Corrosion Science,Vol 23, No. 4, pp. 353-362, 1983 0010-938X/83/040353-10 $03.

00/0
Printed in Great Britain. Pergamon Press Ltd.

CHEMICAL STUDIES OF POLYTHIONIC ACID STRESS--

CORROSION CRACKING

HUGH H . HOROWITZ
Exxon Research & Engineering Co., Box 101 Florham Park, NJ 07932, U.S.A.

Abstract--Low temperature stress corrosion cracking of sensitized stainless steel, promoted by

aqueous solutions of polythionates SxO~-, and related sulfur compounds, particularly thiosulfates,
has been a long known problem in the petroleum industry and more recently has cropped up in the
nuclear power industry. Membrane permeation results presented here show that S~O]- and S20~-
do not function simply as sources of sulfide to promote hydrogen permeation and embrittlement.
They do promote anodic dissolution, also generating an unusual adsorption-related anodic spike in
voltammetric scans. The oxidation of iron sulfide scales, said to be the source of the substances in
petroleum refineries, has been shown to give rise mostly to Fe..O3 and elemental sulfur, with low
yields of both $40~- and S~O~-.

INTRODUCTION

POLYTHIONIC acid stress-corrosion cracking occurs during "turnaraounds" or inspec-

tions of petroleum refinery units processing sulfurous streams, after air enters the
equipment and the temperature drops below the dew point. It is intergranular in
nature. It occurs with stainless steels which have been heat sensitized so as to form
chromium rich carbide granules at the grain boundaries, thereby depleting the
boundary layers of chromium. Air and moisture then react with the sulfide scale on
the surface of the steel when the unit is opened for maintenance, producing a corrosive
aqueous medium, which, under stress, can cause rapid cracking of the steel.
The first incidence of this phenomen was reported to have occurred in 1943 in a
fluid catalytic cracker? However it was not until 1956-1958 that Dravnieks and
Samans implicated polythionic acid in the process. 2 They detected these polaro-
graphically in a furnace condensate. In the laboratory this same condensate promoted
the cracking of U-bend specimens of sensitized stainless steel. Cyclic steaming of
iron sulfide also yielded these substarces, and this liquid also promoted the cracking of
U-bend specimens. They then prepared Wackenroder's liquid, a long known source
of mixed polythionic acids made from SOs, H2S and water, and found that it too was
very potent in the cracking of stressed sensitized stainless steel.
Since then some doubts have been expressed as to the culpability of these materials,
such as by Piehl. 3 The problem is that all the chemical solutions used in the above
experiments are mixtures of various substances and it is possible that one of the

Manuscript received 10 February 1982.

Presented at the Meeting on "Electrochemical Techniques in Corrosion Testing and Research"
held at the Corrosion & Protection Centre in the University of Manchester Institute of Science &
Technology, 4-6 January 1982.
353
354 HUGH H. HOROWITZ

TABLE 1. APPARENT VALENCE OF SULFUR-OXYGEN COMPOUNDS

6 SO~ SULFATE

5 $20~ DITHIONATE

4 SO~ SULFITE
S306 TRITHIONATE
3
$406 TETRATHIONATE
2 $203, $50~ THIOSULFATE,
PENTATHIONATE
$606 HEXATHIONATE
1

0 S SULFUR

-1

-2 S= SULFIDE

impurities, or a reaction product of one of the polythionics and something in the

environment is the true corrodent.
The problem is now being controlled, but not eliminated completely, by the use of
stabilized stainless steels designed to retard chromium carbide formation, and by the
use of special shut-down procedures designed to control the access of air and moisture
to the sulfide scale.
Polythionic acids have the general formula H2SxO e. Both of the protons in the
compound are very strongly acidic so that in water the compounds exist as the ions.
These consist of two sulfonate groups sandwiching a polysulfide chain4:

-O f O-
O-S-(Sx_2)-S-O
0 / "O

There must be at least one sulfur atom linked only to other sulfur atoms for a com-
pound to fit in this class. Thus, dithionate, $20 n, does not belong to this group,
whereas trithionate, tetrathionate, pentathionate, hexathionate, etc. are known.
Table 1 shows the panoply of common sulfur-oxygen ions listed according to the
average sulfur valence. It will be noted that the polythionates fit below the sulfite and
above elemental sulfur.
Note in particular that thiosulfate is a very closely related ion. It may be written
as -S-SO3-, a sulfonate attached to a single sulfur atom. Many of the reactions of the
polythionates involve or form thiosulfate. For example, sulfite reacts with tetra-
thionate to form trithionate and thiosulfate:

