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crude oil in preparation for refining, thiosulfate and oxidation states in the same compound. Some of these
other polysulfur species form and have been identified oxyanions are thiosulfate (S2O32−), trithionate (S3O62−),
as causing IGSCC of sensitized Type 304 stainless tetrathionate (S4O62−), pentathionate (S5O62−), sulfate
steel (SS, UNS S30400), which is now recognized as a (SO42−), sulfite (SO32−), dithionite (S2O42−), dithionate
form of hydrogen-induced cracking (HIC).10 The main (S2O62−), and persulfate (S2O82−), to name but a few
forms of corrosion that have been observed in the of the known members. A comprehensive listing of
presence of the thiosulfate ion in solution are principally the various, currently-known sulfur species, together
pitting,12-14,26 stress corrosion cracking (SCC),27-29 with the thermodynamic data for their formation, is
corrosion fatigue,30 and crevice corrosion.31-32 These are given in Table 1.34 This is considered to be the most
all dangerous forms of corrosion, which frequently lead comprehensive listing currently available and it pro-
to the failure of infrastructure materials under a wide vides the base data for the generation of Pourbaix
range of service conditions. diagrams, volt-equivalent diagrams (VEDs), and cor-
While localized corrosion and/or environmentally- rosion domain diagrams (CDDs) that are of immense
assisted cracking of structural materials in aqueous utility in interpreting the electrochemistry of the sulfur-
solutions containing the thiosulfate anion have been water system. This system is the most complex system
subject of extensive research over the last five decades, in chemistry after the C-O-H system, with the sulfur
no critical review of pitting and SCC of structural displaying a greater range of oxidation state (−2 to 8,
materials in thiosulfate solution is available, except for see Table 1) than does any other element in the peri-
a brief discussion on SCC of sensitized stainless steel odic table.
by Cragnolino and Macdonald,24 published in 1982.
They performed a thorough review of the IGSCC of
Pourbaix Diagrams
austenitic sensitized stainless steel at temperatures
Out of all of the known sulfur species listed in
below 100°C, with specific emphasis on sulfur species.
Table 1, S2O32− is an interesting, metastable anion and
Although the role of thiosulfate in causing IGSCC in
deserves particular attention. S2O32− can be oxidized/
sensitized stainless steel was discussed, the review
reduced, and can disproportionate or decompose under
does not consider the broad corrosion problems en-
varying electrochemical and/or chemical conditions.
countered in other structural materials, as a result of
A typical E-pH (Pourbaix) diagram for the S-H2O system
the presence of thiosulfate anion in aqueous environ-
is shown in Figure 1.42 This diagram does not include
ments. Given the use of thiosulfate salts in various
the stability regions for sulfate or bisulfate (which are
industrial applications, the authors find it imperative to
thermodynamically very stable), in order to depict
review most of the corrosion research performed on
stability regions of the metastable species, such as
steels in thiosulfate environments. Hence, in this re-
thiosulfate, tetrathionate, sulfite, etc. Thiosulfate is
view, an objective is to summarize and analyze previous
thermodynamically stable only in a narrow, elongated
corrosion studies on steels in thiosulfate solutions.
field in neutral and alkaline solutions, as can be seen
While the emphasis in this review is on thiosulfate, it is
from Figure 1. It tends to undergo chemical decompo-
important to note that S2O32− is only one of many
sition in aqueous solutions. It may oxidize to sulfite,
polysulfur oxyanions that exist in the S-H2O system,
polythionates, and ultimately to sulfate, or reduce to
depending upon the pH and redox potential of the
elemental sulfur and sulfide (or to polysulfides),
environment. In order to illustrate the complexity of
depending upon the redox potential and the pH of the
the S-H2O system, this study will discuss other poly-
system. Some of the relevant oxidation, reduction,
sulfur species, including the polysulfides (e.g., Sx2−,
and disproportionation reactions involving thiosulfate
x = 2 − 8) and polythiosulfates, that form in this system,
ion are given in Table 2.
as the need arises. Finally, although the principal
Equation (1) forms a basis for the determination
focus of this review is on the stainless steels and more
of thiosulfate in the solution by iodimetric titration,
specifically on the austenitic stainless steels, occa-
which is based on the quantitative oxidation of thio-
sionally other metals and alloys will be included, in
sulfate by iodine.2 Equations (8) and (9) show that
order to illustrate specific modes of interaction of
thiosulfate has a tendency to disproportionate at a
sulfur-containing species with materials.
low pH to sulfur and sulfur dioxide or in alkaline
solutions to sulfide and sulfate (Equation [10]).2,10
THERMODYNAMICS OF THE SULFUR-WATER Equation (10) also provides a basis for stabilizing
SYSTEM thiosulfate solution by the addition of sulfate.
