Thiosulfate

An Interesting Sulfur Oxoanion That Is Useful in Both Medicine and lndustry-

But Is Implicated in Corrosion
S. W. Dhawale
Division of Natural Science and Math, Indiana University East, Richmond, IN 47374
The family of sulfur oxoanions consists of several chemi- The Stability of Thiosulfate Ions
cally active species, such as sulfite, thiosulfate, and Metastable in Aqueous Solutions
tetrathionate (see Figs. 1-3). Tykodi described the thiosul-
fate ion as a versatile ion whose aqueous chemistry can Aqueous solutions of thiosulfate may impair the local-
illustrate several wnceots in eeneral chemistm. such as ized corrosion resistance of some stainless steels. To under-
gas formation, a l d redox reaction; ti). Some stand the mechanisms of such localized corrosion, one
additional interesting- aspects
- of thiosulfate ions are me- must know the basic facts of thiosulfate behavior in aque-
sented in this paper. ous solutions.
Acwrding to a simplified Pourbaix diagram for the sul-
Problems and Applications in Industry fur-water system at 25 'C and at 1atm, all sulfur species
Studies from various laboratories have shown that thio- whose oxidation numbers lie between -2 and +6 are ther-
sulfate and other sulfur species are highly "aggressive", a modynamically unstable, that is, in ametastable state. An
term that corrosion engineers use to describe a chemically exception is solid sulfur.
active species that provides an environment favorable for
various forms of corrosion. The thiosulfate ion has been Factors That Affect Stability
shown to be a factor in the ambient-temperature stress Thiosulfate is a metastable anion that tends to undergo
corrosion of pressurized borated-water reactors (2). chemical decompositionin aqueous solutions. However, in-
This poses problems in the nuclear industry, where vestigators have reported that thiosulfate solutions pre-
stainless steel tanks are used to store borated thiosulfate pared in freshly boiled double-distilled water or distilled-
solutions. During emergencies or after a nuclear accident, deionized watekare very stable ifstored in air-tight bottles
these stored solution sprays may he used to react with io- (41.Dilute solutions of thio~ulfaterO.01 M or lower, decom-
dine (one of the fission products). pose more rapidly than the concentrated solutio& (0.1 M
Thiosulfate is also found in some industrial effluents as or higher) (5).Weak solutions of sodium thiosulfate are
an impurity or as a product of some reactions. Avrahami more stable when prepared and stored properly.
and Golding (3)found that thiosulfate is one of the promi- Oxidation-state diamams show a clear thermodvnamic
nent products of the oxidation of sulfide and polysulfide tendency for chemicai'disproportionation rewtions"at low
aqueous solutions. pH. The following is one possible reaction.
Like many other sulfur compounds, thiosulfate plays an
important role in technology, pharmaceutical chemistry,
and biochemistry. Sodium thiosulfate finds broad applica-
tion in our society as shown below.
an image-iirdng agent in photography
an antichlor in the paper industry
an antidote to cyanide and arsenic poisoning
a treatment for some forms of parasitic skin disorders
These uses are briefly described later in a section that cov-
ers the miscellaneous uses of thiosulfate.
Figure2. Sulfiteanion (SO;.). This anion and bisulfite (HSOi)are two
ofthe natural products of thiosulfate degradation that are of industrial
and medical importance.

Figure 1. The thiosulfate anion (s,o$-). This metastable anion is a

natural sulfur donor, disproportionatingto form suHite and sulfuror an
active sulfur species. Although this tendency is medically useful, it
can contribute to the corrosion of metals and other materials. This
compound is also subject to action by microorganisms. It can be p r o Figure 3. Telrathionate (s,o;-). This ion can be produced by the ox-
duced by certain bacteria under certain conditions, but it can also be idation of thiosulfate, as in the paper industry. It is also a known met-
degraded by other bacteria to form hydrogen sulfide. abolic product of sulfurbacteria. .,