$4062- + SOs ~- ~ $206 ~- + SiO32-

 Chemical studies of polythionic acid stress-corrosion cracking 355

ate is reducible to thiosulfate:

Also, t e t r a t h i o n
$4062- ÷ 2e ~ 2S2082-

The s t a n d a r d potential for this reaction is near zero versus the saturated calomel
electrode, b u t it occurs o n mercury, polarographically, at a b o u t - - 300 mV/SCE. The
reverse reaction, oxidation of thiosulfate, occurs readily, for example using iodine as
the oxidant. I n fact, this reaction forms the basis of iodimetric titration, familiar to
every analytical chemist.
It was t h r o u g h the relationship of thiosulfate that this general field of oxy-sulfur
i n d u c e d stress-corrosion cracking has enjoyed a recent resurgence of scientific activity.
It was f o u n d that the thiosulfate solutions used in pressurized water nuclear reactors
as a n emergency quenching agent for radioactive iodine, had the power to induce the
stress corrosion cracking of sensitized stainless steels. This has p r o m p t e d research
programs at Ohio State University, sponsored by the Electric Power Research Insti-
tute, 5 a n d at B r o o k h a v e n N a t i o n a l Laboratories, sponsored by the U.S. D e p a r t m e n t
of Energy, 6 some of which will be reported on at this symposium.
It is the aim of this study to shed some light on two questions: D o these substances
p r o m o t e stress corrosion cracking by hydrogen embrittlement, as hydrogen sulfide
does, or do they p r o m o t e anodic dissolution ? Secondly, are they readily formed from
iron sulfide scale by the reaction written by BrophyT:

4 FeS q- 5 . 5 0 ~ -k H 2 0 --~ 2Fc2Oa -~- H2S406 ?

EXPERIMENTAL METHOD
Hydrogen permeation experiments were carried out in a Devanathan-Stachursky apparat,s. 8
A sheet of 4130 carbon steel which had been austenitized, water quenched and tempered was use~t as
the test metal. It was sandwiched between two glass flanges attached to two electrochemical cells.
Each side was fitted with a reference electrode and counter electrode and a potentiostat to control the
current or voltage. The cell on the active side contained 5 ~ sodium chloride and 0.5 ~o acetic acid to
which additional test substances could be added. The cell on the detection side contained 0.1 N NaOH.
This side of the steel sheet was also coated with palladium to promote hydrogen atom activity, while
protecting against substrate corrosion.
The general technique was to fix a cathodic current or potential on the active side, then set the
potential at the detection side so as to anodize all the hydrogen atoms permeating the steel, recording
both currents as a function of the potential of the active side. The results with HaS-saturated electro-
lyte are recorded?
The anodic activity testing was carried out in a one molar phosphate buffer at pH 7 (0.5 M each
NaH2PO4 and Na2HPO4) to which the test substances were added. The electrode consisted of the
same 4130 steel with the same heat treatment as in the hydrogen permeation tests. However, here it
was mounted on a rotating disk assembly where it was operated potentiostaticallyat varying scan rates
or at constant potentials vs a calomel reference electrode.
Reactions of ferrous sulfide with oxygen were carried out using 5 mmol of the substance, freshly
precipitated from hydrated ferrous sulfate with a slight excess of sodium sulfide. The precipitate was
filtered under nitrogen and transferred rapidly to a gas tight round bottomed flask equipped with pH
electrode, magnetic stirrer, gas burette (with water as the leveling fluid) and exit stopcock and bubbler.
The FeS was covered with 30 cm 3of water and the flask was flushed with 5 vol of oxygen before leveling.
When the stirrer was turned on oxygen consumption began. Oxygen absorbed (in cm a) was recorded
vs time.
356 HUGH H. HOROWITZ

TABLE2. EFFECT OF H~S ON H ENTRY INTO STEEL (4130 STEEL, 0.22 m m THICK, 5~o NaCI, 0.5~
ACETIC ACID)

Corrosion Cathodic Permeation

potential current current (%)
(mV/SCE) (t~a cm-2)* (Fta cm-~)t Permeation
Base case (oxided) - 565 2.0 1.7 85
Base case(de-oxided)~ - 570 85 1.2 1.2
+H2S (oxided) - 650 190 145 76
+H2S (de-oxided)~ - 650 180 120 67

*Extrapolated to corrosion potential.

tMeasured at corrosion potential.
~+Byanodizing at - 400 mV/SCE.

