Mechanistic Aspects of Reduction of tris(Pyridine-2-carboxylato) Manganese(III) by S2O32- in Na(pic)-picH Buffer

Kalyan K. Sen Gupta; Nandini Bhattacharjee; Biswajit Pal

doi:10.14233/ajchem.2015.18820

Issue

Vol. 27 No. 7 (2015): Vol 27 Issue 7, 2015

Issue Published : March 29, 2015

This work is licensed under a Creative Commons Attribution 4.0 International License.

Mechanistic Aspects of Reduction of tris(Pyridine-2-carboxylato) Manganese(III) by S2O32- in Na(pic)-picH Buffer

https://doi.org/10.14233/ajchem.2015.18820

Kalyan K. Sen Gupta

Department of Chemistry, Jadavpur University, Kolkata-700 032, India

Nandini Bhattacharjee

Department of Chemistry, Jadavpur University, Kolkata-700 032, India

Biswajit Pal

Department of Chemistry, St. Paul's C.M. College, 33/1 Raja Rammohan Roy Sarani, Kolkata-700 009, India

Corresponding Author(s) : Biswajit Pal

palbiswajit@yahoo.com

Asian Journal of Chemistry, Vol. 27 No. 7 (2015): Vol 27 Issue 7, 2015
Article Published : March 30, 2015

Abstract

The oxidation of thiosulfate ion by tris(pyridine-2-carboxylato) manganese(III) in picolinate-picolinic acid buffer occurs according to the equation 2S₂O₃^2- + 2Mn^III ® S₄O₆^2- + 2Mn^II. The reaction was studied under pseudo-first order conditions. The rate of the reaction is first order with respect to [S₂O₃^2-] and [Mn^III] with no evidence of 1:1 complex formation between the reactants. The influence of pH on the reaction rate is insignificant. The rate of the reaction decreases with the increase in acrylamide concentration. The influence of temperature was studied in the temperature range 288-303 K. The values of DH^¹ and DS^¹ have been calculated to be 33 ± 2 kJ mol^-1 and -137 ± 7 J K^-1 mol^-1, respectively. A one-equivalent electron transfer from S₂O₃^2- to Mn^III takes place to give Mn^II and free radical, the latter subsequently is transformed to S₄O₆^2-. An attempt has been made to compare the results of the oxidation of some other sulfur, phosphorous and nitrogen containing inorganic compounds by this oxidant.

Keywords

tris(Pyridine-2-carboxylato) manganese(III) Na(pic)-picH buffer Thiosulfate Electron transfer reaction

K. Sen Gupta, K., Bhattacharjee, N., & Pal, B. (2015). Mechanistic Aspects of Reduction of tris(Pyridine-2-carboxylato) Manganese(III) by S2O32- in Na(pic)-picH Buffer. Asian Journal of Chemistry, 27(7), 2669–2674. https://doi.org/10.14233/ajchem.2015.18820

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References

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J. Lurie, Hand Book of Analytical Chemistry, Mir Publications, Moscow, p. 311 (1975).
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K.K. Sen Gupta and B. Pal, Inorg. React. Mech., 1, 265 (2000).
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G.T. Morgan and F.H. Burstall, J. Chem. Soc., 1259 (1927); doi:10.1039/jr9270001259.
F. Feigl, L. Anger and R. Oesper, Spot Test in Organic Analysis, Elsevier, New York, edn 7, p. 387 (1966).
B. Pal and K.K. Sen Gupta, Transition Met. Chem., 37, 671 (2012); doi:10.1007/s11243-012-9636-x.
I.A. Derevenkov, D.S. Salnikov, S.V. Makarov, G.R. Boss and O.I. Koifman, J. Chem. Soc., Dalton Trans., 42, 15307 (2013); doi:10.1039/c3dt51714d.
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J.R. van Wazer, Phosphorus and its Compounds, Interscience Publishers, Inc., New York, vol. 1, p. 360, (1964).

References

B. Yatsimurski and V.P. Vasilev, Instability Constants of Complex Compounds, Pergamon Press, Oxford, p. 134 (1960).

J. Lurie, Hand Book of Analytical Chemistry, Mir Publications, Moscow, p. 311 (1975).

F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, edn 3, Wiley Eastern, New Delhi, p. 353, 447 and 453 (1979).

