GPA Research Report

RR-190

GPA RESEARCH PROJECT No. 982-2

An Examination of Interfering Factors in the

ASTM D-1838 Copper Strip Test

ASRL # 888-2005-2006
P.D. Clark and K.L. Lesage,
Alberta Sulphur Research Ltd., c/o Department of
Chemistry, The University of Calgary,
Calgary, Alberta, Canada
March 2006

II. FOREWORD
This project continues GPAs research program on trace specie impact on the Copper
Strip Test (ASTM D-1838). This continuation of Project 982 and was designed to verify
and validate the Copper Strip Test for LP Gas. This work was supported with funding
from the Propane Education and Research Council.
Based on the results presented in this report and the previous work on this project, the
following conclusions can be made:

The Copper Strip Test accurately detects corrosion for several containments
commonly found in LP Gas.

Even with the addition of water as required by ASTM D-1838, Carbonyl Sulfide
does not reliably produce a corrosive test coupon.

Use of the Copper Strip Test requires that one rigorously follow the test
procedure, including the use of the proper apparatus and methods. The findings
of previous studies which did not precisely follow ASTM D-1838 are therefore
suspect.

______________________
Dan McCartney, Coordinator
GPA Project 982

________________________
Arild Wilson,
Sub-group #1 Chairman

______________________
David Bergman,
Section F Chairman

III. DISCLAIMER AND COPYRIGHT NOTICE

GPA publications necessarily address problems of a general nature and may be used by
anyone desiring to do so. Every effort has been made by GPA to assure accuracy and
reliability of the information contained in its publications. With respect to particular
circumstances, local, state, and federal laws and regulations should be reviewed. It is not
the intent of GPA to assume the duties of employers, manufacturers, or suppliers to warn
and properly train employees, or others exposed, concerning health and safety risks or
precautions.
GPA makes no representation, warranty, or guarantee in connection with this publication
and hereby expressly disclaims any liability or responsibility for loss or damage resulting
from its use or for the violation of any federal, state, or municipal regulation with which
this publication may conflict, or any infringement of letters of patent regarding apparatus,
equipment, or method so covered.

Entire contents Copyright 2006 by Gas Processors Association, all rights reserved.

ii

IV. TABLE OF CONTENTS

II. FOREWORD i
III. DISCLAIMER AND COPYRIGHT NOTICE ii
IV. TABLE OF CONTENTS iii
V. LIST OF TABLES ... iv
VI. LIST OF FIGURES iv
VII. INTRODUCTION .. 1
VIII. OVERALL RESULTS AND CONCLUSIONS 1
IX. DISCUSSION OF RESULTS ..2
Test Matrix and Results .2
Interpretation and Conclusions from Individual Sets of Tests ..4
Blank tests .4
Test with Hydrogen Sulfide (H2S) 4
Tests with Elemental Sulfur (S8) ...4
Tests with Carbonyl Sulfide (COS) ...5
Tests with Oxygen (O2) .5
Tests with carbon dioxide (CO2)5
Test with a Combination of H2S and O2 5
Test with a Combination of H2S and CO2 .6
Test with a Combination of COS and O2 ..6
X. EXPERIMENTAL DETAIL ..7
XI. REFERENCES..9
XII. APPENDIX
A-1. Data tables 10
A-2. Figures ..14
A-3. Reaction Schemes for Interaction of Trace Contaminants
with Copper Surfaces .41

iii

V. LIST OF TABLES
Table 1. Matrix of Tests ...3
Table 2. Results of Copper Strip Tests..3
Appendix A1: Gas composition of propane mixtures pre and post copper strip testing
Table A1-1. Propane + H2S ...10
Table A1-2. Propane + COS ......10
Table A1-3. Propane + O2 ..11
Table A1-4. Propane + CO2 ...11
Table A1-5. Propane + H2S and O2 ...12
Table A1-6. Propane + H2S and CO2. ....12
Table A1-7. Propane + COS and O2 .....13

