Kinetics and Mechanistic Study of Oxidation of Ethyl Vanillin by Alkaline Hexacyanoferrate(III)

A. Grace Kalyani; R. Jamunarani; F.J. Maria Pushparaj

doi:10.14233/ajchem.2015.18366

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.

Kinetics and Mechanistic Study of Oxidation of Ethyl Vanillin by Alkaline Hexacyanoferrate(III)

https://doi.org/10.14233/ajchem.2015.18366

A. Grace Kalyani

Research & Development Centre, Bharathiar University, Coimbatore-641 046, India; Department of Chemistry, Nehru Institute of Engineering & Technology, Coimbatore-641 105, India

R. Jamunarani

Department of Chemistry, Government Arts & Science College, Coimbatore-641 018, India

F.J. Maria Pushparaj

Department of Chemistry, Government Arts & Science College, Ooty-643 002, India

Corresponding Author(s) : A. Grace Kalyani

agracekalyani@gmail.com

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

Abstract

The kinetics of oxidation of ethyl vanillin by hexacyanoferrate(III) in aqueous alkaline medium was studied. The reactions are found to be fractional order with respect to substrate & hydroxide ion and first order with respect to oxidant. The rate-determining step is the outer-sphere formation of Fe(CN)₆^4– and free radicals, which is followed by the rapid oxidation of free radicals by Fe(CN)₆^3– to give products. The added product, hexacyanoferrate(II), had a retarding effect on the rate of reaction. Ionic strength and dielectric constant of the reaction medium have little effect on the reaction rate. The effect of temperature on the rate of reaction has also been studied and activation parameters have been evaluated. A mechanism based on the experimental results is proposed and the rate law is derived.

Keywords

Oxidation Ethyl vanillin Kinetics Mechanism Potassium hexacyanoferrate(III)

Grace Kalyani, A., Jamunarani, R., & Maria Pushparaj, F. (2015). Kinetics and Mechanistic Study of Oxidation of Ethyl Vanillin by Alkaline Hexacyanoferrate(III). Asian Journal of Chemistry, 27(7), 2583–2586. https://doi.org/10.14233/ajchem.2015.18366

Download Citation

References

A.W. Adamson, J. Phys. Chem., 56, 858 (1952); doi:10.1021/j150499a009.
F.J.M. Pushparaj, S. Kannan, L. Vikram, L.S. Kumar and K.S. Rangappa, J. Phys. Org. Chem., 18, 1042 (2005); doi:10.1002/poc.968.
S.A. Farokhi and S.T. Nandibewoor, Catal. Lett., 129, 207 (2009); doi:10.1007/s10562-008-9791-z.
N.F. Quadri and N.T. Patel, Asian J. Chem., 15, 1724 (2003).
M.K. Sati, P. Singh, G. Tewary and S.P.S. Mehta, Asian J. Chem., 8, 621 (1996).
A. Goel, G.R. Verma and H.S. Singh, Asian J. Chem., 11, 1353 (1999).
M.K. Sati, P. Singh, G. Tewary and S.P.S. Mehta, Asian J. Chem., 9, 78 (1997).
K. Sharanabasamma, M.A. Angadi, M.S. Salunke and S.M. Tuwar, Ind. Eng. Chem. Res., 48, 10381 (2009); doi:10.1021/ie901049p.
D. Laloo and M.K. Mahanti, J. Phys. Org. Chem., 3, 799 (1990); doi:10.1002/poc.610031205.
A.K. Bera, B. Pal and K.K. Sen Gupta, Int. J. Chem. Kinet., 44, 494 (2012); doi:10.1002/kin.20616.
T.P. Jose, S.T. Nandibewoor and S.M. Tuwar, J. Solution Chem., 35, 51 (2006); doi:10.1007/s10953-006-8938-z.
P.T. Speakman and W.A. Waters, J. Chem. Soc., 40 (1955); doi:10.1039/jr9550000040.
V.N. Singh, M.P. Singh and B.B.L. Saxena, Indian J. Chem., 8, 529 (1970).
V.N. Singh, H.S. Singh and B.B.L. Saxena, J. Am. Chem. Soc., 91, 2643 (1969); doi:10.1021/ja01038a041.
V.N. Singh, M.C. Gangwar, B.B.L. Saxena and M.P. Singh, Can. J. Chem., 47, 1051 (1969); doi:10.1139/v69-165.
P.S. Radhakrishnamurti and B.R.K. Swamy, Proc. Indian Acad. Sci.- Chem. Sci., 88, 163 (1979).
T.E. Furia and N. Bellanca, Fenaroli's Handbook of Flavor Ingredients, Cleveland, The Chemical Rubber Co., Vol. 2, edn. 2, p. 196 (1975).
F. Patty, Industrial Hygiene and Toxicology, In: Toxicology, Interscience Publishers, New York, Vol. 2, edn. 2, p. 1695 (1963).
S. Budavari, ed., The Merck Index-An Encyclopedia of Chemicals, Drugs, and Biologicals, Whitehouse Station, NJ: Merck and Co., Inc., p. 654 (1996).
J. Mendham, R.C. Denney, J.D. Barnes, M. Thomas and B. Sivasankar, Vogel's Text Book of Quantitative Chemical Analysis, Dorling Kindersley (India) Pvt. Ltd., edn. 6, p. 372, p. 383 (2009).
F. Feigl and V. Anger, Spot Tests in Organic Analysis, Elsevier, The Netherlands, ISBN:0-444.40209-8, edn. 7, pp. 212-216 (1966).

