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Measurements of electrochemical processes are made by measuring electrical currents and voltages.
The currents results from the flow of charged ions (positive or negative) and or electrons. Current
measurement can be extremely sensitive as small as 10-15 amps (coulombs per second). Let’s get
“feeling” for the sensitivity of such a measurement.
A M Þ M + + e-
+1
corresponding to 1.6 x 10-19 C/atom of charge. Today we can
easily measure at the nanoamp scale. Suppose we measure a
current density of 10-6 A cm-2 for 1 s or 10-6 C. A full monolayer of
1 cm metal dissolving as a +1 cation results in a charge of 1.6 x 10-19
1 cm C/atom x 1.5 x 1015 atoms/cm2 or ≈ 2.4 x 10-4 C cm-2. Then 10-6 C
corresponds to only of order 0.01 ML.
An electrochemical reaction is a chemical reaction involving electron
transfer.
Faraday’s Law relates the flow of electric current to the mass of metal
reacting.
Ita
m
nF
m= mass of metal reacting (gm)
t = time (s, min, hours, years)
I = current (Amps)
a = atomic weight of metal
n = number of electrons transferred in the reaction
F = 96,500 C; Faraday’s constant which is equal to the
charge associated with 1 mole of electrons.
If , for example, we divide Faraday’s law by the time and area of
A dissolving surface, we obtain a relation describing the rate of this process.
m ia
r
tA nF
Consider the case for steel or iron corrosion. Suppose we make a measurement
of the current associated with the corrosion of 100 cm2 of a steel surface and
find a current of 0.1A. Then dividing through by the area of the sample,
m ia
r Fe Fe2 2e
tA nF
i = 1 mA/cm2
0.001A / cm 2 55.85 g
a = 55.85 g 2.89 107 gm / cm 2 s
F = 96,500 C 2 96,500C
n = 2
We can convert this to a penetration rate (cm/s) by dividing by the density of Fe.
Fe 7.88 g / cm3
0.001A / cm 2 55.85 g
r 2.89 107 gm / cm 2 s
2 96,500C
r 2.89 107 gm / cm 2 s 8
p 3.67 10 cm / s
Fe 7.88 gm / cm 3
Next consider:
Electrochemical Cells
V
H2 at 1Atm
porous barrier
Pt is inert and acts as a catalyst: 2H+ + 2e- = H2
Zn is oxidized: Zn = Zn2+ +2e-
Total reaction: Zn + 2H+ = Zn2+ + H2
H2 at 1Atm
porous barrier
1 M CuSO4
1 M ZnSO4
aA + bB xX + yY
A, B … reactants
X, Y … products
a, b, …., x, y,…. Stoichiometric Coefficients defining how
many moles of A and B produce moles of X and Y
Gproducts Greact 0 OR G 0
A, B … reactants
X, Y … products
(
DG = xGx + yGy + ) - ( aG A + bGB + )=0
Since G ≣ standard free energy change /mole
Gi G RT ln ai
i
0
(
DG = xGx0 + yG y0 + ) - ( aG 0
A
+ bG B0 + )
+RT (x ln ax + y ln a y + ) - RT (aln aA + bln aB + ) = 0
Chemical Equilibrium
Solving for G
x y
a a
DG = -RT ln
0 X Y
a b
= -RT ln K
aa
A B
K is the equilibrium constant for the reaction.
G
K exp( )
RT
When components are not in standard state:
a Xx aYy
DG = DG 0 + RT ln
aAaaBb
Electrochemical Equilibrium
a Xx aYy
DG = DG 0 + RT ln
aAaaBb
Free energy is measured in units of kcal or kJ.
Nernst Equation
Formal Potential
Electrochemical Equilibrium: pH effects
aA mH ne bB dH 2 0
Here A could correspond to some oxidized species such as Fe2+ and B
would be its reduced form, metallic Fe. Alternatively A could be an oxide such as
FeO and B its reduced form, also metallic Fe.
a m
RT é
ë A ù
û éH ù +
E = E0 + ln ë û
nF é B ùb é H O ù d
ë û ë 2 û
Electrochemical Equilibrium and Corrosion
a m
RT é
ë A ù
û éH ù +
E = E0 + ln ë û
nF é B ùb é H O ù d
ë û ë 2 û
It’s convenient at this stage to convert the natural log (Ln) to base 10.
In general:
Also
a
0.059 éë Aùû m
E=E + 0
log b
- 0.059 pH
n éë B ùû n
Electrochemical Equilibrium and Corrosion
a
0.059 éë Aùû m
E=E +
0
log b
- 0.059 pH
n éë B ùû n
Examples:
2
(1) Consider the reaction Fe Fe 2e
First note that for this and all simple metal dissolution reactions there is no
H+ in the reaction and no dependence of the reaction on pH, m = 0
-0.506 0.1
-0.654 10-6
Electrochemical Equilibrium and Corrosion
a
0.059 éë Aùû m
E=E + 0
log b
- 0.059 pH
n éë B ùû n
Examples:
(2) Consider Al2 O3 6 H 6e 2 Al 3H 2 O
Both Al and Al2O3 are solids with unit activity, A=1, B=1.
On a complete EMF series one could find that E Al o
/ Al2 O3 1.55 V.
Also note that m = 6, n = 6 so,
AlO2 4 H 3e Al 2 H 2O
0.059 4
E Al/ AlO - = E Al/
o
AlO -
+ log éë AlO2- ùû - 0.059 pH
2 2 3 3
The ΔE for this reaction is a function of both the dissolved ion content
and the pH of the electrolyte.
Cathode reactions Supporting Corrosion
Hydrogen reduction
+ -
2H + 2e = H2 EH
/ H2
EH0
/ H2
0.059 pH
EH / H 0 0.059 pH
2
Cathode reactions Supporting Corrosion
Oxygen reduction
oxygen evolution
and acidification
EH / H 0 0.059 pH
2
hydrogen evolution
and alkalization
Potential/pH (Pourbaix) Diagram
Generic diagram for a metal
0.4
0.0
Passivation- oxides are stable
-0.4 Corrosion
Immunity-reduced form of the
-0.8
metal is stable
-1.2 Passivation
-1.6 Corrosion
-2.0
Immunity
-2.4
-2 0 2 4 6 8 10 12 14
pH
Potential/pH (Pourbaix) Diagram
A
a
eAl / Al 3 e0
0.059
log
m
0.059 pH
Independent of pH since
B n no H+ is involved.
b
n
log Al 3
0.059
eAl / Al 3 1.662
3 Only depends on Al3+
activity
Potential/pH (Pourbaix) Diagram
= 10-11.4
( Al ) 3+ 2
For (Al3+)=10-6,