VII. LIST OF FIGURES

Figure 1. Reproduction of the ASTM Copper Strip Corrosion Standards Plaque ..14
Figure 2. Instrument Propane Blank ...15
Figure 3. H2S 5 ppmw in Propane ...16
Figure 4. H2S 10 ppmw in Propane .17
Figure 5. H2S 20 ppmw in Propane .18
Figure 6. S8 5 ppmw in Propane ..19
Figure 7. S8 10 ppmw in Propane 20
Figure 8. S8 20 ppmw in Propane 21
Figure 9. COS 5 ppmw in Propane ..22
Figure 10. COS 10 ppmw in Propane ..23
Figure 11. COS 20 ppmw in Propane ..24
Figure 12. COS 100 ppmw in Propane 25
Figure 13. O2 50 ppmw in Propane .26
Figure 14. O2 100 ppmw in Propane ...27
Figure 15. O2 1000 ppmw in Propane .28
Figure 16. CO2 10 ppmw in Propane ..29
Figure 17. CO2 100 ppmw in Propane 30
Figure 18. CO2 1000 ppmw in Propane ..31
Figure 19. H2S 5 ppmw + O2 100 ppmw in Propane ...32
Figure 20. H2S 5 ppmw + O2 1000 ppmw in Propane .33
Figure 21. H2S 10 ppmw + O2 1000 ppmw in Propane ...34
Figure 22. H2S 5 ppmw + CO2 10 ppmw in Propane ...35
Figure 23. H2S 5 ppmw + CO2 100 ppmw in Propane .36
Figure 24. H2S 10 ppmw + CO2 10 ppmw in Propane .37
Figure 25. COS 10 ppmw + O2 100 ppmw in Propane 38
Figure 26. COS 10 ppmw + O2 1000 ppmw in Propane ..39
Figure 27. COS 100 ppmw + O2 1000 ppmw in Propane 40

iv

VII. INTRODUCTION
ASTM D 1838 is a test procedure used to evaluate the potential corrosiveness of liquefied
petroleum gas containing trace impurity components towards copper. In summary, the
test involves immersion of a polished copper strip in the LPG in question at 100F
(37.8C) for 1 hour and then comparison of the appearance of the strip to a set of
commercial standards prepared for use as part of the ASTM procedure. The standards
are differentiated into four categories (1 4) with sub-classifications of 1a - 1b, 2a 2e,
3a 3b and 4a 4c. The categories 1 4 represent slight tarnish, moderate tarnish, dark
tarnish and corrosion respectively and the visual appearance of the categories ranges from
an off-color copper metal for 1, a range of pinks, green/lavender and brassy gold colors
for 2, magenta with over-casts of red and green for 3 and generally dark grays and blacks
for 4. The D-ASTM 1838 procedure recognizes the general difficulty of differentiating
some of the possible test results by not offering definitive guidelines for absolute
assignment of a particular classification within each class.
A review of the literature (refs.) shows that it is generally accepted that hydrogen sulfide
(H2S) and elemental sulfur (S8), even at low levels (1 20 ppmw), result in corrosion of
the copper such that LPG containing these materials will result in 2c 4c results.
Carbonyl sulfide (COS) has been shown not to tarnish copper within the framework of
ASTM D-1838, even up to concentrations of 100 ppmw. However, hydrolysis or
oxidation of COS may result in production of H2S and S8 respectively, thus leading to
field observations that LPG containing COS can fail the copper strip test if air or water
contaminants are introduced at a later date.

VIII. OVERALL RESULTS AND CONCLUSIONS

A series of ASTM D-1838 copper strip corrosion tests was performed using propane as
the base hydrocarbon containing various contaminant species, namely H2S, S8, COS, CO2
and O2. In some cases, a combination of these contaminants was investigated. The
concentrations of these components were chosen to meet the levels expected in
commercial situations.
H2S and S8 were found to result in test failures at lower levels of 5 and 10 ppmw
respectively. H2S resulted in multi-colored green-pink-lavender copper strips at 5 ppmw
and dark grey-black strips > 10 ppmw. S8 produced a grey-black copper strip at 10 ppmw
or greater concentration. Possibly, a very thin grayish film may have been present using
5 ppmw S8 but, overall, these tests were judged to be 1(a). The very weak dark film using
5 ppmw S8 was not visible in the photographic records made for this project (see
Appendix A-2).