K.B. Wiberg, Oxidation in Organic Chemistry, Part A, Academic Press, New York, p. 29 (1965).

F.M. Page, Transac. Farad. Soc., 49, 635 (1953); doi:10.1039/TF9534900635; Transac. Farad. Soc., 50, 120 (1954); doi:10.1039/TF9545000120; Transac. Farad. Soc., 56, 398 (1960); doi:10.1039/TF9605600398.

J.D. Rush and L.J. Kirschenbaum, Inorg. Chem., 24, 744 (1985); doi:10.1021/ic00199a022.

R.K. Panda, G. Neogi and D. Ramaswamy, Int. J. Chem. Kinet., 13, 1001 (1981); doi:10.1002/kin.550131002.

K.K. Sen Gupta, S. Das and S. Sen Gupta, Transition Met. Chem., 13, 155 (1988); doi:10.1007/BF01087810.

J.J. Byerley, S.A. Fouda and G.S. Rempel, J. Chem. Soc. (Dalton), 889 (1973); doi:10.1039/dt9730000889.

D. Chatterjee, S. Shome, N. Jaiswal and S.C. Moi, J. Mol. Catal. Chem., 386, 1 (2014); doi:10.1016/j.molcata.2014.01.029.

R.K. Patil, S.A. Chimatadar and S.T. Nandibewoor, Indian J. Chem., 48A, 357 (2009).

M.D. Johnson and J.F. Read, Inorg. Chem., 35, 6795 (1996); doi:10.1021/ic960480o.

K.K. Sen Gupta, B. Pal, N. Bhattacharjee and S.P. Ghosh, Bull. Chem. Soc. Jpn., 72, 1769 (1999); doi:10.1246/bcsj.72.1769.

K.K. Sen Gupta and B. Pal, Inorg. React. Mech., 1, 265 (2000).

K.K. Sen Gupta and N. Bhatacharjee, Transition Met. Chem., 25, 518 (2000); doi:10.1023/A:1007076609240.

K.K. Sen Gupta and N. Bhattacharjee, J. Indian Chem. Soc., 78, 284 (2001).

S. Ghosh, P.K. Ray, T.K. Bandopadhyay and A.K. Deb, Z. Naturforsch. B, 36, 1270 (1981).

M.M. Ray, J.N. Adhya, D. Biswas and S.N. Poddar, Aust. J. Chem., 19, 1737 (1966); doi:10.1071/CH9661737.

I.M. Kolthoff and R. Belcher, Volumetric Analysis, Interscience Publishers, Inc (New York), vol III, p. 648 (1957).

G.T. Morgan and F.H. Burstall, J. Chem. Soc., 1259 (1927); doi:10.1039/jr9270001259.

F. Feigl, L. Anger and R. Oesper, Spot Test in Organic Analysis, Elsevier, New York, edn 7, p. 387 (1966).

B. Pal and K.K. Sen Gupta, Transition Met. Chem., 37, 671 (2012); doi:10.1007/s11243-012-9636-x.

I.A. Derevenkov, D.S. Salnikov, S.V. Makarov, G.R. Boss and O.I. Koifman, J. Chem. Soc., Dalton Trans., 42, 15307 (2013); doi:10.1039/c3dt51714d.

F.M. Page, J. Chem. Soc., 1719 (1953); doi:10.1039/jr9530001719.

R. Steudel and Y. Steudel, J. Phys. Chem., 113, 9920 (2009); doi:10.1021/jp905264c.

J.O. Edwards, Chem. Rev., 50, 455 (1952); doi:10.1021/cr60157a004.

G.S. Nikolov, Inorg. Chim. Acta, 5, 559 (1971); doi:10.1016/S0020-1693(00)95988-7.

J.R. van Wazer, Phosphorus and its Compounds, Interscience Publishers, Inc., New York, vol. 1, p. 360, (1964).

Issue

Vol. 27 No. 7 (2015): Vol 27 Issue 7, 2015

Mechanistic Aspects of Reduction of tris(Pyridine-2-carboxylato) Manganese(III) by S2O32- in Na(pic)-picH Buffer

Corresponding Author(s) : Biswajit Pal

Abstract

Keywords

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