Thiosulfate was found to be an unintended by-
Sulfur Species product of sodium dithionite, a newsprint brightening
Sulfur is an active, multivalent element and forms agent, and hence, thiosulfate was present in small
many different species, including many oxyanions, amounts in the papermaking process. Thiosulfate acts
that exist over a range of oxidation states from −2 to 8,33 as a neutralizer of the chlorine compounds (e.g., Cl2,
with many oxidations being fractional because of the HClO) that are used as bleaching agents (Equation [2],
presence of several sulfur atoms having different Table 2).1-2 Thiosulfate is helpful in converting toxic
TABLE 1
Thermodynamic Data for Polysulfides and Polythiooxyanions34,(A)
Species ΔGfo kJ/mol ΔHfo kJ/mol S0 J/Kmol Cp0 J/Kmol Reference
cyanides into nontoxic products according to Equa- Equations (6) and (8) also form a significant basis
tion (7).45 Over the last two decades, thiosulfate has for replacing difficult-to-handle sour gas environments
been extensively researched for its use as a leachant in (H2S) by more easily managed thiosulfate solutions in
gold recovery.4,6,43-44 Thus, Equation (3) is of great laboratory experiments. Based on literature reports,
importance in the ammoniacal thiosulfate leaching of thiosulfate can often be used as a substitute for H2S
gold. The presence of cupric ions is known to accelerate because it is reduced to H2S when in contact with
the oxidation of thiosulfate in aqueous gold leaching carbon steel.10 The corrosion potential of carbon steel in
solutions (Equation [3]).46 thiosulfate solutions (at pH ∼2.7 to 3) is reported to be
TABLE 2
Chemical Reactions Involving Thiosulfate
Reaction ΔG0 at 298 K (kJ/mol) Reference Equation
Oxidation
2 S2O32− + I3− = S4O62− + 3 I− −88 2 (1)
S2O32− + 4 Cl2 + 5 H2O = 2 SO42− + 8 Cl− + 10 H+ −829.1 2 (2)
5 S2O32− + Au + Cu(NH3)42+ = Au(S2O3)23− + 4NH3 + Cu(S2O3)35− −14.1 4, 6, 43, 44 (3)
S2O32− + 2 O2 + 2OH− = 2 SO42− + H2O −887.2 45 (4)
S2O32− + ½ O2 + H2O = 2 S4O62− + 2 OH− −61.9 45 (5)
Reduction
S2O32− + 6H+ + 4e− = 2S + 3 H2O −192.8 10, 33 (6)
S2O32− + CN− = SO32− + CNS− −44 45 (7)
Disproportionation
S2O32− + H+ = S0 + HSO3− −3.1 10, 33 (8)
S2O32− + 2 H+ = SO2 + S0 + H2O −18.7 2 (9)
S2O32− + 2 OH− = SO42− + S2− + H2O −53.8 2 (10)
TABLE 3
Reduction Reaction for Sulfur Species Used in Defining the
Volt Equivalent34
Species Reduction Reaction
FIGURE 4. Volt-equivalent diagram for the S-H2O system at 150°C, FIGURE 5. Volt-equivalent diagram for the S-H2O system at 275°C,
pH = 0.34 pH = 0.34
This observation makes it clear that knowledge of the produce the former. A good example is found in the
pH of a system is vital for defining and studying its redox reduction of sulfuric acid by hydrogen sulfide. Thus,
chemistry. data plotted in Figure 5 predicts that, at pH = 0 and at
Temperature is another important parameter in 275°C, the following reaction is thermodynamically
defining a VED. Figure 4 shows a VED for the S/H2O favorable:
system at pH = 0 and at 150°C. Comparison of
+
Figures 4 and 2 suggests that, although the shapes 3H2 S þ SO2−
4 þ 2H ⇔ 4S þ 4H2 O (18)
of the diagrams are similar, the relative positions of
some species are significantly different. This arises because S lies below the line joining H2S and SO42−
because increasing or decreasing the temperature (labeled with green color). Again, use of the thermody-
changes the reduction potential for the relevant spe- namic data contained in Table 1 will confirm that this
cies and hence modifies the redox chemistry of the reaction is spontaneous; that is, the change in Gibbs
system, as expected. energy is negative.