COS, CO2 and O2 did not produce discoloration of the copper strips at < 100 ppmw
concentration, but some discoloration (patchy orange) was observed for COS at 100
ppmw. A greenish tinge was observed for CO2 at high levels but this discoloration was
observer dependent and, again, was not visible in photographs (Appendix A-2).
A combination of H2S and O2` results in consumption of the H2S producing copper strips
similar in appearance to tests with S8 alone. This observation was made when only 10
ppmw H2S was present in the combined contaminant mixture. In general, a combined
test using H2S and CO2 resulted in copper strips similar in appearance to those obtained
without CO2. The exception to these observations was when ca. 1000 ppmw CO2 was
present in combination with H2S. In this case the multi-color strips produced by H2S
alone were replaced by an even dark layer on copper strip.
Tests using a combination of COS and O2 gave results very similar to those without O2
until 1250 ppmw of O2 was present. In this case, the test strips could clearly be
designated as fails at the 3(a b) category.

IX. DISCUSSION AND RESULTS

Test Matrix and Results
The proposed matrix of tests is given in Table 1 and the actual test conditions and result
classification for each test are given in Table 2. Note that the very small quantities of
sulfur compounds and trace contaminants shown as target concentrations in Table 1 were
not achieved precisely because of the experimental limitations in introducing ppm
quantities of sulfur compounds and contaminants to liquid propane.
Classification of the test results according to the ASTM standards is subjective and open
to observer bias. Thus, the determinations given in Table 2 contain the element of
observer judgment. The reader can make his/her own evaluation by consulting the
electronic files and photographic records provided with this report.

Table 1 . Matrix of Testsa

Concentration (ppmw)b

Propane
Contaminant
Blank
H2S

10

20

S8

10

20

COS

10

20

O2

10

100

1000

CO2

10

100

1000

H2S+O2

5+10

5+100

10+100

H2S+CO2

5+10

5+100

10+10

COS+O2

10+10

10+100

100+100

100

a. All tests were conducted according to ASTM D 1838

b. Contaminants quantities may vary by +/ - 25%

Table 2 Results of Copper Strip Tests

The results and conditions for the tests are recorded in Table 2, Figures 1 27 in
Appendix A-2) and Tables A1-1 A1-7 in Appendix A1.
Contaminant Concentrations (ppmw) and Results
A. Blank
B. H2S
C. S8
D. COS
E. O2
F. CO2
G. H2S
O2
H. H2S
CO2
I. COS
O2

None
1a
5.6
3b
5
1a
5.0
1a
51
1a
10.5
1a
5.0
111
3b
4.6
9
3b
10.5
74
1a

None
1a
4.5
3b
5
1a
5.5
1a
------------5.0
100
3b
4.6
9
3b
10.5
74
1a

11.3
3b
10
4a
10.9
1a
115
1a
106
1a
4.6
1110
3b
5.0
128
4a
8.9
932
1a

11.0
3b
10
4a
------------115
1a
5.0
893
3b
5.0
128
4a
8.9
932
1a

20.6
4a
20
4a
22.5
1a
1190
1a
986
1a
12.2
1280
4a
9.0
13
3b
96
1250
3a / 3b

19.2
4a
20
4a
21.9
1a
1178
1a
1173
1a
12.6
1000
4a
9.0
13
3b
96
1250
3a / 3b

106
1b / 3a
2530
1a

Interpretation and Conclusions from Individual Sets of Tests

As already stated, the reader may wish to consult the electronic files and photographic
records provided with this report as assignment of the actual copper strips from each test
condition is subject to observer bias.
Blank tests.
Observation of 1(a) results for tests with no contaminants validates that the experimental
procedures of ASTM D-1838 were followed successfully and that any small amounts O2
or CO2 that are not purged from the apparatus do not cause a fail result. This result
confirms that ASTM D-1838 does give a null result when its procedures are followed.
Tests with hydrogen sulfide (H2S)
A nominal concentration of 5 ppmw H2S in propane results in a 3(b) appearance and 4(a)
when the H2S concentration was increased to 20 ppmw. The blue, green, lavender and
pink striations of the 3(b) results are likely due to films of copper (I) and copper (II)
sulfides lain over the metallic sheen of the copper surface. The darker coloration typical
of the 4(a) result could be the product of copper corrosion by a combination of reactions
involving S8 as S8 can be formed by the oxidation of H2S by the primary corrosion
product copper (II) sulfide (see Appendix A-3) for schemes summarizing the overall
chemistry).
Gas analyses from these tests (Table A1-1)showed that with < 20 ppmw H2S in the initial
charge, all of it was consumed by reaction with either the copper strip or was adsorbed on
the walls of the apparatus. Some residual H2S was observed when the initial amount was
20 ppmw. The detection of small amounts of O2 at the conclusion of the test, when none
had been present at the beginning of a test, may stem from O2 being desorbed from the
walls of the apparatus into the propane during the test or by contamination with air during
sampling.
Tests with Elemental Sulfur (S8)
A 4(a) result was obtained with 10 ppmw or greater amount of S8 dissolved in propane
but interpretation of the 5 ppmw tests is more difficult. A very slight darkening of the
copper strip was observed with 5 ppmw but it was difficult to assign the strips to any of
the standards. S8 appears to form black copper (II) sulfide as the only product thus the
degree of darkening of the strip is homogeneous and dependent on the amount of S8 in
the system. 5 ppmw of S8 appears to be near the level at which a fail copper strip test is
produced by ASTM D-1838 but it seems that the strip appearances step from 1(a) directly
to 4(a) as the concentration of S8 increases.