12 Journal of Chemical Education

Since wlloidal sulfur and bisulfite ions (HSOi) are meta- brass specimenn that have been corroded in thiosulfate so-
stable in an acid environment, they undergo further reac- lutions obviouslv show the deteriorating- effects of sulfur
tions to !zive various products. compounds.
when; thiosulfate-solutionis titrated against standard
sulfuric acid or hydrochloric acid, the solution becomes Microbial Corrosion and Sulfur Oxoanions
cloudy. Approximately &lo% of the total sulfur precipi- Thiosulfate and other sulfur oxoanions are common in-
tates between pH 3 and 2. The solution also shows a strong termediates in the ahiological as well as biological oxida-
buffering action, thus suggesting the formation of a weak tion of sulfide.Also, many microomanismscan reduce thio-
acid and its salt (unpublished results from my laboratow). sulfate to hydrogen sulfide, whichcan then be excreted or
Also, the concentration of thiosulfate ions decreasesin retained.
the presence of copper (5) and copper-base alloys (unpub- Thiosulfate stimulates growth of a marine pseudomonad
lished results from my lab). In short, many factors influ- growing on low acetate (14). Sulfur-reducing bacteria wu-
ence the stability of thiosulfate solutions, as summarized ple the oxidation-reduction of organic carbon to the redox
below (5,6). system of inorganic sulfur. Thiosulfate and tetrathionate
have been detected in these culture solutions.
the purity of the water used as the solvent Sulfate-reducing bacteria are responsible for the corro-
the concentration and pH of the solution sion of type 304 and type 316 stainless steels in the paper
the presence of certain metals or alloys industry (14, 15).Buried carbon steel and cast-iron pipe-
the presence of certain metals and sulfur bacteria lines can also undergo localized corrosion in the presence
exposure to ultraviolet light
of anaerobic sulfur bacteria, accumulated thiosulfate, and
Corrosion and Thiosulfate Ions other sulfur oxoanions.
Corrosion chemistry is of vital importance to industries. Miscellaneous Uses of Thiosulfate
Sulfur and sulfur comoounds are usuallv blamed for dam-
Photographic Development
aging a variety of str&tures and materiks.
'steam power plants Photography involves various processes to produce per-
cement manent images. The development of exposed film can be
old art structures summarizedas below
almost all industrially useful common metals AgBr + developer -t Ag + B F + oxidized developer
some alloys
Generally, the development process leaves unreduced
Stress-Corrosion Cracking of Stainless Steels grains on the parts of the film that were exposed to low
light intensities. To prevent darkening of the film by the
In the early 1950's intergranular stress-corrosion crack- residual silver halide grains, these grains must be re-
ing of sensitized stainless steel became recognized as a moved during the fixing process. Usually sodium thiosul-
technological problem in the petroleum industry. Even the fate solution (hypo)is the fixing agent. It converts residual
highly corrosion-resistant 304 stainless steel was found to silver halide to water-soluble complex ions that are re-
undergo stress-corrosion cracking in petroleum and other moved during the washing process.
industries due to sulfur wmpounds. As discussed below
thiosulfate ions have been implicated in various forms of Paper Making
corrosion.
Dhawale et al. (7,s) Isaacs et al. (9)and Newman et al. Sodium thiosulfate is also used as a neutralizer of the
(10) investieated stress-corrosion crackine of sensitized chlorine wm~oundsthat are used as bleaching aeents in
stainless steels, type 304, in the presence orthiosulfate so- k
the paper iniustry One of the reactions used <he neu-
lutions. The data from all these investieations indicate tralization of bleaching solution (hypoclorite)can be writ-
that intergranular stress-corrosioncracking occurs within ten as below.
a specific wtential ranee in the presence of thiosulfate so- HOCl+ 2 ~ ~ 0 :+
- Cl- + ~ ~ 0+ ;OK
-
lutions. ~;)rat?dsodium thiosulfate solutions, as dilute as
10" M to 10.' M. caused stress-corrosion cracking under Pharmaceutical Applications
the experimeutal'conditions.
Sulfur-containing compounds have played a significant
Pitting and Crevice Corrosion role in the treatment of superficial fungal infections. A so-
lution containg 25% sodium thiosulfate, salicylic acid, iso-
Pitting of stainless steels in the paper and pulp industry propyl alcohol, and propylene glycol is highly effective in
is believed to be caused bv thiosulfate ions (11).Sodium the treatment ofinfection caused by the fungus I'ilyrospor-
hydrosulfite is used as a whitening or brightening reagent unz orbiculare (tinea veriwlor,. Sodium thiosulfate solu-
in the paper pulp industry, and it can produce thiosulfate tion is also used as a footbath in prophylaxis of ringworm.
ions. Newman (12) demonstrated that thiosulfate ions low-
ered the pitting potential of stainless steel alloys, making Medical Research
the material more susceptible to pitting corrosion. In addi-
tion, studies on crevice corrosion (13) indicate that very Thiosulfate can convert cyanide to nontoxic products by
small amounts of thiosulfate ion can promote crevice cor- the following reaction.
rosion of stainless steels.
The generally accepted mechanism of these electrochem-
ical forms of corrosion suggests that a disproportionation In humans this reaction is catalyzed by the mitochon-
of thiosulfate ions oroducG an active sulfur snecies at a drial enzyme sulfurtransferase, which can detoxify the
low pH. Active su1f;r species aid the dissolution of metd small amounts of cyanide that are inadvertantly ingested
and prevent the repassivation of the metal surface, thus with food. Since thiosulfate is a natural sulfur donor in cy-
promoting corrosion. anide detoxification, it can be used as an antidote for cya-
Thiosulfate also causes general corrosion of copper and nide poisoning (16).
copper-base alloys. A demonstration can be easily pro- In some animals, such as dogs, the sulfurtransferase ac-
duced to convince students. Stainless steel, copper, and tivity is very low. Experiments on dogs have shown that