VEDs are also useful in studying a chemical system In addition, the interpretation of the diagrams fol-
in the following ways. First, if a species lies above a lows the following rules:
line joining any two other compounds, this species • Any two species connected by a straight line will
will tend to disproportionate into the other two com- tend to react to produce all of the species that lie below
pounds. Thus, in Figure 5, for example, the decompo- that line. Thus, the reaction of S2− and H2S2O4 is pre-
sition of S2O32− in acidic solution is illustrated by dicted to generate essentially all other species plotted on
this principle (labeled with red color). It is clear that the diagram.
S2O32− lies above the line joining S and S4O62−. This • If a species lies above the straight line joining two
suggests that, although the decomposition of S2O32− is other species, it will tend to disproportionate to produce
a complex reaction forming many products, one reac- the latter. Thus, S22− lies above the line joining HS− and
tion that may occur is: S32−, so the disproportionation reaction 2S22− + H+ →
HS− + S32− is predicted to occur.
+
3 þ 6H → 2S þ 2S4 O6 þ 3H2 O
5S2 O2− • If several species lie on or close to a straight line
2−
(17)
joining two terminal species, the solution will contain all
This reaction is spontaneous because the resulting species in equilibrium at finite concentrations.
change in the Gibbs energy is negative, which may be The reactivity of any given species toward a metal,
confirmed by using the data given in Table 1. This in which a metal sulfide is formed, is measured by the
shows that it is thermodynamically possible for thio- value of the VE. The more reactive species are charac-
sulfate, i.e., S2O32−, to undergo a redox self-dispro- terized by high (more positive) VE values. Indeed the
portionation reaction into a reduction product, S, and most reactive species tend to be located in the upper left
an oxidation product, S4O62−. It is reactions of this quadrant, implying high reactivity and high electron
type that have led to the partially oxidized or reduced density being simultaneously present, followed by
sulfur species being termed “highly labile.” species in the upper right quadrant. Species in the lower
Second, if a species lies below a line joining any quadrants tend to be the least reactive toward a
two other compounds, the latter will tend to react to metal.
FIGURE 6. Pourbaix diagram for: (a) Fe-S-H2O, (b) Cu-S-H2O, and (c) Ni-S-H2O at 25°C (S = 1 mol/kg).
†
Trade name. which, upon rearrangement yields:
FIGURE 7. Corrosion domain diagram displaying the conditions FIGURE 8. Corrosion domain diagram for copper in water + HS− as a
under which corrosion is and is not possible. function of temperature.
FIGURE 9. Corrosion domain diagrams for copper in the presence of polysulfur species, trisulfide (S32−), tribithiosulfite
(HS3O3−), thiosulfuric acid (H2S2O3), and bithiosulfate (HS2O3−).
build up or reactants are depleted at the interface. This near-field environment is compacted, rehydrated
will continue until P = Pe and if the system is closed, the bentonite clay, which is sufficiently impervious that the
system will become stationary at equilibrium. For an canister is predicted to contain the waste for many
open system, in which products may migrate away hundreds of thousands of years.