Tests with Carbonyl Sulfide (COS)

COS had no tarnish effect on copper up to concentration of 20 ppmw but a slight
discoloration was observed for tests conducted with 100 ppmw. The 100 ppmw tests
might be interpreted as either 1(b) or 3(a). These results show that COS does not
hydrolyze to H2S under the conditions of ASTM D-1838 despite the presence of free
water in the test. Even if the 100 ppmw test is judged to be 3(a) (an orange
discoloration), the absence of the classic multicolor striations observed with small
amounts of H2S offers further evidence that COS is not hydrolyzed rapidly to H2S under
the conditions employed with ASTM-D1838.
The gas analysis data (Table A1-2) show that little or no COS was consumed when the
initial quantity was 20 ppmw or less, but the reduction in COS noted for the 100 ppmw
experiment is in agreement with the copper strip appearance change observed at this level
of COS.
Tests with Oxygen (O2)
The background effect of O2 is of interest because copper (II) oxide is black. However,
incorporation of O2 in the 50 2500 ppmw range did not produce a positive test
illustrating that O2 does not corrode copper over the time-frame of the test.
It is unclear from the gas analysis data (Table A1-3) whether O2 was consumed in any of
the experiments with added O2. Thus, the reductions observed at the highest added level
could simply be due to adsorption onto the test cylinder surfaces.
Tests with Carbon Dioxide
Tests using a CO2 range of 10 ca. 1000 ppmw yielded 1(a) tests in all cases although at
the highest level a general greening of the copper may have been apparent (observer
dependent, but not recorded on the photographs). Since it is well known that exposure of
copper to the atmosphere will lead to a green color over prolonged periods, it is
concluded that the timeframe and conditions of ASTM D-1838 do not duplicate long
term environmental exposure of copper to the atmosphere.
The gas analysis data (Table A1-4) reveal that some CO2 was consumed when the
propane was charged with ca. 1000 ppmw thus offering an explanation for the eye-only
observation of a green tinge.
Tests with a Combination of H2S and O2
Since it is well known that O2 converts H2S to S8, a copper strip test with a combination
of the two materials may yield corrosion patterns more reminiscent of sulfur.
Examination of Table 2 shows that, as expected, the combination of H2S and O2 results in
5

