(6) Wajon, J. E.; Alexander, R.; Kagi, R. I. Chemosphere 1985, 14,
85-89.
(7) Campbell A. T.; Reade, A. J.; Warburton, I.; Whiteman, R. F. J.
Inst. Water. Environ. Man. 1994, 8, 52.
Appendix A
Polysulfanes obey the following acid dissociation and dis-
proportionation equilibria
(8) Khiari, D.; Suffet, I. H.; Barrett, S. E. Water Sci. Technol. 1995,
31, 93.
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122.
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p 104.
(19) Wajon, J. E.; Heitz, A. Water Sci. Technol. 1995, 31, 87.
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Water Res. 1998, 32, 1789.
-
H2Sn f H+ + HSn
(A1)
2-
HSn- T H+ + Sn
(A2)
(A3)
H2Sm T S + H2Sn
where, for simplicity m ) n + 1. The total concentration of
the oligosulfides of specific sulfur length, n, is given by
CSn ) [H2Sn] + [HSn-] + [Sn
]
(A4)
2-
[ ] and { } denote concentrations and activities, respectively.
[H2Sn] is given by
[H2Sn] ) CSn{H+}2(cKa1,Sn Ka2,Sn + {H+}cKa1,Sn
+
c
(21) Ginzburg, B.; Dor, I.; Chalifa, I.; Hadas, O.; Lev, O. Environ. Sci.
Technol. 1998, 32, 2130.
{H+}2)-1 (A5)
(22) Korchevin, N. A.; Turchaninova, L. P. Zh. Obshch. Khim. 1989,
59, 1785.
(23) Clarke, E. T.; Solouki, T.; Russel, D. H.; Martell, A. E.; McManus,
D. Anal. Chim. Acta 1994, 299, 97-111.
(24) Dickson, D. M.; Wyn Jones, R. G.; Davenport, J. Planta 1980,
150, 158-165.
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(26) Boren, H.; Grimvall, A.; Palmborg, J.; Savenhed, R. J. Chromatogr.
1985, 348, 67-78.
c
cKa1,Sn and Ka2,Sn are the first and second dissociation
constants for the polysulfanes (in concentration units). The
values of cKa1,Sn and cKa2,Sn were reported to be (5.0, 9.7); (4.2,
7.5); (3.8, 6.3); (3.5, 5.7) for n ) 2-5 respectively.33 Thus,
higher polysulfanes are stronger acids. From equilibrium
relationship eq A3 is manifested in
(27) Henatsch, J. J.; Juttner, F. Arch. Hydrobiol. 1990, 119, 315-323.
(28) Lindstrom, K. Hydrobiol. 1985, 70, 77-85.
(29) Eaton, A. D.; Cleseceri, L. S.; Greenberg, A. E. Standard methods
for the examination of water and wastewater, 19th ed.; American
Pub. Health Association: Washington, DC, 1995.
(30) Giggenbach, W. Inorg. Chem. 1972, 11, 1201-1207.
(31) Boulegue, J. Electron. Acta 1978, 42, 1439-1445.
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(33) Schwarzenbach, G.; Fisher, A. Helv. Chim. Acta 1960, 169, 1365-
1383.
KSn/ Sm ) {S}{H2Sn}/ {H2Sm}
(A6)
Introducing eq A5 into A6 and rearrangement gives
c
C
Sm/ CSn ) ({S}/ KSn/ Sm)(cKa1,Sm Ka2,Sm + {H+}cKa1,Sm
+
{H+}2)/ (cKa1,Sn Ka2,Sn + {H+}cKa1,Sn + {H+}2) (A7)
c
(34) Pickering, T. L.; Saunders, K. J.; Tobolsky, A. V. J. Am. Chem. Soc.
1967, 89, 2364-2367.
(35) Grant, D.; Van Wazer, J. R. J. Am. Chem. Soc. 1968, 86, 3012-
3017.
Thus, for unit activity of sulfur (or for constant dissolved
sulfur concentration) CSm/ CSn in eq A7 is a monotonically
c
c
decreasing function of {H+} since the Ka1,Sm and Ka2,Sm are
c
c
larger than Ka1,Sn and Ka2,Sn for m > n. For example, for very
low pH the value [CSm/ CSn]/ [{S}/ KSn/ Sm] ) 1 while for very
(36) Canfield, D. E.; Des Marais, D. J. Science 1991, 251, 1471-1473.
(37) Elliot, S.; Lu, E.; Sherwood, R. In Biogenic Sulfur in the
Environment; Saltsman, E., Cooper, W. J., Eds.; American
Chemical Society: Washington, DC, 1988.
(38) Chin, H. W.; Lindsay, R. C. In Sulfur compounds in foods;
Mussinan, C. J., Keelan, M. E., Eds.; ACS Symposium Series,
564; American Chemical Society: Washington, DC, 1993; p 90.
(39) Boulegue, J. Geochim. Cosmochim. Acta 1977, 41, 1751-1758.
(40) Chen, K. Y.; Morris, J. G. Environ. Sci. Technol. 1972, 6, 529-
537.
(41) Steudel, R. Ind. Eng. Chem. Res. 1996, 35, 1417-73.
(42) Drotar, A.; Burton, G. A.; Tavernier, J.; Fall, R. Appl. Environ.
Microbiol. 1987, 1626-1631.
(43) Tolstikov, G. A.; Shul’ts, E. E.; Tolstikov, A. G. Russ. Chem. Rev.
(Engl. Transl.) 1997, 66, 813-826.
basic pH (i.e. pH . pcKa2,Sm) it is given by Ka1,Sm Ka2,Sm
-
c
c
(cKa1,Sn Ka2,Sn
)
-1 which always is >1 (for m > n). So, higher pH
c
increases the average molecular weight of the polysulfanes
in accordance with the pattern observed in Table 2.
Literature Cited
(1) Sulfur compounds in Foods; Mussinan, C. J., Keelan, M. E., Eds.;
ACS Symposium Series 564; American Chemical Society: Wash-
ington, DC, 1993.
(2) Aisenshtat, Z.; Lipiner, G.; Cohen, Y. In Microbial mats:
stromatolites; Cohen, Y., Casteholz, R. W., Halvorson, H. O.,
Eds.; Alan R. Liss: New York, p 471.
(3) Richards, S. R.; Rudd, J. W. M.; Kelly, C. A. Limnol. Oceanogr.
1994, 39, 562-572.
(4) Monzcvinz, J. T.; Ainsworth, L. D. J. AWWA 1974, 537-539.
(5) Wnorowski, A. U.; Scott, W. E. Water Sci. Technol. 1992, 25,
225-232.
Received for review June 22, 1998. Revised manuscript re-
ceived November 9, 1998. Accepted November 13, 1998.
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