from, and reactants may migrate toward, the interface, Similar diagrams can be derived for iron and nickel,
the system will exist in steady state and the metal will but to our knowledge this has not yet been done. The
continue to corrode at a rate that is governed by the relevance is readily discerned when it is noted that,
rates of mass transport of products from, and reactants in the stainless steels and nickel-based alloys (e.g., Alloy
to, the metal surface. Thus, the rate of corrosion 600), the precipitation of chromium carbides (e.g.,
becomes controlled by mass transport processes in the Cr23C6) on the grain boundaries during sensitization
near-field environment. In the case of copper canisters denudes the boundaries of chromium, thereby pre-
in the Swedish HLNW disposal technology, the venting the formation of a sulfur-resistant, defective
chromic oxide (Cr2+xO3−y) barrier layer of the passive material of construction of the clarifiers, storage
film on the boundaries. Thus the boundaries, which tanks, digesters, and recausticizing equipment in pa-
comprise mostly Fe and Ni, become susceptible to ac- per print machines. Wensley, et al.,21 report an in-
tivation by sulfide and thiosulfate as described above crease in the corrosion potential of mild steel with
for copper, resulting in rapid intergranular attack increasing amount of polysulfides in white liquor. The
and IGSCC. presence of sulfide and thiosulfate in the solution were
found to impair the ability of steel to passivate and
CORROSION OF METALS AND ALLOYS IN hence, for this reason were thought to be corrosion
THIOSULFATE SOLUTIONS activators. However, as noted, sulfide and polysulfur
oxyanions, such as S2O32−, S4O62−, etc., can also activate
As discussed above, several of these sulfur com- a metal by giving rise to a partial anodic process (for-
pounds are metastable, hence most often a mixture of
mation of an unprotective metal sulfide) at a potential
sulfur compound is found in the aqueous solution,
that is significantly more negative than that for the
including many, if not most, of those listed in Table 1.
formation of a protective oxide. Those sulfur oxyanions
Marcus and Protopopoff50-53 attempted to derive the
that do not have donatable sulfur (e.g., sulfite and sul-
conditions of potential and pH for reduction of thio-
fate) are reported to have no effect on the corrosion
sulfate to form adsorbed sulfur on the surfaces of Fe, Ni,
rate of mild steel.21
and Cr at 25°C and 300°C in water. They successfully
Newman and coworkers studied thiosulfate-
constructed E-pH diagrams for Fe, Ni, and Cr with
induced corrosion for more than a decade, and inves-
adsorbed sulfur and oxygen in water containing
tigated the effect of thiosulfate on the pitting of Types
HS2O3−, S2O32−, H2S, and HS−. The principal motivation
304 and 316 (UNS S31600) SS using potentiodynamic
behind their work was to elucidate the experimental
and scratching techniques.12-14 Sharp pit initiation was
observation that the presence of thiosulfate ions in
observed in 0.25 M NaCl + 0.01 M Na2S2O3 solution,
aqueous solution were detrimental to the corrosion
which was characterized by sharp increase in current
resistance of alloys such as stainless steels and various
(Figure 10), as observed during potentiodynamic
nickel-based alloys,12-15,21,27,31,54-63 which was
polarization testing.13 The pits formed in thiosulfate
attributed to the formation of adsorbed sulfur on the
solutions were never observed to repassivate above the
metal surface. It was reported that the adsorbed sulfur
pitting potential and contained a black deposit, which
layer could cause the observed detrimental effect
dissolved in dilute sulfuric acid with the evolution
by inhibiting the repassivation process. The subse-
of H2S.13 This observation suggested the presence of
quent sections discuss the role of thiosulfate in envi-
metal sulfides within the pit, although spectroscopic
ronmental degradation of steels.
analysis was not performed. If the thiosulfate concen-
tration was sufficiently high that the barrier layer
Pitting of Steels in Thiosulfate-Chloride Solutions of the passive film was the sulfide (e.g., FeS), then the
This section presents a survey of literature related black deposit is likely to be the remnants of the passive
to localized corrosion/pitting of stainless steels in film that had collapsed into the pit after initiation.
thiosulfate-containing solutions, particularly for the However, the sulfide may also form by the reaction of
austenitic Type 304 SS or variants thereof. Table 4 metal cations and sulfide ion resulting from the re-
contains a condensed summary of papers extracted duction of thiosulfate on the metal surface, with this
from the literature, including information on alloy, mechanism being applicable when the barrier oxide
environment, and testing procedure involved, and is is a metal oxide.
only meant to provide a general overview for comparison Further studies by Newman, et. al,14 and Garner15
purposes, rather than be an exhaustive review. also showed that thiosulfate ion can pit sensitized
Localized corrosion and pitting as a result of thio-
Type 304 SS, even in the absence of chloride ion,
sulfate were first observed in the pulp and paper in-
provided that the relative concentration of sulfate and
dustry.21 Thiosulfate is not intentionally added to the
thiosulfate were within a narrow range. Severe pitting
white liquor, but is normally found as an impurity and
was observed for the SO42−:S2O32− ratios of 6 to 23.