failing tests [3(b)] for low H2S concentrations (4 - 5 ppmw) and 4(a) for 12 ppmw H2S.
Interestingly, the 12 ppmw test was more similar in appearance to the corresponding 10
ppmw S8 test than to the 10 ppmw H2S test (with no added O2) in that a generally even,
dark discoloration was observed. Inspection of the gas data collected from these tests
(Table A1-5) show that all of the H2S was consumed during the one hour period as was
the case for H2S tests with up to 10 ppmw H2S (no air) . However, since O2 levels also
decrease, this observation is in accord with its consumption by reaction with H2S. H2S
can also be moved from the propane by reaction with copper or adsorption onto the test
apparatus surfaces.
Tests with a combination of H2S and CO2
A test with 4.6 ppmw H2S and 9 ppmw CO2 resulted in a 3(b) result with similar
appearance to the equivalent test without CO2. Likewise tests with 9 and 13 ppmw H2S
and CO2 yielded 3(b) results with similar appearances to the test without CO2. However,
the test employing 5 and 128 ppmw H2S and CO2 respectively yielded a 4(a) result. In
particular, the appearance of these strips was quite different to the 3(b) multi-colored
appearances of the 5 ppmw H2S tests without CO2. These results lead to the conclusion
that CO2 at > 100 ppmw will result in a change in appearance of the copper strip, most
probably as a result of formation of a carbonate film at the copper surface.
Gas analysis data (Table A1-6) show that all H2S was consumed and CO2 is also
absorbed on copper surfaces.
Tests with a Combination of COS and O2
One possible outcome of these tests was that COS would be oxidized to S8 thus causing a
fail test. With ca. 10 ppmw COS and either 74 or ca. 1000 ppmw O2 only minimal
discoloration of the test strip was observed such that the result might be classified as 1(a),
possibly 1(b). However, when 100 ppmw COS was present with 1250 ppmw O2, the
strips were discolored with classification as 3(a b). Oxidation of COS would yield both
CO2 and S8 suggesting, perhaps, that a dark coloration would have been observed. Since
this is not the case, it can be concluded that the oxidation of COS is slow and, most
likely, follows a complex pathway which does yield S8 as a prime product.
Interestingly, the gas analysis data (Table A1-7) indicate that very little of the COS was
reacted, even when quite high levels of O2 were present. However, it appears that a
considerable quantity of O2 was absorbed onto the Copper Strip Vessel (CSV) and copper
surfaces. Thus, the fail test observed with 100 ppmw COS may result from a complex
combination of species arising from co-absorption of both COS and O2.

X. EXPERIMENTAL DETAIL
Overall Procedure: The basic procedures outlined in ASTM D-1838 were followed
rigorously with deviations described below being employed to add the required
contaminants.
Apparatus and Materials: All experiments were conducted in a copper strip vessel using
copper strips which met the specifications for the ASTM D-1838 procedure (Koehler
Instruments). Sulfur free, liquid propane (Instrument Grade) was supplied by Praxair. The
propane purity was validated by gas chromatography fitted with a thermal conductivity
detector (detection limits: O2 < 3 ppmw ; CO2 < 4 ppmw) and with a pulsed flame
photometric detector for sulfur compounds (COS, H2S, CS2, MeSH, detection limit < 1
ppmw). In most experiments, trace contaminates were added to propane contained in a
500 mL SS charge cylinder. The exact composition of the propane was analyzed by GC
prior to purging and filling a CSV. For the binary contaminate experiments (e.g. H2S and
O2), one contaminate was added to the charge cylinder and the other was introduced
separately into the CSV just prior to propane introduction. In this manner the binary
composition was created at the start of the test. In the case of the experiments utilizing
S8, the required amount of sulfur was added as a hexane solution to each individual CSV
which was then charged with propane. The specific details relating to each experiment
will be discussed separately. A GC sampling system was utilized that allowed for
removal of a liquid propane sample into a 250 L sampling loop at 212F (100oC). A
pneumatic valve then injected the contents of the sample loop into the gas
chromatograph. Gas analysis was performed on the propane in the charge cylinder prior
to the start of the test as well as on the propane in the CSV at the conclusion of the test.
The wetted parts of the test system were 316 SS with fused silica and nylon transfer lines.
Blank Tests: Blank tests were necessary to verify the purity of the propane, the
cleanliness of the apparatus and the analytical methodology. The blank test consisted of
filling the charge cylinder with propane and performing the ASTM D-1838 test as a
propane sample. Gas analyses were performed on the propane that was loaded into the
charge cylinder as well the propane in the CSVs at the conclusion of the test.
Tests with H2S: In these tests the charge cylinder was flushed with pure H2S gas. Liquid
propane was then introduced and the charge cylinder to fill it to capacity. Due to the high
solubility of H2S in liquid propane the resulting mixture had an H2S concentration > 100
ppmw. The required concentration was prepared by venting a given weight from the
charge cylinder and then re-filling with more propane. The exact concentration was
verified by gas chromatography prior to the start of the copper strip test.
Tests with S8: In these tests a solution of S8 (re-crystallized from toluene) in hexanes was
prepared and added to the individual CSVs. Each CSV was determined to contain 60 +/-

