Physics
Scientific paper
Dec 1963
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1963gecoa..27.1265c&link_type=abstract
Geochimica et Cosmochimica Acta, vol. 27, Issue 12, pp.1265-1298
Physics
2
Scientific paper
Numerous measurements have been made of the pH, Eh, and the potential of a silver-silver sulfide electrode in sodium sulfide and sodium polysulfide solutions. By suitably estimating the second dissociation constant of hydrogen sulfide and various activity coefficients, it has been possible to derive a consistent model for the distribution of the polysulfide and sulflde species, S -2 , S 4 -2 , S 5 -2 , S 6 -2 and HS -1 , at strengths up to l M and for pH values between 7 and 13. This model differs markedly from the models given previously by and (1949) and by (1959b), who include S -2 , S 2 -2 , S 3 -2 , S 4 -2 , S 5 -2 and HS -1 . The free energy of formation values proposed here are 16.36 ± 0.10 kcal/mole for S 6 -2 , 15.97 ± 0.10 kcal/mole for S 5 -2 and 16.29 ± 0.10 kcal/mole for S 4 -2 . Tentative figures for di- and tri-sulfide ions are 21.0 ± 3.0 kcal/mole for S 3 -2 and 22.7 ± 3.0 kcal/mole for S 2 -2 . Those are based on a value of 21.42 kcal/mole for S -2 .
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