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EMA 4324 Problem Set 7

3-6. Using appropriate polarization diagrams, determine the effect of the


following parameters on the corrosion potential and corrosion rate of
metal M corroding to M+ in an acid solution: [a] increasing jo of the
anodic reaction, [b] increasing jo of the cathodic reaction, [c]
increasing the concentration of dissolved [H+] and [d] increasing the
Tafel constant for the anodic reaction.
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Starting condition - note positions of


rg or 0l u 1 c

Icorr corrosion potential and corrosion current


Ec
n e

t
o

potential
r

n
t

re
r
current

u
0

r
c
c

r
1

Icorr
r lu

r
Icorr I corr
r

g o l0

g o l0

o
o
t gn e or

Ec

Ec

Ec
o

potential
potential
r

potential
r

increase jo(a) increase jo(c) increase jo(c), Eeq


r

parameter Ecorr Icorr


c1

Icorr
r
ul0

increase jo(a) decrease increase


o
r

Ec

increase jo (c) increase increase


r o

potential
increase [H+] increase increase
ge

increase β (a)
n

increase decrease
t

increase β(a)
3-8. [a] Plot the appropriate polarization curves for the following half-cell
reactions and determine the corrosion potential and corrosion rate
[current density] assuming activation control of both the anodic and
cathodic processes. [b] Same as [a], but assume the limiting current
density for the reduction reaction is 10-5 A/cm2. Again, determine the
corrosion potential and corrosion rate [current] from your plot.

reaction ENernst jo β
M = M+ + 1e- -0.70 v 10-8 A/cm2 βa = +0.1
2H+ + 2e- = H2 +0.10 v 10-6 A/cm2 βc = -0.1
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0
log current, log(10) amperes

-2
I corr [AC]
-4
I corr [DL]
-6

-8

Ecorr [DL] Ecorr [AC]


-10
-1.00 -0.50 0.00
potential, volts SHE
3-10. Plot the polarization data current, potential,
shown below for an Log I
A v SHE
electrode of 1.13 cm2 of the
metal M in an acid solution 2x10-4 -0.4843 -3.699
of unit activity bubbled with 5x10 -4 -0.4939 -3.301
pure hydrogen [p(H2)=1??]. 1x10-3 -0.5075 -3.000
How might the potentials in 2x10 -3 -0.5287 -2.699
this data have been measured 5x10 -3 -0.5663 -2.301
experimentally? From your 1x10-2 -0.6067 -2.000
plot, determine the 2x10 -2 -0.6425 -1.699
corrosion rate [current 5x10-2 -0.7117 -1.301
density] and the exchange 1x10-1 -0.7375 -1.000
current density for the
hydrogen reduction reaction on the surface of M. Comment on the
accuracy of your determinations.
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0.0

-1.0

-2.0
log current, log I

-3.0
icorr = 10^(-2.97)
-4.0 = 1.07x10^(-3)

-5.0

-6.0 io = 10^(-6.6) = 2.51x10^(-7) A

-7.0 Ecorr = -0.480v


-8.0
-0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1
potential, volts SHE

Only 5/6 data points to do a Tafel extrapolation - where you lay the
line is subjective and subject to error. Data points might have been
generated using either galvanostatic or potentiostatic polarization
methods. Jcorr = 1.07x10-3 A/1.13 cm2 = 9.47x10-4 A/cm2.