Beruflich Dokumente
Kultur Dokumente
Practical Corrosion
Petrica Banea
Coen Smits
4125525
4039688
1
Question 1.
Give a summary table of all measurement data and observations schematically of
both the agar experiments, the oxygen cell and the i-E values of zinc and steel. Also
note the observations of the passivation of the nail.
Set-up
A
Visual result
Measurements of potential differences between 2 nails in salt water after adding pure
oxygen to the water:
T (s)
0
180
300
420
540
Potential difference
-123mV
-52,5mV
-42,7mV
-36,1mV
-32,1mV
Zn
30mA
Potential (V)
-1,065
-1,042
-1,039
-1,033
-1,029
-1,024
-1,016
-1,009
-1,005
Zn(changed polarity)
-1,081
-1,117
-1,184
-1,203
-1,359
-1,394
-1,434
-1,436
-1,445
we couldnt read this
because we couldnt reach
-1,001 the 30mA to do the reading
Fe
Curent (V)
-0,671
-0,631
-0,613
-0,601
-0,59
-0,582
-0,566
-0,553
-0,543
-0,534
Fe(changed polarity)
-0,711
-0,846
-0,897
-0,918
-0,935
-0,96
-1,168
-1,22
-1,244
-1,264
We also passivated a nail by putting a cleaned nail in Nitric acid. When we did this, for a
very short moment some yellow/brown gas appeared and then nothing happened
anymore. This seemed to be the passivation process.
Question 2.
Answer all the questions from the Experimental Procedure in the right order
Question: Under what conditions will they cause a color change?
-
Phenolphtalein will turn pink when the pH of the solution rises to between 8,2 and
12.
Potassium ferricyanide turns blue in the presence of Fe2+ ions
Question: What gas will evolve during the etching of the nails? Give the reaction equation.
Hydrogen. 2Fe (s) + 6HCl (aq) 2FeCl3 (aq) + 3H2 (g)
Question: Which nail has the lowest potential after O2 gas is blown through the solution?
Which reactions will occur during the O2 gas bubbling? Which nail is then the cathode?
Negative values The nail at the red wire has the lowest potential and is therefore the
anode. The nail at the black wire is the cathode.
At the anode, oxidation will occur:
Fe Fe2+ + 2e
Question 3.
Give a complete explanation of the observed corrosion phenomena with the agar
experiments.
Setup A
In setup A a steel nail and a copper rod were short-circuited
placed in the agar. The result after 2 days was pink colored
agar around the copper rod and dark blue agar around the nail.
The indicators used show that around the copper, reduction
occurred (the amount of OH- increased and rose the pH) and
around the nail oxidation occurred (Potassium ferricyanide
proofed the existence of Fe2+ ions).
At the anode (steel, oxidation):
Fe Fe2+ + 2e
In setup B, a zinc bar replaced the copper rod. Since zinc is less
noble than steel, oxidation in this case occurred at the zinc bar
and reduction occurred at the steel nail. The agar around the
steel nailed turned pink, proofing the existence of OH- and
turned white around the zinc bar. The white color is caused by
Zn2+ ions, which were lost to the solution.
At the anode (zinc, oxidation):
Zn Zn2+ + 2e
In setup C, the zinc bar was replaced. This time a platinum wire
was short-circuited with the nail and both were put in the agar.
Reduction occurred around the platinum wire, oxidation
occurred at the steel nail.
At the anode (steel, oxidation):
Fe Fe2+ + 2e
Setup D
For this setup, we used the same setup as in setup C, but now
removed the short circuit plug and a voltage of 0,5V was
connected to the 2 electrodes. Because we chose the nail to be
the cathode (black pole), we expected a cathodic reaction at this
side. But since the platinum wire is more noble, this side could
also be expected to be the cathodic side. After 2 days, a bit of
both occurred. At the surface of the agar reduction- and at the tip
of the nail, oxidation occurred.
The platinum wire is no longer protected now, since no OHappeared in the solution.
