Elemental selenium dissolves in sulfite solution to form selenosulfate ion: Se + SO,'-= SeSo3'-. The formation constants for this equilibrium at temperatures from 0 to 35°C are reported for the first time. The isomeric thioselenate anion, SseO,*-, is not, however, produced by the reaction of sulfur with selenite nor is the selenoselenate ion, Se20,'-, formed from selenium and selenite. Selenotrithionate is formed rapidly from the reaction of selenous acid with sulfite and hydrogen sulfite according to: HSe0,-+ 3 HS0,-= s~(so,),~-+ SO: -+ 2 H20. Two isomers of the selenotrithionate ion are observed by Se-77 NMR and Raman spectroscopy, one with 0-bonded Se, s~(oso,),~-, and the other with S-bonded Se, Se(.SO,),'-. Both isomers are formed in reactions with hydrogen sulfite but only the 0-bonded isomer is formed in sulfite solutions at ambient temperatures. The Raman and Se-77 NMR spectra of the various sulfur-selenium anions formed are given and the parallel with the reactions of selenous acid and thiols is discussed.Key words: selenium, sulfite, selenosulfate, selenotrithionate, Se-77 NMR, Raman spectroscopy, equilibria, aqueous solutions.Resum6 : Le stltnium Cltmentaire se dissout dans une solution de sulfite pour former l'ion sClCnosulfate : Se + SO,'-= S~SO?-. On a d6terminC pour la premikre fois les constantes de formation pour cet Cquilibre, B des temperatures allant de 0 B 35°C. Toutefois, l'ion isomkre thiosCICnate, SS~O,'-, n'est pas produit par la reaction du soufre avec le selenite; l'ion ~ClenosClCnate, se20,'-, ne se forme pas non plus i partir du sClCnium et du sC1tnite. Le sClCnotrithionate se forme rapidement par la rtaction de l'acide sClCneux avec le sulfite et le sulfite d'hydrogkne, suivant I'tquation : HSe0,-+ 3 HSO< = s~(so,),~-+ SO,' -+ 2 H'O. On a observt deux isomkres de l'ion stltnotrithionate par RMN du 7 7~e et par spectroscopie Raman; l'un comporte un 0 lit au Se, Se(oS0,);-, et l'autre comporte un S liC au Se, Se(~0,);-. Les deux isomkres se forment au cours de rCactions avec le sulfite d'hydrogkne; toutefois, B la temptrature ambiante, en solutions dans le sulfite, il ne se forme que l'isomkre comportant une liaison 0 . On rapporte les spectres RMN du 7 7~e des divers anions soufre-sCltnium obtenus et on discute du parallkle qui existe avec les rtactions de I'acide sCltneux et des thiols.
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