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Corrosion of Iron in an
H 2s-co 2-H 20 System Composition and
Protectiveness of the Sulfide Film as a
Function of pH *
By J. B. SARD ISCO *and R. E. PITTS *
INTRODUCTION

ABSTRACT

Composition of the iron sulfide film, formed as a

result of lfquid phase H 2 S-COrH 2 0 corrosion
of Armco( 1 iron, has been related to the H 2 S
concentration in the H2 S- C0 2 gas and to the time
of exposure of the metal to the corrodent. 1 ' 2 It
has been shown also that the addition of FeS to
the H 2 S-COrH 2 0 solutiori alters the nature of
th e iron sulfide film. 2 It was not ascertained,
however, which species of the bivalent sulfur
(H 2 S, HS- or s=) was responsible for altering
the nature of the sulfide film as the total bivalent
sulfur concenrration was changed.

Composition and protectiveness of the

iron sulfide film, formed as a result
of the liquid phase H 2 S-C0 2 -H 2 0
corrosion of Armco iron, have been
related to the initial pH of the solution.
Composition of the film was determined
by electron diffraction analysis.
Protectiveness of the film was determined by measuring the weight loss
of iron specimens previously corroded
and covered by sulfide films formed
in H 2 S-C0 2 -H 2 0 solutions of different
pH values .

The purpose of the investigation reported herein

w 2. s twofold: (l) to measure the composition and
protectiveness of the iron sulfide film, formed
during the corrosion of Armco iron by liquid
p~rnse H 2 S-C0 2 -H 2 0 at various pH values, and
(::') to determine which, if any, of the bivalent
species (H 2 S, HS- or s=) contributed to the
relative non-protectiveness of the sulfide film.
Protectiveness of the film is defined as the
extent to which the film, after it is formed ,
protects the metal from further corrosion.

C:XP ERi MENTAL APPARATUS AND TECHNIQUES

'.V eight loss, weight of film remaining on the
sp2cimens and film composition were obtained at
V<Gious initial pH values. In addition, the protectiveness of the sulfide film was measured at different
pH values.
'Y~' ight

Loss and Weight of Film

The apparatus in which the corrosion reaction

wos carried out, the specimen preparation and
the experimental procedure are described in detail
elsewhere. 2
For this phase of the investigation Armco iron
specimens, 19 mils thick, were corroded. Two
corrosion cells were used, each containing three
specimens with a surface area of 9. 68 cm 2 and
2
two of 1.61 cm each. From the six 9. 68 cm 2
s pe cimens average weight loss and weight-of-film
,,:, .-: c~ rr.itte<l for publication AprJI 5, 1965.

* L: n:z.:cd Gas Corporation, Shreveport, Louisiana.

11
<

Armco Sceel Corporation, Middletown, OhJo.

Composition and the protectiveness

of the iron sulfide film were affected
by the initial pH of the H 2 S-C0 2 -H 2 0
solution. The film was least protective
in the pH region of about 6.5 to 8. 8.
The film that was least protective
contained essentially kansite, whereas
the film that was most protective
contained pyrite and troilite along with
kansite.

Because the HS- anion is the predominant species in the pH region

of about 6. 5 to 8. 8, it is indicated
that the HS- was at least partially
responsible for the film being less
protective.
data were obtained and on the l. 61 cm 2 specimens
electron diffraction analyses were made. The
corrosion reaction was carried out for 43 hours
at 24 ::'.:: l C (75 F). Specimen preparation and
corrosion reactions were carried out in a dry box.