RESULTS AND DISCUSSION

Despite the fact that polythionic acid stress-corrosion cracking occurs with stain-
less steel, the present studies were carried out with a carbon steel. The rationale was
that during stress cracking the liquid in the growing crevice contacts steel which has
been depleted of chromium and has thereby lost its "stainless" characteristic. We had
also considerable history on this batch of 4130 steel and had found it excellent for
detecting the wide range of hydrogen permeation and anodic activity effects resulting
from exposure to hydrogen sulfide?

Hydrogenpermeation experiments
The electrolyte chosen for these experiments consisted of " N A C E " solution not
treated with H2S. This electrolyte has the advantage over strong acid electrolytes in
that it permits the retention of the original surface oxide layer on the steel, until
removed by anodization or by reaction with added corrodents.
In previous work on the effects of H~S, it was found that the original steel was
coated with a more or less thick layer of oxide dependent on the conditions of quench-
ing and tempering. With the oxide covered surface the corrosion current was low, but
the fraction of hydrogen entering into the steel and passing through it was high, as
much as 85 ~ of the total cathodic current (Table 2). When the oxide coating was
removed by anodization the corrosion current increased, but the percent of hydrogen
permeation decreased, as the H atom recombination reaction to form gaseous H2
was also catalyzed by the fresh surface. When the electrolyte was saturated with H2S
the corrosion current rose even further and the percent permeation rose to about
70 ~ . This was true regardless of whether the original oxide had been anodically
removed or not. The H~S effectively removed the protective oxide coating. In addition,
the H2S produced a drop in the open circuit or corrosion potential, meaning that the
anodic reaction was accelerated more by H~S than the cathodic.
When either sodium tetrathionate or sodium thiosulfate was added to the base
electrolyte at the same concentration as the H~S (0.1 M), the results were not the same
(Tables 3 and 4). The corrosion current measured in the cathodic direction was
increased significantly, but the percent hydrogen permeation was decreased to the
 Chemical studies of polythionic acid stress-corrosion cracking 357

TABLE 3. EFFECT OF TETRATHIONATE ON H ENTRY INTO STEEL (4130 STEEL, 5 % NaCI, 0.5 % ACETIC
ACID)

Corrosion Cathodic Permeation

potential current current (%)
(mV/SCE) (~ta/cm2) (Fa/cm2) permeation

Base electrolyte - 583 6.6 2.45 37 %

+ 0.I M $40~- - 572 460 17.5 3.8%
Base electrolyte - 579 6.9 2.1 30 %
4 0.1 M $40~- - 572 500 11.2 2.2%

TABLE 4. EFFECT OF THIOSULFATE ON H ENTRY INTO STEEL 4130 STEEL, 5 ~oo NaCI, 0.5 % ACETIC ACID)
Corrosion Cathodic Permeation
potential current current (%)
(mV/SCE) (~ta cm-2) (Fa cm-~) permeation

Base electrolyte - 630 12.9 3.15 24%

+ 0.1 M $20]- - 598 118 2.8 2.4%
Base electrolyte - 593 5.3 2.8 53 %
+ 0.1 M $20~- - 608 530 10.8 2.0%

2 - 4 % level. The open circuit potential was not significantly altered, in contrast to the
reduction caused by H2S.
A typical plot of the experimental results obtained with thiosulfate is given in
Fig. 1. The large cathodic current increase caused by the thiosulfate is evident, as is
the decrease in per cent permeation, indicated by the increasing spread between the
curves.

4130 STEEL, 5% NaCI, 0.5% HOAc = 0.1M $20~

-600

~J
uJ -650
E
~" -700

©
a. -750

• \
CATHODIC CURRENT ~ /~"
-800 -- • PERMEATION CURRENT BASE
ELECTROLYTE

10 100 1000
CURRENT DENSITY, pa/cm 2

FIG. 1. Effect of thiosulfate on H permeation.

358 HUGHH. HOROWITZ

4130 STEEL
ROTATING DISK
20 1M Nal.5H 1.5P04
pH 7, 24°C
3000 RPM
SCAN RATE 50 mV/SEC

15
~E • + .I M Na2S406

--- BUFFER ALONE

l~1,11111
-.8 -.6 -.4 -.2 0
VOLTAGE VS, SCE

FIG. 2. Effect of tetrathionate on passivation of carbon steel.

The H atom permeation results in the presence of the three substances are sum-
marized here:

H~S 67, 76
Na~S~Os 2.0, 2.4
Na2S4OE 2.2, 3.8~o

It is clear that the present sulfur compounds are not acting like H~.S in promoting
intensive hydrogen penetration into the steel, but they are promoting anodic dissolu-
tion. We therefore turned our attention to the anodic activity of steel in the presence
of these materials.