2 g of propane when was filled with propane. Therefore, to perform a 20 ppmw S8 test a
solution of 1.2 mg/mL S8 in hexanes was prepared. One mL of this solution was added to
the CSV after water wetting and prior to filling with propane. It was assumed that the act
of filling the CSV mixed the hexane solution with the liquid propane. No initial analytical
determination of the S8 content was made. At the conclusion of the test the contents of
the CSV was collected to determine the residual S8 content.
Tests with COS: These tests were performed in a manner similar to that described for
H2S. I.e., the charge cylinder was flushed with pure COS gas. The COS was also very
soluble in the liquid propane and subsequent venting and dilution of the charge cylinder
contents was necessary.
Tests with O2: The tests performed with O2 as an impurity were unique with respect to
the fact that O2 gas has a very limited solubility in liquid propane. Initially it was thought
that the higher concentration of O2 in liquid propane were unattainable at ambient
temperatures. It was found, however, that the O2 concentration could be increased
substantially by maintaining an overpressure of pure O2 over the liquid propane in the
charge cylinder. It was realized that some of this dissolved O2 would be lost after
charging the CSV but each concentration was verified before the start of the test.
Tests with CO2: For tests performed with CO2 as an impurity the charge cylinder was
initially filled with propane. A small amount of CO2 gas was added via the lower valve
on the charge cylinder. (CO2 delivery pressure = 800 psig). Analysis of the charge
cylinder contents showed that an equilibrium CO2 concentration was established rapidly.
The CO2 was found to be quite soluble in liquid propane and the overpressure in the
charge cylinder, even at 1000 ppmw, was negligible.
Tests with H2S + O2: For these tests a saturated solution of H2S in hexanes was prepared.
It was found that the solution as prepared was not stable and lost H2S rapidly perhaps as
oxidation to S8. Therefore, a freshly saturated hexane solution was prepared and 20 mL
aliquots were sealed in glass ampoules. On a given day of testing an ampoule was opened
and decanted into a vial. It was found that 0.25 or 0.50 mL of the solution gave a 5 or 10
ppmw H2S concentration in the CSV. The concentration was analyzed at the beginning of
the day to verify that the H2S initial concentration was correct. The charge cylinder was
prepared with the required O2 concentration as per the O2 tests and its concentration was
also verified by GC. The correct amount of H2S in hexane (0.25 or 0.50 mL) was added
to the water wet CSV which was then sealed with a polished copper strip. The O2 in
propane was added from the charge cylinder making the assumption that adequate mixing
was accomplished during the filling operation. At the conclusion of the test the liquid
propane in the CSV was analyzed. Another aliquot of H2S in hexane (0.25 or 0.50 mL)
was added to a dry CSV and filled with propane to again verify the H2S concentration
(final). The average value of the initial and final H2S result was the value that was
reported for that particular test.

Tests with H2S + CO2: These tests were performed in an analogous manner to the H2SO2 tests with CO2 being substituted for O2 in the charge cylinder. The same ampoules of
H2S in hexanes were used for these tests.
Tests with COS + O2: For these tests a solution of COS in hexanes was prepared and
sealed in ampoules. A fresh ampoule was used daily in a manner similar to that described
for H2S. It was found that COS was very soluble in the hexanes. One hundred microliters
or 1 mL of solution gave COS concentrations of 10 or 100 ppmw respectively in the
CSVs. Again the COS concentration was checked at the beginning (initial) and at the
end (final) of the actual copper strip test as separate determinations. A significant portion
of the initial COS remained in the CSVs at the conclusion of the tests. This result
indicates that the rate of COS oxidation is slow, relative to the time scale of the ASTM
D1838 copper strip test.

XI. REFERENCES
Ferm, R.J. The Chemistry of Carbonyl Sulfide. Chem Rev. 1957, 57, 621.
Svoronos, P.D.N.; Bruno T.J. Carbonyl Sulfide: A Review of the Chemistry and
Properties. Ind. Eng.Chem. Res. 2002, 41, 5321-5336.
Chalk, G. MetroGas, Inc., Denver, CO. Personal Communication, 2001.
Andersen, W. C.; Bruno, T.J. Kinetics of Carbonyl Sulfide Hydrolisis. 1. Catalyzed
and Uncatalyzed Reactions in Mixtures of Water + Propane. Ind. Eng. Chem. Res.
2003, 42, 963-970.
Thompson, H.W.; Kearton, C.F.; Lamb, S.A. The Kinetics of the Reaction between
Carbonyl Sulphide and Water. J. Chem. Soc. 1935, 1033.