The different pH values of the H 2 S-C0 2 -H 2 0

solution were obtained by adding NaOH or HAc
to distilled water, removing the oxygen from the
solution and then saturating the solution with the
H 2 S- C0 2 gas. Initial pH values were measured
in a cell at the end of the rrain of corrosion
cells. H2 S-C0 2 gas was bubbled continuously
through the cells at approximately 10 cc/min
for the duration of the test.
350

November 1965

PROTECTIVENESS OF SULFIDE FILMS

Protectiveness of the Sulfide Film

For this part of t.he investigation the apparatus
and experimental procedure were identical to that
discussed above with the following exceptions.
2
Three 9.68 cm
Armco iron specimens were
placed in each of four corrosion cells. At an
adjusted pH the corrosion reaction was carried
out for 41 hou:rs. From the specimens of two
of the cells the weight loss and weight of the film
remaining on the specimen were obtained at that
pH. The specimens of the other two cells were
rinsed with acetone, dried and then, with the film
still on the specimen, recorroded for an additional
24 hours in a fresh oxygen-free H 2 S-C0 2 -H 2 0
solution. The pH of the fresh oxygen- free solution
for each test was about 4. 0. Finally, the weight
lossE:s of these specimens were measured. The
protectiveness (P) of the sulfide film formed at
the various pH values was calculated from the
following expression:
l/ P

= W L/g

of film,

where
W L = weight loss at 65 hours - weight loss
at 41 hours, and
g of film= \Veight of film remaining on the specimens after the initial 41 hours of
corrosion.
Film Composition

,.--...

The corrosion product of the small specimens

2
(1.61 cm ), which were corroded for 43 hours,
was analyzed by transmission and reflection diffraction. The experimental procedures employed
for both of these techniques have been discussed
in detail elsewhere. 1 ' 3
For the transmission diffraction studies the
film was stripped from tte Armco iron by a
water-free I 2 -CH 3 0H solution in the dry box. 4
The stripped film was transferred to the electron
microscope without the film coming in contact
with air.
Specimens used for reflection diffraction studies
were mounted on the diffraction manipulator of
the microscope in the dry box and transferred to
the microscope in a plastic bag. The specimens
came in contact with air for 2 to S seconds.
Processing the Electron Diffraction Data

The radii of the rings of the electron diffraction

plates were measured by a diffraction plate
comparator. Ring intensities were visually
estimated. A program for the electronic computer
.....---._ was written to aid in the identification of the
iron sulfide films. The sulfide films consisted
of one to four components. Input data for the
computer were radii of the rings and values of
the microscope constant. Interplanar distances
were calculated from the equation:

351

dh k l

= K/2R

where dh k 1 is interplanar distance, K is the

microscope constant and R is the radius of the
ring. The computer output contained the following:
l. Interplanar
ring intensities;

distances, radii diameters and

2. Suspected compounds along with the ratio of

the number of rings matched to the number that
should have matched;

3. Average error
e ach compound;

for all pairs of rings for

4. The compounds found in the corrosion product,

each marked by an asterisk.

Figure 1 contains two examples of electron

diffraction patterns interpreted by the computer.
Arrows indicate components that were identified
also by manual methods. It was decided arbitrarily
that one minor ring of a component could be
missing without negating the presence of that
component. See, for example, pyrite, troilite and
marcasite of plate S28R and troilite of plate
579R. Interpretation of the patterns by the computer
has been verified by manual methods for at least
180 of 200 patterns analyzed. It is to be noted,
however, that this program is being used as an
aid in analyzing the diffraction patterns and not
as an absolute method.

RESULTS AND DISCUSSION OF RESULTS

Table 1 contains results obtained by electron
diffraction analysis of films formed at various
initial pH values. Components of the films were
troilite, kansite and pyrite or marcasite . Because
the diffraction patterns of pyrite and marcasite
are very similar, no distinction was made between
them. The numerator of each fraction in the table
is the number of diffraction plates in which each
component was identified and the denominator is
the total number of diffraction plates obtained at
that pH.
From the data in Table 1, the following inferences
can be made. In the pH region of6.6 to 8.4, kansite
was the only component in the film. In the pH
regions 4. 0 to 6. 3 and 8. 8 to 11. 0, kansite, FeS 2
(pyrite or marcasite) and troilite were present
in the film with kansite being the major component.
Because kansite is responsible for the non1 5
protectiveness of the iron sulfide film, '
the
film should be most protective in the pH regions
where the film contains components in addition
to kansite.
Figure 2 contains the non-protectiveness factor
(l / P) of the sulfide film as a function of the
initial pH of the H 2 S- C0 2 - H 2 0 solution. The data
are tabulated in Table 2. The non-protectiveness
of the film formed at each pH was measured by
the technique described in the experimental section.
Figure 2 shows that the film was least protective