Promotion of anodic activity by S~Os~-, $4062-

To look at the effects of these oxy-sulfur anions on the anodic activity of a carbon
steel, an electrolyte was chosen in which the active-passive transition could be easily
observed, namely a phosphate buffer at pH 7. A typical scan in the base electrolyte
is shown as the dashed line in Fig. 2. It shows rising current, presumably due to ferrous
ion formation as the potential moves anodically, followed by a drop-off in current
as the surface passivates. The peak height here was proportional to the rotation speed
indicating diffusional effects, similar to the results of Armstrong & Coates with
carbonate buffer. 1° There was little effect of scan rate. Upon reversing the scan direction
anodic current was again observed, indicating the reversible reduction of the passive
film. A steady state current could be maintained at each potential in the range of the
peak in the scan.
The results in the presence of 0.1 M thiosulfate or tetrathionate were in sharp
contrast to all this. A sharp anodic current spike was superimposed on the normal
 Chemical studies of polythionic acid stress-corrosion cracking 359

4130 STEEL
ROTATING DISK
1M Nal,sH1.sPO4.
20 pH 7
24°C
SCAN RATE 20 mV/SEC

15

:'- 10

5 -

J I J i I I [
-,7 -.5 -,3
V O L T S VS. SCE

FIG. 3. Effect of thiosulphate on passivation of carbon steel.

base electrolyte curve (Figs 2 and 3). The height of this current spike was not dependent
on the rotation speed. It was, however, proportional to the square root of the scan
speed. Thus, by increasing the scan speed and reducing the rotation rate it was possible
to make the current spike completely dominate the picture. The spike did not appear
in the reverse scan and there was no steady state current above the base case in the
potential region of the current spike. It could only be made to reappear by waiting at
open circuit or cathodizing until some surface reaction or adsorption occurred.
Since there are no reactions of thiosulfate or tetrathionate in the potential range
observed, we can only conclude that these substances are accelerating the anodic
oxidation of the iron either by removing an inhibiting substance from the surface or by
adsorbing on the surface and catalyzing the removal of ferrous ions via complex
formation, etc., until the adsorbed or reacted layer is exhausted.
The number of coulombs under the anodic spike was almost but not quiet a
constant--an increase of a factor of 10 in the scan rate produced a decrease in the
charge by about a factor of two. In the range of scan rates examined, the charge under
the spike ranged from 12 to 32 mC cm -1, corresponding to about 20-60 monolayers of
iron. It is possible that surface roughness may account for this number being greater
than one. However a freshly polished electrode surface still gave a 36 monolayer peak.
We may speculate that removal of a single ferrous ion from the surface by complex
formation with the sulfur anion may trigger the removal of many more iron atoms
before surface repassivation occurs.

Evidencefor complexformation with thiosulfate

We have noted that thiosulfate and tetrathionate act similarly in both hydrogen
permeation and anodic stimulation experiments. The reason for this is very likely
that the open circuit potential is about 0.3 V cathodic to the half wave potential for
360 HUGHH. HOROW[TZ

pH 4 ACETATE BU F F E R, . 0 0 5 M $20:~

-11111 r ~ irl I , , , i ,,1~ I i i i , ,,,~ I

POSSIBLE Fe++(S20~)n PARAMETERS /

:~ -120

O -14Q

•'~ -160 i

.J) I I III1 J , , ,,,,,I , ~ , ,tJJ,I

.01 0,1 1.0
CONCENTRATION OF Fe ++, M O L E S / L I T E R

Fie. 4. Shiftof polarographic E½ of S~O~due to ferrous ion addition.

the reduction of tetrathionate to thiosulfate on mercury.

It is very likely therefore that tetrathionate is being reduced to thiosulfate at the
iron surface and that the true active corrodent is thiosulfate in both cases. While no
distinct reduction wave could be seen on the steel rotating disk electrode in the presence
of 0.005 M tetrathoinate, the cathodic current was increased. Running cathodic at
25 mA cm -2 overnight produced a 50 ~ yield of thiosulfate, determined polaro-
graphically, with total loss of the original tetrathionate. Thus tetrathionate can be
reduced to thiosulfate on a steel surface. While this has not yet been demonstrated at
the open circuit potential, it is very likely to occur.
Thiosulfate is a well known complexing agent, being used for example, as "hypo"
to remove unreacted silver halides from photographic film. An attempt was therefore
made to look for a ferrous ion-thiosulfate complex using the polarographic technique.
The addition of ferrous sulfate did indeed produce a shift in the polarographic half
wave potential for 0.005 M thiosulfate in an acetate buffer (Fig. 4). The curve could not
fitted exactly by assuming any single set of values for the value of n in Fe
(S,O3)-t2n-9) and the value of the association constant, K, but values of n of 1 and 2,
coupled with appropriate K values gave the best fit.
In view of problems with non-constant ionic strength, unknown activity co-
efficients at the high ferrous ion concentrations required, possible sulfate effects etc.
it would not be possible to quantify the effect at present, but the anodic half wave
potential shift of the anodic $203 polarographic wave by ferrous ion certainly suggests
complex formation.

