 EXAMPLES
i =zFv
z = number of electrons/molecule F = Faradays constant = 96487 Coulomb/mol v = reaction rate (mole/ m2 s)
va = v c ia = ic
WHERE
aa , ac = TRANSFER COEFFICIENTS
FOR ANODIC AND CATHODIC PROCESSES
fo = (EQUILIBRIUM) ELECTRODE
POTENTIAL
io = EXCHANGE CURRENT
io = 104 A/m2 Cu = Cu2+ + 2e ; io = 5 A/m2 Zn = Zn2+ + 2e ; io = 10-2 A/m2 H2 = 2H+ + 2e (on Pt) ; io = 102 A/m2 H2 = 2H+ + 2e (on Fe) ; io = 10-2 A/m2 H2 = 2H+ + 2e (on Pb) ; io = 10-9 A/m2
Ag = Ag+ + e ;
ex ~ 1 + x inet = io (z F h/RT)
h = ba log(inet / io )
ANODIC TAFEL EQUATION
h = bc log(inet / io )
CATHODIC TAFEL EQUATION
w=
hres = I R
3.5 EXAMPLES I
EXERCISE: SHOW THAT A NET CURRENT DENSITY OF 1 A/m2 IS APPROXIMATELY EQUIVALENT TO A UNIFORM CORROSION WASTAGE RATE OF 1 mm/year
3.5 EXAMPLES II
Fe = Fe2+ + 2e
3.5 EXAMPLES IV
Fe ELECTRODE
e38.94h 1.47 2.18 7.00 49.11 e-38.94h 0.68 0.46 0.14 0.02 inet / io 0.80 1.72 6.85 49.09
3.5 EXAMPLES V
EXERCISES
VERIFY THE GIVEN EXPRESSIONS FOR ia ic AND inet FOR NONEQUILIBRIUM ELECTRODES EXPLORE THE SENSITIVITY OF inet TO THE VALUES OF THE TRANSFER COEFFICIENTS. CALCULATE THE THEORETICAL VALUES OF THE TAFEL SLOPES
3.5 EXAMPLES VI
EXERCISE: CALCULATE THE LIMITING CURRENT DENSITY FOR THE OXYGEN REDUCTION REACTION IN WATER SATURATED WITH OXYGEN D ~ 10-9 m2/s Cbulk ~ 0.3 mole/m3
4 CORROSION KINETICS
4.1 ANODIC AND CATHODIC REACTIONS 4.2 POLARIZATION 4.3 WAGNER AND TRAUDS SUPERPOSITION PRINCIPLE 4.4 STERN AND GEARYS ANALYSIS 4.5 EXAMPLES
2 H+ + 2e = H2
OXYGEN REDUCTION
O2 + 4e + 2H2O = 4OH-
4.2 POLARIZATION I
WHEN A METAL CORRODES ITS ELECTRODE POTENTIAL BECOMES ANODICALLY POLARIZED hA > 0 THE ELECTRODE POTENTIAL OF THE CORRESPONDING CATHODIC REACTION BECOMES CATHODICALLY POLARIZED hC < 0
4.2 POLARIZATION II
BECAUSE OF POLARIZATION THE ELECTRODE POTENTIALS OF THE TWO REACTIONS MOVE TOWARDS EACH OTHER AND IF THE ELECTROLYTE RESISTANCE IS LOW
fa = Ea = fc = Ec = f* = Ecorr
ia = ic = icorr Ia = Ic = Icorr
4.2 POLARIZATION IV
E
CATHODIC CURVE
Ecorr
log icorr
ANODIC CURVE
log i
4.2 POLARIZATION V
E
CATHODIC CURVE ANODIC CURVE
Ecorr Icorr
M = M+ + e
ia =
ic = icorr
inet = ia + ic =
icorr { exp(aaa F [f - f*]/RT)
JUST LIKE BUTLER-VOLMER
exp(-acc F [f - f*]/RT) }
slope = bc
Di
Df
Ecorr
slope = ba
icorr i
4.5 EXAMPLES I
THE EVANS SALT DROP EXPERIMENT
3% NaCl SOLUTION IN H2O POTASIUM FERRICYANIDE (BECOMES BLUE IN PRESENCE OF Fe2+) PHENOLPHTALEIN (BECOMES PINK IN PRESENCE OF ALKALI) FINELY ABRADED Fe SURFACE
