Abstract
The kinetics of osmium(VIII) catalyzed oxidation of sulfanilic acid (p-aminobenzenesulfonic acid) by hexacyanoferrate(III) (HCF(III)) in alkaline medium was studied spectrophotometrically. The reaction showed first order kinetics in hexacyanoferrate(III) and osmium concentrations and an order of less than unity in sulfanilic acid (SAA) and alkali concentrations. The rate of reaction increased with increase in alkali concentration. Increasing ionic strength and dielectric constant of the medium increased the rate of the reaction. A retarding effect was observed by one of the products i.e. hexacyanoferrate(II) (HCF(II)). A mechanism involving the formation of a complex between sulfanilic acid and osmium(VIII) species, [(OsO5(OH)]3− (in presence of high OH− concentrations), has been proposed. The main products were identified by spectral studies. The reaction constants involved in the mechanism are evaluated.
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Kelson EP, Ericson PP (2000) Int J Chem Kinet 32:760
Vovk AI, Muraveva IV, Kukhar VP, Baklan VF (2000) Russ J Gen Chem 70:1108
Speakman PT, Waters WA (1955) J Chem Soc 40
Singh VN, Singh MP, Saxena BL, Singh MP (1969) Can J Chem 47:1051
Singh VN, Singh MP, Saxena BL (1970) Indian J Chem 8:529
Brewster RQ, Mcewen WE (1971) Organic chemistry, 3rd edn. Prentice-Hall, New Delhi
Morrison RT, Boyd RN (2001) Organic chemistry, 6th edn. Prentice-Hall, New Delhi, p 862
Panigrahi GP, Nayak RN (1982) React Kinet Catal Lett 21:283
Caro A, Cortes G, Cerda V (1990) Analyst (London) 115:753
Otto M, Werner G (1980) Z Chem 20:379
Dziegiec J (1979) Pol J Chem 53:1821
Bontschev PR, Alexiev AA (1970) J Inorg Nucl Chem 32:2237
Bontschev PR, Alexiev AA, Dimitrova B (1969) Talanta 16:597
Agrawal MC, Upadhyay SK (1983) J Sci Ind Res 42:508
Sirsalmath KT, Hiremath CV, Nandibewoor ST (2006) J Appl Cat A Gen 305:79
Farokhi SA, Nandibewoor ST (2003) Tetrahedron 59:7595
Jeffery GH, Bassett J, Mendham J, Denney RC (1996) Vogel’s textbook of quantitative chemical analysis, ELBS Longman, 5th edn. Essex, England, p 339
Sexena OC (1967) Microchem J 12:609
Furniss BS, Hannaford AJ, Rogers V, Smith PWG, Tatchell AR (1994) Vogel’s textbook of practical organic chemistry, ELBS, 5th edn. Essex, England
Upadhyay A, Upadhyay K, Nath N (1993) Biophysical chemistry principles and techniques, 1st edn. Himalaya Publishing House, Bombay, India, p 235
Feigl F (1975) Spot tests in organic analysis. Elsevier, New York, pp. 283, 289, 195
Silverstein SM, Clayton BG, Terence CM (1991) Spectrometric identification of organic compounds, 5th edn. Wiley, New York
Bellamy LJ (1958) The IR spectra of complex organic molecules, 2nd edn. Methuen and Co., London, p 425
Jeffery GH, Bassett J, Mendham J, Denney RC (1996) Vogel’s textbook of quantitative chemical analysis, ELBS Longman, 5th edn. Essex, England, p 384
Lide DR (Ed) (1992) Hand book of chemistry and physics chemical rubber publishing company, 73rd edn. London, pp 8–51
Swinehart JH (1967) J Inorg Nucl Chem 29:2313
Singh MP, Ghosh S (1955) Z Phys Chem (Leipzig) 204:1
Sing MP, Ghosh S (1957) Z Phys Chem (Leipzig) 207:187
Singh MP, Ghosh S (1957) Z Phys Chem (Leipzig) 207:198
Wiberg KB, Nigh WG (1965) J Am Chem Soc 87:3849
Kochi JK, Graybill BM, Kwiz M (1964) J Am Chem Soc 86:5257
Singh VN, Singh MP, Saxena BBL (1969) J Am Chem Soc 91:2643
Hiremath SC, Chimatadar SA, Raju JR (1994) Transition Met Chem 19:636
Lancaster JM, Murray RS (1971) J Chem Soc (A) 2755
Nandibewoor ST, Hiremath GA, Timmanagoudar PL (2000) Transition Met Chem 25:394
Martinez M, Pitarque MA, Eldik RV (1996) J Chem Soc Dalton Trans 2665
Rangappa KS, Anita N, Made Gowda NM (2001) Synth React Inorg Met Org Chem 31:1499
Amis ES (1966) Solvent effects on reaction rates and mechanism. Academic, New York
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Farokhi, S.A., Nandibewoor, S.T. Mechanistic Studies of Osmium(VIII) Catalysed Oxidation of Sulfanilic Acid by Hexacyanoferrate (III) in Alkaline Medium. Catal Lett 129, 207–214 (2009). https://doi.org/10.1007/s10562-008-9791-z
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DOI: https://doi.org/10.1007/s10562-008-9791-z