Setup E
Setup F
Setup G
Same as setup H, but now we placed a passivated nail with a filed
tip. By passivation, a protective layer appeared around the nail,
with filing we removed this at the tip of the nail. The result is the
same as in setup H.
At the tip (anodic, oxidation):
Fe Fe2+ + 2e
Fe Fe2+ + 2e
O2 + 2H2O + 4e 4OHFe2+ + 2OH- Fe(OH)2
4 Fe(OH)2 + O2 2 (Fe2O3 x H2O) + 2H2O
Fe Fe2+ + 2e
O2 + 2H2O + 4e 4OHFe2+ + 2OH- Fe(OH)2
4 Fe(OH)2 + O2 2 (Fe2O3 x H2O) + 2H2O
The nail next to the O2 supply is the cathode and has the highest potential. The other nail
is the anode.
4d. Explain the change of potential after the start of blowing with oxygen gas.
The free oxygen in at the cathode decreases, slowing down the creation of free electrons
and the system is trying to create an equilibrium.
Question 5.
The measured data for the electrode potential of zinc and steel in seawater can be read
in the following tables:
Current
value
i[mA]
0
3.2
4
6
8
10
15
20
25
30
Table 01
Natural
Logarithm
of i lni
1.163
1.386
1.792
2.079
2.303
2.708
2.996
3.219
3.401
Zn (zinc)
Measured Electrode Potential [V]
Normal
Inversed Polarity
polarity
-1.065
-1.081
-1.042
-1.117
-1.039
-1.184
-1.033
-1.203
-1.029
-1.359
-1.024
-1.394
-1.016
-1.434
-1.009
-1.436
-1.005
-1.445
-1.449
-1.001
Current
value
i[mA]
0
2
4
6
8
10
15
20
25
30
Table 02
Natural
Logarithm
of i lni
0.693
1.386
1.792
2.079
2.303
2.708
2.996
3.219
3.401
Fe (steel)
Measured Electrode Potential [V]
Normal
Inversed Polarity
polarity
-0.671
-0.711
-0.631
-0.846
-0.613
-0.897
-0.601
-0.918
-0.590
-0.935
-0.582
-0.960
-0.566
-1.168
-0.553
-1.220
-0.543
-1.244
-0.534
-1.264
9
Question 6.
a) According to the Table 01 and Table 02, that contains the measured data for the Zn
(zinc) electrode and Fe (steel) electrode, respectively, the Evans diagrams are
constructed as they are shown in the graphs below.
Zn-electrode: scatter data
0.000
0.000
1.000
2.000
3.000
4.000
5.000
-0.200
-0.400
-0.600
Zn(A)
-0.800
Zn(K)
-1.000
-1.200
-1.400
-1.600
10
1.000
2.000
3.000
4.000
5.000
-0.200
-0.400
-0.600
Fe(A)
Fe(K)
-0.800
-1.000
-1.200
-1.400
b)
In order to find the mixed (corrosion) potential for Zn and Fe electrode from the
diagrams, we have to linearly interpolate the existing lines. The following graphs show
the intersections of the cathodic and anodic lines through which we found the exact
values of the mixed potential as they are shown in figure 03 & 04 and later we compared
them with the measured values.
For this purpose we used the Excel graphs tool in order to plot the interpolated line of
the scattered measured data. This can be achieved by selecting the option Add
Trendline to the displayed scatters. This command is translated into a line, that has the
linear equation of the y = ax + b form.
The coordinates of the intersection point of the two Trendlines were calculated with
Excel and they represent the mixed potential (y-value Emix) and the corrosion current
(x-value icorr).