4.5 EXAMPLES II
EXERCISE: CONSTRUCT POLARIZATION CURVES FOR
Fe Fe Zn Zn CORRODING IN ACID SOLUTION CORRODING IN BASIC SOLUTION CORRODING IN ACID SOLUTION CORRODING IN BASIC SOLUTION
4.5 EXAMPLES IV
EXERCISE: VERIFY THE GIVEN STERN&GEARY EXPRESSION FOR
inet
EXERCISE: USE THE GIVEN STERN&GEARY EXPRESSION FOR inet USE THE GIVEN TO COMPUTE
THE f - log inet POLARIZATION CURVE FOR THE FOUR SYSTEMS IN EXAMPLES II ABOVE
4.5 EXAMPLES V
DETERMINE THE CORROSION POTENTIALS AND CORROSION CURRENT DENSITIES FOR THE FOUR SYSTEMS IN EXAMPLE II ABOVE
4.5 EXAMPLES VI
EXERCISE: VERIFY THE GIVEN EXPRESSIONS FOR ba AND bc IN THE STERN-GEARY ANALYSIS
i = F S zi Ni
MATERIAL BALANCE
dCi/dt = - div Ni
ELECTRONEUTRALITY CONDITION
S zi Ci = 0
div v = 0
i = - k grad f
WHERE k IS THE CONDUCTIVITY OF THE SOLUTION
div grad f = 0
LAPLACES EQUATION
vf = v s
df/dn = 0
CONDUCTING BOUNDARIES (POTENTIAL PROBLEMS)
df/dn = i/k
f = 0 ON 2-3
5.5 EXAMPLES I
GALVANIC CORROSION
5 4
ELECTROLYTE
y
1 METAL A
2
METAL B
5.5 EXAMPLES II
GALVANIC CORROSION (contd)
ELECTROLYTE (LAPLACES EQUATION)
2 2 d f/dx
2 2 d f/dy
= 0
df/dx = 0
df/dy = 0
BOUNDARY 1-2
df/dy = iA/k
BOUNDARY 2-3
df/dy = iB/k
5.5 EXAMPLES IV
GALVANIC CORROSION (contd) FINITE DIFFERENCE FORMULAE (ELECTROLYTE; INTERIOR NODES)
(fE + fW - 2 fP )/Dx2 +
(fN + fS - 2 fP )/Dy2 = 0
5.5 EXAMPLES V
INTERIOR NODES
N
Dy
P W
Dx
S
5.5 EXAMPLES VI
FINITE DIFFERENCE FORMULAE (BOUNDARY NODES; BOUNDARY 1-2-3)
l = Dy/Dx
-N
5.5 EXAMPLES IX
SOLUTION BY SUCCESIVE OVERRELAXATION ITERATION FOR ALL MESH POINTS. SOR EQUATION FOR MESH POINT i IS
5.5 EXAMPLES X
EXERCISE: DERIVE THE FINITE DIFFERENCE FORMULAE GIVEN EXERCISE: DERIVE THE S.O.R. FORMULAE GIVEN EXERCISE: EXPLORE THE SENSITIVITY OF THE GALVANIC SYSTEM
REFERENCES I
West, Corrosion y Oxidacion: Fundamentos, Limusa, Mexico, 1986 Shreir, Jarman & Burnstein, Corrosion, 3d ed., 2 V, Butterworth, London 1994 Hack (ed.), Galvanic Corrosion, ASTM, Philadelphia, 1988
REFERENCES II
Charlot, Badoz-Lambling & Tremillon, Las Reacciones Electroquimicas, Toray-Mason, Barcelona, 1969 Bockris & Ready, Modern Electrochemistry, 2 V, Plenum, New York, 1977 Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, NACE, Houston, 1974
REFERENCES III
Gileadi, Electrode Kinetics, VCH, New York, 1993 Newman, Electrochemical Systems, 2nd ed., Prentice-Hall, Englewood Cliffs, 1991 Iserles, A First Course in Numerical Analysis of Differential Equations, Cambridge UP, Cambridge, 1996