'~ 52

CORROSION - NATIONAL ASSOCIATION OF CORROSION ENGINEERS

PLATE
RJNG

'28R

B 0, 0 KV,

tNTENS!TY

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2,094

0,3

0.658

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0,352

0,70

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0,42

Q,85b

2,H6J

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0,45"4

Q,908

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0. 5 1

1.10

1,900

0,582

1. lb

1 ,7990

O,b12

1.22

1. HOB

60

XB5

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20

10

TEST

Vol. 21

0. 6
60

10
1.

1,2.,.
B

50

13

-+ KANSITE
-+PYRITE
TRO!LITE
-+ARCAS!TE

bib
617
5/6
bl7
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PLATE

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1.898

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0,660

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1.5171

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1,3077

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1.956

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10

Figure 1 - Computer Print- Out.

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4.0.----.---.,---~---,------,--------~

...J

:-J

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I .01f-----j---j-- - - j - - -- - -- C - - - - - -- - i --

10

--<

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Figure 2 - Non-protectiveness (l/P) of the film vs pH at ::rn

H2 S concentration of 2. 00 psi a.

There is a slight maximum in the potential of

the steel electrodes in the saturated hydrogen
6
sulfide solution versus pH curves of Ewing in the
pH region of about 6. 8 to 8. 8. This observation
is another indication that the protectiveness of
the film varies as the pH of the solution is
changed. There is, however, no obvious correlation
between weight loss at 43 hours of Figure 3 and
non-protectiveness of the film.

pH

area 29. 04 cm".

in the pH region of about 6.5 to 8. 8 and becomes

more protective at the pH value of about 9.2.

Tot:i.l specime n surface

Differences in the physical appearance of the

sulfide films formed at different pH values are

November 1965

borne out by the replica electron micrographs of

Figure 4. The relatively protective films formed
at pH values of 3. 2 and 11. 0 appear to be more
tightlv pao:ked than the less protective film formed
at a pH of 7.2.
10:-T

il
"'9

'

!0

T..\BLE 1 - Electron Diffraction Results

- We .i qht loS!: at 43 hour<

Loss , o! 5 hours

i 6- We1~ht

5'

Initial
pH

[Experomentol err'or wos :+:0.2 X 10-2grom~

uf

(/)

I
I

In the intermediate pH region (7. 0 to 11. 0), HS is the predominant species. As was brought out in
the preceding paragraphs, 6.6 to 8.8 is the pH
region in which the sulfide film formed is least
protective . It appears that the bi sulfide ion
suppresses formation of FeS 2 and troilite. As a

1- - 1 - - - -1--+---+---+---1---~

353

PROTECTIVENESS OF SULFIDE FILMS

'

',.

4. ()
4.2
6.3

4.0

~'

- ----~.,..~--.:_,-

50

6.0

7.0

--- =~- - - - ---:?

I

'

8 .0

9.0

10.0

2/3
2/3
5/5
5/6
4/ 4

3.1

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1
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i

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Component
Pyrite
Troilite

4~
' ----".'----l-----'----1----'------l.--~

Kansite

6.6

7.2
8.4
8.8

11.0

pH

Figure 3 - \\.eigr.t loss and film weight vs pH at an H 2 S

concenrratio" of 1. 12 psia in H 2 - C0 2 gas. Total
specimen surface area 20. 04 cm;;.