11
-0.200
-0.400
Zn(A)
-0.600
-0.800
Zn(K)
(0.512 , -1.05608)
y = 0.0186x - 1.0656
Emix = -1.05608
-1.000
ln(icorr) = 0.512
Linear (Zn(A))
-1.200
Linear (Zn(K))
-1.400
-1.600
y = -0.153x - 0.9778
-1.800
Figure 03. Interpolation of the cathodic and anodic line for Zn-electrode
From the graph we can extract the linear equation of the anodic and cathodic lines and
with the help of the Goal Seek function in Data/What-if Analysis/, we are able to
calculate the coordinates of the intersection point between the two lines. This
intersection of the anodic and cathodic line for each metal will supply the mix potential
[Emix] and the corrosion current [icorr]. Therefore the values are:
-
x-value
0.512
y-value Emix =
x-value ln(icorr) =
y1-value
-1.056083217
y2-value
-1.056083217
0.512
icorr = eln(icorr) =
-1.056083217 V
y1-y2
0
1.668049553 mA
12
-2.000
0.000
-0.200
-0.400
2.000
4.000
6.000
y = 0.0364x - 0.6625
Fe(A)
Fe(K)
-0.600
(0.083 , -0.65949)
-0.800
Emix = -0.65949
ln(icorr) = 0.083
-1.000
Linear (Fe(A))
Linear (Fe(K))
-1.200
-1.400
y = -0.1773x - 0.6448
-1.600
Figure 04. Interpolation of the cathodic and anodic line for Fe-electrode
For the Fe-electrode the procedure is similar to the one for Zn-electrode. Therefore the
Emix and icorr are as follows:
-
x-value
0.083
y-value Emix =
x-value ln(icorr) =
y1-value
-0.659485119
y2-value
-0.659485119
-0.659485119 V
0.083
icorr = eln(icorr) =
EmixZn =
EmixZn =
EmixFe =
EmixFe =
y1-y2
0
-1.0561
-1.0510
-0.6595
-0.7030
1.086353193 mA
icorrZn =
icorrFe =
1.6680
1.0864
Comparing the results between the mixed corrosion potential and the measured values
for each metal, we can notice a slightly difference between them.
13
mA
mA
Question 7.
The corrosion rate (in mm/year) of the zinc (Zn) electrode is determined as follow:
For the mix potential of Zn EmixZn = - 1.0561 V,
the corrosion current is
icorrZn = 1.6680 mA
With the Faraday Law we can calculate the corrosion rate for Zn.
t Time
= 2;
= 65.409
= 7.14
;
3
= 12.82 ;
= 96484.56
= 60 60 24 365 = 31536000
65.409
0.001668 31536000
=
= 2
= 17.83
96484.56
17.83
3
=
= 2.499
7.14
=
=
10 = .
12.8
The corrosion rate (in mm/year) of the steel (Fe) electrode is determined as follow:
For the mix potential of Fe EmixZn = - 0.6595 V,
the corrosion current is
icorrZn = 1.0864 mA
With the Faraday Law we can calculate the corrosion rate for Fe.
z The valence of the metal ion
M Molar mass
Fe Fe density
F Faradays constant
SFe the surface of the Fe-electrode
W The amount of deposited or dissolved metal
t Time
= 2;
= 55.845
14
= 7.86
;
3
= 12.82 ;
= 96484.56
= 60 60 24 365 = 31536000
55.845
0.0010864 31536000
2
=
= 9.91
=
96484.56
9.91
3
=
=
= 1.261
7.86
=
=
10 = .
12.8
Question 8.
The corrosion rate (in mm/year) of the steel (Fe) electrode when it is short-circuited
with the zinc (Zn) electrode is as follows:
In this case, the least noble metal is then the anode. Therefore, the zinc (Zn) becomes the
anodic and steel (Fe) becomes the cathodic. Intersection can be read in the figure 05.