References

A.W. Adamson, J. Phys. Chem., 56, 858 (1952); doi:10.1021/j150499a009.

F.J.M. Pushparaj, S. Kannan, L. Vikram, L.S. Kumar and K.S. Rangappa, J. Phys. Org. Chem., 18, 1042 (2005); doi:10.1002/poc.968.

S.A. Farokhi and S.T. Nandibewoor, Catal. Lett., 129, 207 (2009); doi:10.1007/s10562-008-9791-z.

N.F. Quadri and N.T. Patel, Asian J. Chem., 15, 1724 (2003).

M.K. Sati, P. Singh, G. Tewary and S.P.S. Mehta, Asian J. Chem., 8, 621 (1996).

A. Goel, G.R. Verma and H.S. Singh, Asian J. Chem., 11, 1353 (1999).

M.K. Sati, P. Singh, G. Tewary and S.P.S. Mehta, Asian J. Chem., 9, 78 (1997).

K. Sharanabasamma, M.A. Angadi, M.S. Salunke and S.M. Tuwar, Ind. Eng. Chem. Res., 48, 10381 (2009); doi:10.1021/ie901049p.

D. Laloo and M.K. Mahanti, J. Phys. Org. Chem., 3, 799 (1990); doi:10.1002/poc.610031205.

A.K. Bera, B. Pal and K.K. Sen Gupta, Int. J. Chem. Kinet., 44, 494 (2012); doi:10.1002/kin.20616.

T.P. Jose, S.T. Nandibewoor and S.M. Tuwar, J. Solution Chem., 35, 51 (2006); doi:10.1007/s10953-006-8938-z.

P.T. Speakman and W.A. Waters, J. Chem. Soc., 40 (1955); doi:10.1039/jr9550000040.

V.N. Singh, M.P. Singh and B.B.L. Saxena, Indian J. Chem., 8, 529 (1970).

V.N. Singh, H.S. Singh and B.B.L. Saxena, J. Am. Chem. Soc., 91, 2643 (1969); doi:10.1021/ja01038a041.

V.N. Singh, M.C. Gangwar, B.B.L. Saxena and M.P. Singh, Can. J. Chem., 47, 1051 (1969); doi:10.1139/v69-165.

P.S. Radhakrishnamurti and B.R.K. Swamy, Proc. Indian Acad. Sci.- Chem. Sci., 88, 163 (1979).

T.E. Furia and N. Bellanca, Fenaroli's Handbook of Flavor Ingredients, Cleveland, The Chemical Rubber Co., Vol. 2, edn. 2, p. 196 (1975).

F. Patty, Industrial Hygiene and Toxicology, In: Toxicology, Interscience Publishers, New York, Vol. 2, edn. 2, p. 1695 (1963).

S. Budavari, ed., The Merck Index-An Encyclopedia of Chemicals, Drugs, and Biologicals, Whitehouse Station, NJ: Merck and Co., Inc., p. 654 (1996).

J. Mendham, R.C. Denney, J.D. Barnes, M. Thomas and B. Sivasankar, Vogel's Text Book of Quantitative Chemical Analysis, Dorling Kindersley (India) Pvt. Ltd., edn. 6, p. 372, p. 383 (2009).

F. Feigl and V. Anger, Spot Tests in Organic Analysis, Elsevier, The Netherlands, ISBN:0-444.40209-8, edn. 7, pp. 212-216 (1966).

Issue

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

Kinetics and Mechanistic Study of Oxidation of Ethyl Vanillin by Alkaline Hexacyanoferrate(III)

Corresponding Author(s) : A. Grace Kalyani

Abstract

Keywords

Full Article

Download Citation

References

Table Of Contents