Volume 70 Number 1 January 1993 13

the LD50 of cyanide can be increased 3-fold by sodium Literature Cited
thiosulfate. A great degree of protection against cyanide 1. %kodi, R. J. J cham. E&. 1880,67,14614%
2. U. S. Nuele.wRe&.tolr Commission Cirmlar No. 7606, November 1916.
was obtained in experimental by injeding sulfur- 3. Avrahami, M.; Goldulg, R. M. J. Chem. Soc. 141 1888, &I.
transferase with thiosulfate (17). 4. Rice, F 0.;~(l~patric. w
M.. JI; kmlun, J ~ mthem. . sac.isas,4s.1361-1365.
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""-b .ace
A"-".

Conclusion 6. Kemp, E.; nyne,~. B.;h i e , W.J. kt.rl sulfur chm. (A) iwi, 1.69.
7. Dhswale, S.; Cragnolino, G.: MacDonald, D. D.EPRIRojifRP lm,11661.
Thiosulfate provides examples of various types of &em- 8. Dhawale, 8.;Cragnolino, 0.;~ a a o n a l dD.
, D. E P R r m . w mrn,4,148.
9. Isaes, H. S.;Vyas, B.; Kendig, M . W Tha InlemotloMi Cormsion Forum, NACE,
ical reactions that might be interesting to chemistry in- 1981.26.
stmctors. D i s- ~ r o ~ d i o n a t i oreadion
n of thiosulfate ions~-~
~
is 10. Newman, R C.;Siaadeki, K, Isaaca. H. S.Motollu'giml l i a i m l o c t i a ~l ~a , 13A.
A
2015-2026.
believed to cause different forms of corrosion in sensitized 11. Q ~ , , A P U Io ~n d ~ p ~ ~ ~ x d~u a t~r y ~ i o swediah
~ ~arm ~ g bIihati-
on k ~ ~ ;
stainless steels that are highly corrosion-resistant. Such tute, Stockholm, 1983: Vol. 4, p 266.
corrosion is of industrial significance. Thiosulfate can be a
,, ,man, R, C. Cormsion 1986,41,450-453,
13 T ~D.; pdetiek,
~ L ~cormslon~ 1954, 40,655639.
,
of energy for the of some sulfur bacteria that 14. Ntiaw, J. 0.; Hem. J. D. Svlfvr in the Enuimnment, Part U: Emiaglnrl Impct*;
WSey: New York,1978.
may cause biochemical corrosion. Thiosulfate solutions are 15. cramo~ino, G.: nwnien, o H. ha I ~ C ~ ~ M ~coPiii ~ " M I F O I U ~NACE,
, 1963.
in photography and and in the paper and paper No. 241.
16. Chen, K X.;fiw, C. L.:C b w e , G.H h t l r m J. M w l Sci. 1954,188,167.
nuclear industries. , I.; ~orbo,B.A& ~ h w i o lscad.
11. Clemedmn, C. J.; ~ u l t m a nH . 1~x54,32,245.

14 Journal of Chemical Education