15
Zn(A)-Fe(K)-Zn(K)-Fe(A)
-12.000 -10.000
1.500
-8.000
-6.000
-4.000
-2.000
0.000
2.000
4.000
6.000
1.000
0.500
0.000
y = 0.0364x - 0.6625
-0.500
y = 0.0186x - 1.0656
-1.000
y = -0.1773x - 0.6448
-1.500
y = -0.153x - 0.9778
-2.000
Zn(A)
Zn(K)
Fe(A)
ln(icorr)Zn(A)Fe(K) = 2.148
ln(icorr)Fe(A) = -9.977
Fe(K)
EmixZn(A)Fe(K) = -1.0256
Linear (Zn(A))
Linear (Fe(A))
Figure 05. Interpolation of the cathodic and anodic line for Fe-electrode
Using the same procedure as for the Question 6, we then can find out the intersection
points of the anodic(Zn) and cathodic(Fe) line.
-
x-value
y1-value
y2-value
y1-y2
16
2.148
-1.0256
y-value Emix =
-1.0256 V
x-value ln(icorr) =
2.148
-1.0256
icorr = eln(icorr) =
0
8.5680 mA
From this intersection point, we can then deduce the corrosion current on the
anodic(Fe) line.
-
y-value Emix =
x-value ln(icorr) =
y-value
-1.0256
-1.0256 V
-9.977
icorr = eln(icorr) =
With the Faraday Law we can calculate the corrosion rate for Fe.
0.000046477 mA
t Time
= 2;
= 55.845
= 7.86
;
3
= 12.82 ;
= 96484.56
= 60 60 24 365 = 31536000
55.845
0.000000046477 31536000
2
=
=
= 0.000424
96484.56
0.000424
3
=
= 0.0000539
7.86
=
=
10 = .
12.8
17
Conclusion: After the connection of Fe with Zn, the corrosion rate of steel decreases with
a factor of 23348 times (0.985/0.0000422). The method is proving very effectively for
corrosion prevention and it shows the importance of Zn as a sacrificial metal for the
longer lasting life of steel in corrosive medium.
Question 9.
-
In order to calculate after how many days the zinc (Zn) electrode has been
sacrificed we use the Faradays law using t as the unknown value.
With the Faraday Law we can calculate the corrosion rate for Zn.
t Time
= 2;
= 65.409
= 7.14
;
3
= 12.82 ;
= 96484.56
= 60 60 24 = 86400
65.409
8.568 103 86400
2
=
=
= 0.251
96484.56
0.251
3
=
= 0.0351
7.14
=
=
10 = 0.0274
12.8
Considering that per day the Zn-electrode is corroding by 0.0351 cm3 and the total
volume of the electrode is 2 cm3, this will take 56.98 days for the Zn-electrode to
completely dissolve.
Similarly for the Fe-electrode using the results determined in question 8, (assuming that
the surface remains constant during corrosion), with a dissolve ratio of.
the Fe-electrode, which has the same dimensions as the Zn one and will dissolve in
approximately 37105 years.
18
The results presented above are an example of galvanic corrosion in which one metal (in
our case Zn) is sacrificed to protect another metal (Fe) and it can be notice the
difference between the results from question 7 and question 9, when due to the short
circuiting the Fe and Zn, the life span of Fe-electrode is increasing considerably.
Question 10.
a) Reducing the anodic surface by a factor of 3 means that the current i will get a value of i/3.
This means that the anodic line will get shifted with ln(3).
1
1
ln = ln + ln() = ln() 1.1
3
b) If we reduce the cathodic surface with the same coefficient of ln(3) we will see in the below
Evans diagram, the shifted cathodic line, from which we extrapolate the new mixed potential
and corrosive current.
EmixFe = - 0.645 V,
ln(icorrFe) = -0.809 icorrFe = e-0.809= 0.4453 mA
c) The corrosion of the steel electrode is a cathodic-controlled process. This is obvious because
19
-2.000
0.000
2.000
4.000
-0.200
-0.400
y = 0.0364x - 0.6225
-0.600
Fe(A)
Fe(K)
Fe(K)-ln(3)
-0.800
Linear (Fe(A)-ln(3))
Linear (Fe(A))
-1.000
Linear (Fe(K))
Linear (Fe(K)-ln(3))
-1.200
-1.400
-1.600
Fe(A)-ln(3)
Figure 06. Evans diagram of the shifted cathodic and anodic line for Fe-electrode
Question 11.