its generation is the result of air oxidation of the sulfide
Hence, the inhibition of pitting of steels as a result of the
or hydrosulfide, according to the reactions:69
presence of sulfate ions in the solution, as observed by
Leckie, et al.,70 may not necessarily be observed if
2HS− ðaÞ þ 2O2 ðaÞ = S2 O2−
3 ðaÞ þ H2 O (28) thiosulfate ion is present. It was further reported that
the thiosulfate pitting occurred not only in the narrow
2Na2 Sx þ 3O2 = 2Na2 S2 O3 þ 2ðx − 2ÞS0 (29) range of ionic concentration, but also over a limited
range of potential, as shown in Figure 11.14 If the
Therefore, thiosulfate is only present at a very low potential is too oxidizing, the absorbed sulfur species
concentration. However, even a very low concentration cannot be generated and the alloy behaves as though
of thiosulfate has the potential to cause severe cor- thiosulfate was absent. Consequently, when the
rosion of carbon steel,21 which was the conventional chloride ion concentration is low, no pitting will
TABLE 4
Summary of a Few Critical Studies Performed on the Pitting of Stainless and Carbon Steels in Thiosulfate Solutions
Critical Results
Material Environment Testing Details Observed Reference
Type 304 SS 0.25 M NaCl + (0.001 M − 0.1 M) Potentiodynamic and scratch a) Severe pitting for 0.25 M 13
Na2S2O3 electrode measurements NaCl + 0.01 M Na2S2O3
b) Inhibition of pitting for large
concentrations of thiosulfate
(0.1 M Na2S2O3)
Fe-17Cr alloy 0.02 M NaCl + 30 ppm S2O32− Potentiodynamic polarization Pitting was observed and pitting me- 55
and XPS chanism by reduction of thiosulfate into
sulfur on active surfaces of steel
was established and confirmed by
XPS results
Alloy 304 SS 7 × 10−4 M Cl− and 8 × 10−5 M Polarization and Severe pitting was observed 59
S2O32− scratch testing
Alloy UNS 300 mg/L Cl− + (0 to 1,800 mg/L) Cyclic polarization, Pitting and crevice corrosion, 58
S30403 SS SO42− + 50 mg/L S2O32− contact electric resistance pitting is inhibited for Cl−/SO42− ≤ 0.5
technique, scratch tests
Type 304 SS (1 to 1,000) mM NaCl + (1 to Galvanostatic and Pitting was observed in a specific thio- 66
1,000) mM Na2S2O3 potentiostatic sulfate/chloride concentration range. No
polarization pitting in only-thiosulfate solutions
AISI 304, 1 M NaCl + 0.01 M Na2S2O3 Crevice corrosion Crevice corrosion penetration rates 31
AISI 316L, testing underwent ten-fold increase in presence
UHB 904L of thiosulfate
304, 316, 317L, (0 to 1,000) ppm Cl− + Weight loss and a) Relative performance of the alloys, 15
Ferralium 254 (0 to 200) ppm S2O32− + potentiostatic tests AISI 304 (sensitized) < 304 < 316
100 ppm SO42− (sensitized) < 317 L < Ferralium 255
(Sensitized) < Ferralium 255
b) Pitting could occur even in the absence
of Cl− if sufficient sulfate is present
for AISI 304 L (SO42−/S2O32− = 6 to 23)
Fe-19Cr-10Ni 0.25 M Na2SO4 + 0.025 M Scratch testing Pitting occurred in limited range of 12
Na2S2O3 potentials and concentrations
16Mn Low-Alloy Bayer solution + 5 g/L S2O32− Polarization and cyclic The presence of thiosulfate decreased 67
steel voltammetry the corrosion rate of steels in alkaline
Bayer solutions containing sulfide ions
AISI 316 0.1 M NaCl + (0.01 to 0.03) M Potentiodynamic, a) Addition of thiosulfate ion to chloride 26, 68
Na2S2O3 potentiostatic polarization, solutions shifted critical pitting tempera-
and SEM ture to lower temperature and decreased
pitting potential
b) The presence of thiosulfate increased
the frequency of metastable pitting
occurrence and the probability of transi-
tion from metastability to stability
of iron oxide and a hydroxide.77-78 The inner (barrier potential.80 However, in presence of anions such as
layer) is an n-type semiconductor because of the prin- Cl−, thiosulfate aggravates the localized corrosion/
cipal point defects being oxygen vacancies pitting because of the postulated inhibition of repassi-
and (primarily) metal interstitials, both of which are vation process generally, as a result of its reduction/
electron donors, and can be described by the formula: decomposition into adsorbed sulfur.14,16 The stability
Cr2 + xO3 − y, as indicated previously. Thus, surface of the film formed on stainless steels in thiosulfate
