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EMA 4324 Problem Set 11

6-5. Equal 1-cm2 areas of metals P and Q are immersed together in


sulfuric acid of unit H+ activity having no other dissolved oxidizers.
Using the electrochemical parameters listed below:

material Eeq io(A) io(C,H)


P -0.5 3x10-7 10-6 0.1
Q -0.6 2x10-6 10-5 0.1

[a] Determine corrosion potential and corrosion rate for each,


when they are uncoupled;
****************************************************
log[icorr] = {[EC-EA]+Alog[io(A)]+Clog[io(C)]}/[A+C]

for [P],
log[icorr] = {[0-(-0.5)]+0.1log[3x10-7]+0.1log[10-6]}/[0.1+0.1]
= -3.76; icorr(P) =1.73x10-4 A
Ecorr = EA + Alog[icorr/io(A)] = -0.5 + 0.1log[1.73x10-4/3x10-7]
Ecorr(P) = -0.223 V
for [Q],
log[icorr] = {[0-(-0.6)]+0.1log[2x10-6]+0.1log[10-5]}/[0.1+0.1]
= -2.35; icorr(Q) =4.47x10-3 A
Ecorr = -0.6 + 0.1log[4.47x10-3/2x10-6]; Ecorr(Q) = -0.265

[b] When P and Q are electrically coupled, determine the potential and
current passing in the galvanic couple so formed;
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Assume io(C) = 10-5+10-6 = 1.1x10-5 A
log[icorr](P+Q) =
{[0-(-0.265)]+0.1log[4.47x10-3]+0.1log[1.1x10-5]}/[0.1+0.1]
= -2.33; icorr(P+Q) =4.69x10-3 A
Ecorr(P+Q) = -0.265 + 0.1log[4.69x10-3/4.47x10-3];
Ecorr(P+Q) = -0.258
[c] Determine the corrosion rates for P and Q when the two are
galvanically coupled;
****************************************************
at Ecorr(P+Q) = -0.258V,

logiP = log[3x10-7] + [-0.258-(-0.5)]/0.1


= -4.10; iP =7.89x10-5 A

logi Q = log[2x10-6] + [-0.258-(-0.6)]/0.1


= -2.28; iQ = 5.26x10-3 A

[d] Which metal is cathodically protected upon galvanic coupling?;


****************************************************
Metal P, at least to some extent.

[e] On which metal is the hydrogen evolution rate increased upon


galvanic coupling?
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Metal P, since it has been cathodically polarized upon coupling

6.6 By appropriate changes in electrochemical parameters use


polarization diagrams to show conditions in which the couple
potential between the two metals will not fall between the
uncoupled corrosion potentials of the two metals. For such
conditions, which of the two metals is cathodically protected?
Which of the two is galvanically corroded?
*******************************************************
Cant be done. On the other hand, the metal with the more noble
potential is not necessarily cathodically protected when coupled to
a metal with a more negative Nernst potential....be prepared to
give example[s] on 11/8/2001.
6-7. Plot the polarization curves and determine the galvanic corrosion rate
[a] when 1-cm2 of metal C is coupled to 1-cm2 of metal A in a
corrosive solution.; [b] when 10-cm2 of C is coupled to 1-cm2 of A in
the same solution; [c] when a solution resistance of 3000 ohms is
present between A and C in [b].

material A, volts C, volts jcorr, A/cm2


A 0.05 0.1 10-7
C 0.04 0.1 10-6
Ecorr(C) - Ecorr(A) = 0.500 v, with C noble to A
*******************************************************
Technically, theres a problem with the problem in that the cathodic
reaction parameters are not included [as they were with 6-5]. So, how
do we know what the total cathodic current is going to be on surfaces
of A and C? One way would be to neglect cathodic reactions on
A and anodic reactions on C. At least it makes the solution of the
coupled Tafel equations possible:

[a] A = 0.05log[igalv/10-7]; igalv = 10-7*10[(A)/0.05]


C = 0.10log[igalv/10-6]; igalv = 10-6*10[(C)/0.10]
10[(A)/0.05] = 10*10[0.5-(A)/0.10]
10[20(A)] = 10*10[5-10(A)]
0.1 = 10[5-30(A)]; taking logs of both sides,
-1 = 5 -30A; A = 0.200v; igalv = 10-3 A

[b] for AC = 10AA, icorr(C) = 10-5 A

going through the algebra again, ...


A = 0.233v; igalv = 4.57x10-3 A

[c] lets forget [c].....


6.5 revisited [Evans Diagram Analysis]

logarithm current, log10[I], Amps 2

-2
icorr Quc
icorr Puc
-4 H/Q
-6

-8 Q H/P
P
Ecorr Quc Ecorr Puc
-10
-1.000 -0.500 0.000 0.500 1.000
electrode potential, volts SHE

2
logarithm current, log10[I], Amps

-2

-4

-6

-8

-10
-1.000 -0.500 0.000 0.500 1.000
electrode potential, volts SHE