Oxidation of ferrous sulfide

The oxidation of ferrous sulfide to form Fe203 and tetrathionic acid postulated in
Brophy's equation above would require 1.375 tool of O9 per mode of FeS. The actual
uptake levelled off clearly at 0.75 tool O~ per FeS (Fig. 5). This corresponds to the
reaction:
FeS + 3/40~ --~ 1/2 Fe208 + S.
 Chemical studies of polythionic acid stress-corrosion cracking 36l

PURE O2, 5 M MOLES FeS IN 30cc H 2 0

t .75
90 I 1
z :. ":_

80_

70

5O
r~ 6O
u.

50 ¢
o
~J

4o

25
30

FeS + .75 02 • ~1F e 2 0 3 ÷ S

20

10

L
1 2 3
HOURS

FIo. 5. Oxidation of FeS at 23.5°C.

The final product was a yellow to rust coloured powder from which FezO 3 could
be removed by dissolution in HCI and the residual sulfur could be dissolved in
isopropanol. These were obtained in 89 and 81 ~ yields respectively. There were
polarographically active materials in the supernatant liquid, which were tentatively
identified from their half wave potentials as ferric ion, thiosulfate, tetrathionate, and
elemental sulfur. The ferric ion observed proved to be only a fraction of the total iron
content of the solution, for on exposure to air or treatment with hydrogen peroxide
it increased in concentration. Rough estimates of the yields of these various substances
are given in Table 5. It will be seen that the polarographically active materials in

TABLE 5. PRODUCTS OF FeS-O2R E A C T I O N *

Substance Concentration (mM) ~ Yield

Fe (in Fe203) In solid 89.1

Elemental S In solid 81.1
Soluble Fete: 16.7 10.1
S~O~2:~ 0.6 0.7
S~0~2~. 0.9 2.1
S~: 1.4 0.8

*5 mmol FeS suspended in 30 cm3 water.

f38 ~ Ferric ion, 62 % Ferrous
:~Identified and roughly estimated by differential pulse
polarography.
362 HUGH H. HOROWITZ

solution account for only a small percentage of the sulfur in the original FeS. The
dissolved iron species exceed in concentration the anions detected polarographically.
The remainder of the iron is probably present at the sulfate which is polarographically
inactive, but which is known to be the final oxidation product of any of these sulfur-
oxygen anions.
Whether or not the soluble compounds come from the original FeS or from the
product sulfur remains to be determined. The effect of the crystalline form and degree
of non-stoichiometry of the FeS on the yield of active corrodents is also to be inves-
tigated.

SUMMARY AND CONCLUSIONS

The findings of this work may be summarized as follows:
1. Tetrathionate and thiosulfate act similarly in their effects on hydrogen permeation
and anodic dissolution, probably because the former is reduced to the latter at
the corrosion potential.
2. These substances do not increase the percent permeation of hydrogen into steel,
and therefore probably do not function by promoting hydrogen embrittlement in
the manner that H~S does.
3. These substances do increase the corrosion rate of carbon steel by increasing the
anodic and cathodic half cell reactions about equally. They adsorb on or react
with the metal surface so as to produce a sharp increase in the rate of anodic
dissolution. There is slight evidence for the formation of a ferrous ion-thiosulfate
complex, which may play a role in this process.
4. Ferrous sulfide reacts with water and oxygen to generate principally Fe~O3 and
elemental sulfur, but low yields of water-soluble sulfur compounds are also
produced, which may be sufficient to account for the stress-corrosion cracking.
Many points remain to be clarified in this picture, but at the present time we lean
toward the hypothesis that the polythionates are acid stable progenitors of thiosulfate
ion, which may be the true corrodent, by virtue of its complexation or adsorption
abilily.
Acknowledgements--The author wishes to acknowledge the technical assistance of J. I. Haberman
and J. Rota, who performed all of the experimental work.

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