XII. APPENDIX A-1. Data Tables

(Note: all CSV data were obtained at the conclusion of the tests)
TABLE A 1-1: Propane + H2S
Gas Composition (ppmw in Propane)
Nominal
PPMW H2S

Sample

O2

CO2

COS

H2S

Charge Cylinder(1)

<3

<4

<1

5.4

CSV-1

31

<4

<1

<1

CSV-2

35

<4

<1

<1

Charge Cylinder(1)

<3

<4

<1

11

CSV-1

25

<1

<1

CSV-2

20

<4

<1

<1

Charge Cylinder(1)

<3

<4

<1

19.2

CSV-1

20

<4

<1

12.1

CSV-2

15

<4

<1

3.5

10

20

(1) - Average of 3 or more Determinations

TABLE A 1-2: Propane + COS

Gas Composition (ppmw in Propane)
Nominal
PPMW COS
5

10

20

100

Sample

O2

CO2

COS

H 2S

<3

<4

5.5

<1

CSV-1

<4

4.3

<1

CSV-2

111

<4

4.5

<1

<3

<4

10.9

<1

CSV-1

<3

<4

7.5

<1

CSV-2

41

<4

9.5

<1

<3

<4

21.9

<1

CSV-1

<3

<4

16.0

<1

CSV-2

<4

15.2

<1

<3

<4

106

<1

CSV-1

<4

83

<1

CSV-2

<3

<4

87

<1

Charge Cylinder

Charge Cylinder

Charge Cylinder

Charge Cylinder

(1)

(1)

(1)

(1)

(1) - Average of 3 or more Determinations

10

TABLE A 1-3: Propane + O2

Gas Composition (ppmw in Propane)
Nominal
PPMW O2

Sample

O2

CO2

COS

H2S

50

Charge Cylinder(1)

51

<4

<1

<1

CSV-1

151

<4

<1

<1

CSV-2

237

<4

<1

<1

Charge Cylinder(1)

115

<4

<1

<1

CSV-1

20

<4

<1

<1

CSV-2

109

<4

<1

<1

Charge Cylinder(1)

1189

<4

<1

<1

CSV-1

635

<4

<1

<1

CSV-2

598

<4

<1

<1

Charge Cylinder(1)

2530

<4

<1

<1

CSV-1

990

10

<1

<1

CSV-2

502

<1

<1

100

1000

2500

(1) - Average of 3 or more Determinations

TABLE A 1-4: Propane + CO2

Gas Composition (ppmw in Propane)
Nominal
PPMW CO2
10

100

1000

Sample

O2

CO2

COS

H2S

<3

10.5

<1

<1

CSV-1

11

<1

<1

CSV-2

10

16

<1

<1

<3

115

<1

<1

CSV-1

98

<1

<1

CSV-2

373

<1

<1

<3

986

<1

<1

CSV-1

696

<1

<1

CSV-2

448

<1

<1

Charge Cylinder

Charge Cylinder

Charge Cylinder

(1)

(1)

(1)

(1) - Average of 3 or more Determinations

11

TABLE A 1-5: Propane + H2S and O2

Gas Composition (ppmw in Propane)
Nominal
PPMW H2S
- PPMW O2
5
-100

5
-1000

10
-1000

Sample

O2

CO2

COS

H2S

100

<4

<1

5.0

CSV-1

115

29

<1

<1

CSV-2

68

<4

<1

<1

1110

<4

<1

4.6

CSV-1

329

<4

<1

<1

CSV-2

225

<4

<1

<1

1280

<4

<1

12.2

CSV-1

131

<4

<1

<1

CSV-2

225

<4

<1

<1

Charge Cylinder

Charge Cylinder

Charge Cylinder

(1,2)

(1,2)

(1,2)

(1) - Average of 3 or more Determinations

(2) - H2S added separately to CSV's as a C6 solution

TABLE A 1-6: Propane + H2S and CO2

Gas Composition (ppmw in Propane)
Nominal
PPMW H2S
- PPMW CO2
5
-10

5
-100

10
-10

Sample

O2

CO2

COS

H2 S

<3

<1

4.6

CSV-1

16

<4

<1

<1

CSV-2

<4

<1

<1

<3

128

<1

5.0

CSV-1

15

27

<1

<1

CSV-2

<3

25

<1

<1

<3

13

<1

9.0

CSV-1

<3

<4

<1

<1

CSV-2

<4

<1

<1

Charge Cylinder

Charge Cylinder

Charge Cylinder

(1,2)

(1,2)