analysis indicates significant presence of iron and nickel, solutions are known to be greatly disturbed by adsorbed
in the barrier layer of Fe-Cr-Ni alloys and even of mo- sulfur on steel surfaces.55
lybdenum-containing alloys, such as Type 316 SS. As It is well accepted that one of the decomposition
noted above, the Fe and Ni content is attributed to products of thiosulfate is elemental sulfur (Equation [6],
the presence of the interstitials, Fe3+i and Ni2+
i , respec- Table 2). The corrosion of carbon steel in the presence of
tively, as a result of the transmission of these elements wet elemental sulfur was studied extensively by Hyne,
through the barrier layer lattice, while the molybde- Macdonald, and Roberts.81-82
num is believed to be substituted upon the Cr cation Examination of the data displayed in Figures 15
sublattice as immobile Mo3+ Cr . Electrochemical imped- and 16 leads to the following generalizations concerning
ance spectroscopy79 indicates that in the case of Alloy 22 the reaction of carbon steel in wet elemental sulfur:
(UNS N06022, nominally [wt%] Ni 58, Cr 22, Mo 13.0, (1) it is a form of acid attack as evidenced from the
Fe 3.0, W 3.0), more than 99% of the passive current observed increase in pH (Figure 15); (2) it is charac-
is carried by metal interstitials (as opposed to oxygen or terized by an induction time that decreases with in-
cation vacancies) and the same is found for stainless creasing initial pH with the induction time being greater
steels. under anaerobic conditions than under aerobic condi-
As stated, the thiosulfate ion alone does not have tions (Figure 16); (3) the reaction is autocatalytic, with
any deleterious effect on the electrochemical localized the rate after induction being similar under aerobic
corrosion of stainless steels, because thiosulfate ion, conditions and anaerobic conditions (Figure 15); and
alone, does not seem to initiate the breakdown of the (4) during autocatalytic attack, the corrosion potential
protective character of the passive film.13,16,55 It was becomes more positive.81
further reported that polysulfur species, such as Further, the corrosion rate decreases with cycle
thiosulfate ion, activate anodic dissolution at the pit number upon cyclical exposure of the steel to wet sulfur
initiation sites, but does not assist in the initial and the atmosphere (Figure 17).82 The ennoblement of
breakdown of the passive film on the surface of stainless the corrosion potential during the autocatalytic phase
steels,16 although it may inhibit this event.14 Fig- indicates that the reaction is cathodically-controlled,
ure 1480 shows the anodic polarization curves mea- while the initial induction time is consistent with the
sured for stainless steel in solutions containing only depassivation of the surface and the formation of a
1 mM Na2S2O3 without chloride ion at pH = 3.5, 4.0, surface phase that catalyzes the cathodic reaction. This
and 5.0. In these solutions, the surfaces of the stainless phase is identified as mackinawite, Fe1+yS (y < 0.15),
steel were completely passivated at the corrosion an electronically-conductive iron (II) sulfide, the
FIGURE 19. Measured coupling current between the crack and the external surfaces upon SCC in sensitized Type 304 SS in
0.5 M thiosulfate solution illustrating periodicity in the current.28-29
Contrary results on the mechanism were re- migration in response to the coupling current will result
ported by Gomez-Duran, et al.28-29 By measuring the in deposition of atomic sulfur at the crack tip. Noting
coupling current between the crack tip and external that a high acidity also promotes some hydrogen evo-
surfaces, the crack was shown to grow via a series lution on the brittle fracture surface, and that atomic
of microfracture events, which induced periodic noise in sulfur has been postulated to inhibit the recombination
the coupling current (Figure 19). of hydrogen atoms on the surface,110 thereby promoting
Assuming that the microfracture events are semi- the entry of hydrogen into the steel, the involvement
circular of radius r, B/2r such events must occur on of hydrogen in the fracture process is mechanistically
average along the crack front for the crack to advance by reasonable. Thus, it is envisioned that the hydrogen,