Calculate the molar volume of Fe2O3 and iron. Is the volume change such that after
oxidation of the iron a good adherence between the metal and the oxide will
occur?
Vm = M /
2 iron atoms and 3 oxygen atoms give molar mass M for Fe2Oe of 159,6887
The mass density of Iron is 7,874
20
2 3
30,4
=
= 4,29
7,092
4,29 > 1,8 Too large, so the oxide layer easily spalls from the surface. Result: poor
protection.
Question 12.
Also calculate the molar volume of copper and CuO. What is your conclusion about
the protective capability of the oxide?
Vm = M /
3
3
12,606
=
= 1,78
7,092
1,2 < 1,78 < 1,8
This means the oxide layer is compact and continuous and it gives a good protection.
Question 13.
What are the reaction equations for the corrosion of steel in surface water and the
corrosion of zinc in diluted hydrochloric acid?
For the steel, the same happens as explained before:
1. Fe Fe2+ + 2e
2. O2 + 2H2O + 4e 4OH3. Fe2+ + 2OH- Fe(OH)2
4. 4 Fe(OH)2 + O2 2 (Fe2O3 x H2O) + 2H2O
For the zinc, the reaction formula describes the oxidation of zinc:
21
Corrosion current
Emix = - 0.45 V
icorr = 10-4 A
b) 75% of anodic regions covered with inhibitor it means that the current i is 1/4i, so
log(i) is log(i/4).
y = a (logx) + b
(Emix = a log(i) + b)
a = 0.1
b = 0.0102
a = -0.1
b = -0.85
Emix = -0.42 V
icorr = 510-5A
c) Similar to the question above, but for this time the anode is unchanged, the function of
the anode is:
Anode: -0.45 = a log(10-4) + b
-0.55 = a log(10-5) + b
a = 0.1
b = 0.05
= 55.845
= 7.86
;
3
= 96484.56
= 4 5 4 + 4 4 2 = 1122 ;
= 60 60 24 365 = 31536000
55.845
3.162 106 31536000
2
=
=
= 0.0289
96484.56
22
0.0289
3
=
= 0.0037
7.86
=
=
10 = .
112
d) The electric current that the power source should deliver, such that the mixed
potential should be maintained at -0.60V is:
Using the Evan diagram from figure xx, we then determine the values of ianodeFe and
icathodeFe
Figure 07. Evans diagram of the cathodic and anodic line of Fe-electrode
=
= 105.5 102.5 = 0.00316A
Because the anodic current is negligible compared to the cathodic one, to keep the steel
plate at -0.6V a cathodic current of 0.00316A should be flowing.
23
e) If the Fe plate is short circuited with the Al one, then the data collected from the
Evans diagram are as following:
Mix potential
Emix = - 0.65 V
icorr = 10-2 A
Corrosion current
But, in the case of the short circuit, the anodic current of the Fe-plate will have the
corresponding value of icorr = 10-6 A.
= 55.845
= 7.86
;
3
= 96484.56
= 4 0.5 4 + 4 4 2 = 402 ;
= 60 60 24 365 = 31536000
55.845
106 31536000
2
=
=
= 0.0009
96484.56
0.0009
3
=
= 0.00115
7.86
=
=
10 = .
40
The amount of corroded Fe will decrease considerable over a year time if the Fe plate is
short circuited with Al.
24
Figure 08. Evans diagram for a certain steel and aluminum in North Sea water.
f) To determine the time in which the Al plate will dissolve, we use the Faradays Law
and calculate the corrosion rate.
26.98
102 31536000
=
= 3
= 32.664
96484.56
=
62.664
3
=
= 12.098
2.7
Aluminum can be used as a sacrificial anode because of its high electronegativity and
can protect the steel from corrosion.
25