3/3

4/4

4/ s
4/4

11. 0

pH 7 .2

pH 3.2

0
1/3

1/ 3
1/3

2/5

2; 5

1/ 6
l/4
0
0

1/6
0
0
0

l/S

l/S

3/4

1/4

pH 11.0

Figure 4 - Replica electron micrographs of iron sulfide film formed at various pH values.

:.HOO X

T ..;BLE 2 - Data for Protectiveness Sh1dies

Concenrration of the H2 S in the H2 S-C0 2 gas was 2.0 ps ia.

AVERAGES OF THREE COUPONS

Test
No.
l

2
3
4
~.

5
6
7
8
(l)
2

.fl Hr
Wt Loss< 1 l

41 Hr
Film Wt

. 0870
.0365
.0482
.0257
.0239
. 0022
.0031
.0035

.0054
.0108
.0068
. 0090
0102
.0069
.0069
.0104

65 Hr
Wt Loss< 1 l
.0975
.0567
. 0630
.0478
.0499
.0240
. 0265
.0201

Corrected for Blank Weight Loss

pH
pH/ar Time

I/P

Initial

l. 94
l. 87

3. 2
3.4
L3
6.4
6. 5

3. 7/30
4. 8/ 24
4 . 6/24
6. 4/ 23

7 .-1

7. 0/22 Hours
8.6/22 Hours
7.8/24 Hours

2.18
2. 46
2.55
3. 16
3 . 39
1.60

S.4
9.1

Hours
Hours
Hours
Hours

Normality
Na OH
(0.093)
0
0.003< 2 )
0.015
O.Ol?
0. 15 2 l
0.32
0.5
(Normality
Acetic Acid)

l Initi:i.l pH adjusted by adding acetic acid.

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CORROSION - NATIONAL ASSOCIATION OF CORROSION ENGINEERS

REFERENCES

result, in this intermediate region, the film

contained essentially kansite and is the least
protective.

CONCLUSIONS
It can be concluded that the composition and
pr otectiveness of the iron sulfide film were affected
by the change in the initial pH of the H 2 S-C0 2 -H 2 0
solution and that the film was least protective
in the pH region of about 6. 5 to 8. 8. The sulfide
film that was the 1 east protective contained
essentially kansite.

l. J. B. Sardisco, Wm. B. Wright and E. C. Greco. Corrosion

2.

3.
4.

ACKNOWLEDGMENTS
The authors express their appreciation to Jack
D. Wisterman of the Computer Section of the
l ' nited Gas Research Laboratory for writing the
r--- computer program and to Joseph E. Rountree
for the electron diffraction analyses.

Vol. 21

5.

6.

of Iron in an H 2 S-C0 2 -H 2 0 System: Corrosion Fi L'll Properties

o n Pure Iron. Corrosion, Vol. 19, No. 10, 354t-359t (1963i
October.
J. B. Sardisco and R. E. Pitts. Corrosion of Iron in an
H 2 S-COrH 2 0 System: Mechanism of the Sulfide Film Formation and Kinetics of the Corrosion Reaction . Corrosion,
Vol. 21, 1\o. 8, 245-253 (1965) August.
C. J. Arceneaux. Techniques for Handling Air-Sensitive
Materials in Preparations for Electron Microscopy. Norelco
Reporter, 7, 16 ff (1960) January-April.
W. H. J. Vernon, F. Wormwell and T. J . Nurse. The Thickness
of Air-Formed Oxide Films on Iron. J. Chem. Soc., 621-632
(1939).
F. H. Meyer, 0. L. Riggs, R. L . McGlasson and J. D.
Sudbury. Corrosion Products of Mild Steel in Hydrogen
Sulfide Environments. Corrosion, Vol. 14, No . 2, 109t-115t
( 1958) February.
S. P. Ewing. Electrochemical Studies of the Hydrogen Sulfide
Corrosion Mechanism . Corrosion, Vol. 11, No. 10, 497c-50lc
(1955) November.