the distance r, where B is the thickness of the C(T) once it enters the steel at the crack tip or at juxtapo-
specimen. If the frequency of the microfracture events is sition surfaces on the microfracture flanks, is trans-
f, then the crack growth rate (da/dt) is: ported by the stress field ahead of the crack tip and
recombines within creep-induced voids on the chro-
da fr mium-depleted grain boundaries, or simply embrittles
= = 2f r2 =B (36)
dt B=2r the strain-induced martensite, resulting in a fracture
dimension that is determined by the distance ahead of
Rearrangement of Equation (36) yields the microfrac- the crack tip (which commensurate with the transport
ture dimension as: properties of hydrogen). Thus, as a “back-of-the-
pffiffiffiffiffiffiffiffiffi
sffiffiffiffiffiffiffiffiffiffiffiffi
envelope” estimation may be written r≈ D=f , where D
B da
r= dt
(37) is the diffusivity of hydrogen and f is the frequency of
2f the microfracture events (0.01 s−1 to 0.1 s−1). While the
exact composition of the chromium-depleted zone is
For the 4 h sensitization case, the crack growth rate, unknown, it is expected that the grain boundary
da/dt = 1.7 × 10−6 cm/s, B = 1.416 cm, and f = chromium concentration is of the order of 10 wt%.
0.01 s−1 to 0.1 s−1, which yield a microfracture di- Elboujdaini111 gives hydrogen diffusivity data for
mension of 35 μm to 108 μm. The lower end of this range Fe-Cr-Ni alloys as a function of composition and from
is of the order of the grain size of the steel, while the these data, D = 10−6 cm2/s was selected. Thus, r is
upper end is supra-grain size of approximately 3 times estimated to range between 32 μm and 100 μm, in
the average grain size. In the opinion of the authors reasonable agreement with the value estimated from the
(Duran and Macdonald28-29), this dimension is too large noise in the coupling current combined with the known
to be accounted for by brittle mechanical fracture crack growth rate. This lends credence to the postulate
resulting from the existence of strain-induced mar- that hydrogen plays an important role in causing
tensite on the chromium-depleted grain boundaries SCC in sensitized Type 304 SS in 0.5 M thiosulfate
alone. The only viable explanation is HIC. Thus, the solution. Thus, there is consensus on the part of de-
decomposition of thiosulfate can be written as: position of S in the neighborhood of the crack tip by
thiosulfate reduction or thiosulfate disproportionation
+ −
3 þ H → S þ HSO3
S2 O2− (38) and its role in retarding passivation and/or hydrogen
injection. Sulfur species are reported in other studies
indicating that the polysulfur oxyanion is acid unstable. to effectively catalyze the entry of atomic hydrogen into
Transport of S2O32− into the acidified crack via the metals and alloys, including stainless steels.110,112
During kraft pulping process, 5% to 10% sodium iodine in the event of a loss-of-coolant accident, into the
hydroxide (NaOH) and sodium sulfide (Na2S) solution at boric acid/lithium hydroxide primary coolant.7
170°C (∼150 psi, 1.03425 MPa) are used to convert Thiosulfate corrosion may also present a problem
wood chips into chemical pulp by cooking chips in large for gold-leaching hydrometallurgical circuits. In
digesters. The oxidation of sulfide ions used in this general, cyanidation is a very effective and preferred
process may generate thiosulfate. Moreover, a slight gold leaching technique. However, because of the en-
change was made in brightening chemistry by the ad- vironmental concerns over the safe usage of cyanides,
dition of sodium hydrosulfite (Na2S2O4), in order to alternatives to the cyanidation technique have been
protect aquatic life in the rivers,20 which could generate researched extensively in last decade. In this effort, the
thiosulfate anion as a metastable byproduct of the use of environmentally-benign thiosulfate solutions
Na2S2O4. The presence of thiosulfate anion in the for gold leaching has recently gained widespread re-
pulping process caused cracking/pitting of not only search and commercial interest. In fact, the use of
cast martensitic and sensitized austenitic SS rolls, but thiosulfate has also become attractive in the leaching of
also of bronze. Preventive measures were taken to copper-gold complexes and carbonaceous gold ores,