(1,2)

(1) - Average of 3 or more Determinations

(2) - H2S added separately to CSV's as a C6 solution

12

TABLE A 1-7: Propane + COS and O2

Gas Composition (ppmw in Propane)
Nominal
PPMW COS
- PPMW O2
10
-100

10
-1000

100
-1000

Sample

O2

CO2

COS

H2 S

74

<4

10.5

<1

CSV-1

<4

7.9

<1

CSV-2

25

<4

7.0

<1

932

<4

8.9

<1

CSV-1

100

<4

9.0

<1

CSV-2

26

<4

10.5

<1

1250

<4

96

<1

CSV-1

<4

86

<1

CSV-2

12

<4

95

<1

Charge Cylinder

Charge Cylinder

Charge Cylinder

(1,2)

(1,2)

(1,2)

(1) - Average of 3 or more Determinations

(2) - COS added separately to CSV's as a C6 solution

13

XII. APPENDIX A-2. Figures

Figure 1. Reproduction of the ASTM Copper Strip Corrosion Standards Plaque

14

Figure 2. Instrument Propane Blank

15

Figure 3. H2S 5 ppmw in Propane

16

Figure 4. H2S 10 ppmw in Propane

17

Figure 5. H2S 20 ppmw in Propane

18

Figure 6. S8 5 ppmw in Propane

19

Figure 7. S8 10 ppmw in Propane

20

Figure 8. S8 20 ppmw in Propane

21

Figure 9. COS 5 ppmw in Propane

22

Figure 10. COS 10 ppmw in Propane

23

Figure 11. COS 20 ppmw in Propane

24

Figure 12. COS 100 ppmw in Propane

25

Figure 13. O2 50 ppmw in Propane

26

Figure 14. O2 100 ppmw in Propane

27

Figure 15. O2 1000 ppmw in Propane

28

Figure 16. CO2 10 ppmw in Propane

29

Figure 17. CO2 100 ppmw in Propane

30

Figure 18. CO2 1000 ppmw in Propane

31

Figure 19. H2S 5 ppmw + O2 100 ppmw in Propane

32

Figure 20. H2S 5 ppmw + O2 1000 ppmw in Propane

33

Figure 21. H2S 10 ppmw + O2 1000 ppmw in Propane

34

Figure 22. H2S 5 ppmw + CO2 10 ppmw in Propane

35

Figure 23. H2S 5 ppmw + CO2 100 ppmw in Propane

36

Figure 24. H2S 10 ppmw + CO2 10 ppmw in Propane

37

Figure 25. COS 10 ppmw + O2 100 ppmw in Propane

38

Figure 26. COS 10 ppmw + O2 1000 ppmw in Propane

39

Figure 27. COS 100 ppmw + O2 1000 ppmw in Propane

Note: The top part of the middle strip was exposed to propane vapor due to leakage of
some propane

40

XII. APPENDIX A-3.

Reaction Schemes for Interaction of Trace Contaminants with Copper
Scheme 1
Copper Strip Chemistry in the Presence of H2S and Sulfur
(Simplified)
H2S

H2O

Cu
(surface)
II

H2O

2 Cu S
+ H2S
(primary corrosion
product)

Cu

1/
8

II

Cu S +
(black)
I

2 Cu S + 2 H+ +
(green/red)

H2O

S8

H2

1/
8

S8

II

Cu S
(black)

Key points

Colors will be dependent of corrosion film thickness

I

Cu S overlain on a copper surface may produce multi-color test

II

Reaction with S8 to form Cu S could be the reason for even black discoloration

Scheme 2
Copper Strip Chemistry in the Presence of CO2 and H2S

Cu

CO2

H2O

CuCO3

(surface)

CuCO3

H2

(blue-green)

H2O

Cu (OH)2

+ CO2

(blue-green)

Cu (OH)2 +

II

H2S

Cu S

2 H2O

(black)
Key points

An initial carbonate and hydroxide corrosion film may result in an even black
discoloration when H2S is present

41

Scheme 3
Copper Strip Chemistry in the Presence of COS

COS

Cu

COS

O2

COS

H2O

H2O

No immediate chemistry

100F
H2O

CO2 +

1/
8

CO2 +

H2S (very slow)

S8 (very slow)

Key points

None of these reactions take place at a significant rate, although the reaction
with O2 may occur to small degree over the time frame of the test

42