minimize the deleterious effect of thiosulfate by using which could not be satisfactorily leached using cyani-
more corrosion resistant alloys such as Type 316L SS dation.44 Thiosulfate leaching may also present eco-
and duplex stainless steel. Also, S2O32− is now mini- nomic benefits, as thiosulfate salts are considerably
mized by much more careful chemistry control. Many cheaper than cyanides.6 As discussed, thiosulfate may
other chemicals are now used and some like sulfite cause the localized corrosion/SCC of stainless steels,
(SO32−) and carbonate (CO32−) are present in sufficient which are widely used as construction materials in
concentrations that they inhibit pitting (Figure 21). hydrometallurgical applications for preparing/building
In the case of the petroleum industry, the sulfur plant infrastructures. There have been no studies
present in sour crude oil, as an impurity in feedstock, reported in the literature that are related to the elec-
produces iron sulfide scale. When equipment is opened trochemical corrosion of stainless steels in thiosulfate
to the atmosphere for inspection and repair during solutions relevant to gold leaching technologies. More-
shutdowns, these scales are exposed to oxygen and over, the thiosulfate gold leaching process is still in
moisture. Subsequently, this leads to the formation of its developmental stages and the long-term impact of
polythionic acids (H2SxO6, x = 3, 4, 5) and other the thiosulfate species and leach conditions on plant
oxyanions, such as S2O32−, which can cause pitting infrastructure is not yet well known. Hence, if the
corrosion and SCC, unless preventive measures are thiosulfate gold leaching technology is to be success-
implemented. The synergistic presence of thiosulfate fully implemented, there is a definite need for devel-
and chloride ions in some nuclear reactors that use oping material selection guidelines for thiosulfate
Alloy 800 tubing is also speculated to cause severe solutions relevant to thiosulfate gold leaching circuits.
corrosion problems.7 The difficulty with this hypothesis
is that there is no obvious source of sulfate or thio-
sulfate, because of the tight water chemistry con- CONCLUSIONS
straints in nuclear power reactors. However, there have
Because thiosulfate has been implicated as an
been several incidents of failure of steam generator
aggressive species in variety of industries, this review
tubing, including the notorious event at the Three Mile
provides a brief summary of the literature to date. The
Island nuclear power plant in Pennsylvania in 1979,
following general conclusions can be drawn:
where the root causes have been quite evident. In the
v The presence of thiosulfate ions causes severe
case of Three Miles Island, the reason for these failures
localized corrosion/pitting of stainless steels in the
was identified as being leakage of the building spray
synergistic presence of chloride and/or sulfate ions.
solution, which contained thiosulfate to fix radioactive
There exists a critical ratio of thiosulfate and chloride
ion in order to cause severe pitting of stainless steels. In
most of the studies, this ratio of thiosulfate/chloride
was found to be less than one.
v There is a general consensus on the role of adsorbed
sulfur in causing pitting of stainless steel by the ac-
celeration of anodic dissolution and the retardation
of repassivation. Sulfur is generally produced by the
reduction of thiosulfate ions on the film-free surfaces of
alloy substrate.
v Thiosulfate ion alone does not appear to play any role
in breaking down the passive film, and cannot cause
any localized corrosion/pitting, which may be attrib-
FIGURE 21. Schematic of the pitting caused by thiosulfate anion in
uted to the inability of thiosulfate ions to be reduced into
presence of acid-formers, but inhibited by neutralizers.20
absorbed sulfur on the intact compact passive film, but
it may do so by dissociation. In general, there have been 14. R.C. Newman, W.P. Wong, H. Ezuber, A. Garner, Corrosion 45
(1989): p. 282-287.
very limited studies concerning the characterization 15. A. Garner, Corrosion 41 (1985): p. 587-591.
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