Thermodynamic and Kinetic Study for Protonation Reaction of Anion Radicals of Some Dinitroaromatics in Acetonitrile

Farzana Hanif; Ghazala Yasmeen; Rashida Perveen; Muhammad Aamir

doi:10.14233/ajchem.2014.16319

Issue

Vol. 26 No. 16 (2014): Vol 26 Issue 16

Issue Published : July 28, 2014

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

Thermodynamic and Kinetic Study for Protonation Reaction of Anion Radicals of Some Dinitroaromatics in Acetonitrile

https://doi.org/10.14233/ajchem.2014.16319

Farzana Hanif

Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan

Ghazala Yasmeen

Institute of Chemical Sciences, Bahauddin Zakariya University, Multan, Pakistan

Rashida Perveen

Department of Plant Pathology, University College of Agriculture, Bahauddin Zakariya University, Multan, Pakistan

Muhammad Aamir

Institute of Chemical Sciences, Bahauddin Zakariya University, Multan, Pakistan

Corresponding Author(s) : Ghazala Yasmeen

ghazala31pk@yahoo.com

Asian Journal of Chemistry, Vol. 26 No. 16 (2014): Vol 26 Issue 16
Article Published : August 4, 2014

Abstract

Cyclic voltammeric method has been employed to investigate the protonation of anion radicals of 1,2-, 1,3-, and 1,4-dinitrobenzenes in acetonitrile in the temperature range 5, 15, 25 and 35 °C. Glassy carbon electrode and hanging mercury drop electrode are used as working electrodes. Benzoic acid and salicylic acid are used as protonating agents. Thermodynamic parameters are calculated by disproportionation constant. Homogeneous rate constant is calculated by using Nicholson and Shain equation. The position of nucleophilic attack in dinitrobenzenes has been investigated by calculation of charge densities using MNDO and SCF-UHF molecular orbital methods. The heterogeneous rate constant ks, h for the first reduction process in dinitrobenzenes is determined by digital simulation of the cyclic voltammograms.

Keywords

Anion radicals Dinitrobenzene Acetonitrile Glassy carbon electrode Hanging mercury drop electrode Protonation reactions

Hanif, F., Yasmeen, G., Perveen, R., & Aamir, M. (2014). Thermodynamic and Kinetic Study for Protonation Reaction of Anion Radicals of Some Dinitroaromatics in Acetonitrile. Asian Journal of Chemistry, 26(16), 5063–5072. https://doi.org/10.14233/ajchem.2014.16319

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References

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K.A. Conner, T. Gennett, M.J. Weaver and R.A. Walton, J. Electroanal. Chem., 196, 69 (1985); doi:10.1016/0022-0728(85)85081-6.
M. Mohammad and M. Aslam, J. Chem. Soc. Pak., 33, 12 (2011).
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D.D. Perrin, Purification of Laboratory Chemicals, Pergamon Press, Oxford, edn 1, p. 58 (1966).
J.W. Ross, R.D. DeMars and I. Shain, Anal. Chem., 28, 1768 (1956); doi:10.1021/ac60119a039.
D.O. Wipf and R.M. Wightman, Anal. Chem., 60, 2460 (1988); doi:10.1021/ac00173a005.
R.S. Nicholson and I. Shain, Anal. Chem., 36, 706 (1964); doi:10.1021/ac60210a007.
D.H. Evans, Chem. Rev., 108, 2113 (2008); doi:10.1021/cr068066l.
Z.V. Todres, Ion-Radical Organic Chemistry: Principles and Applications, CRC Press, Taylor & Francis Group, Boca Raton, Fla, USA, edn 2 (2009).
A.S. Mendkovich, M.A. Syroeshkin, L.V. Mikhalchenko, A.I. Rusakov and V.P. Gultyai, Russ. Chem. Bull., 57, 1492 (2008); doi:10.1007/s11172-008-0193-6.
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A.J. Bard and L.R. Faulkner, Electrochemical Methods, John Wiley & Sons, New York, edn 2 (2001).
D. Britz, Digital Simulation in Electrochemistry, Springer, Berlin (1981).
D.K. Gosser and P.H. Rieger, Anal. Chem., 60, 1159 (1988); doi:10.1021/ac00162a014.
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References

G.H. Williams, Advances in Free Radical Chemistry, Logos Press, Academic Press, New York, vol. I (1965).

N.S. Kosower and E.M. Kosower, in ed.: W.A. Pryor, Free Radicals in Biology, Academic Press, New York, vol. II (1976).

W.J. Bowyer and D.H. Evans, J. Org. Chem., 53, 5234 (1988); doi:10.1021/jo00257a008.

D.H. Geske, J.L. Ragle, M.A. Bambenek and A.L. Balch, J. Am. Chem. Soc., 86, 987 (1964); doi:10.1021/ja01060a004.

P.H. Rieger and G.K. Fraenkel, J. Chem. Phys., 39, 609 (1963); doi:10.1063/1.1734301.

J. Bard and L.R. Faulkner, Electrochemical Methods, John Wiley & Sons, New York, edn 2 (2000).

M. Mohammad, A.Y. Khan, M.S. Subhani, W. Begum, N. Ashraf, R. Qureshi and R. Iqbal, Res. Chem. Intermed., 16, 29 (1991); doi:10.1163/156856791X00165.

M.A. Syroeshkin, A.S. Mendkovich, L.V. Mikhalchenko, A.I. Rusakov and V.P. Gul'tyai, Mendeleev Commun., 19, 258 (2009); doi:10.1016/j.mencom.2009.09.008.

M.A. Syroeshkin, A.S. Mendkovich, L.V. Mikhal’chenko, A.I. Rusakov and V.P. Gul’tyai, Russ. Chem. Bull., 58, 468 (2009); doi:10.1007/s11172-010-0034-2.

S. Mendkovich, M. A. Syroeshkin, L.V. Mikhalchenko, M.N. Mikailov, A.I. Rusakov and V.P. Gul'tyai, Int. J. Electrochem., Article ID 346043 (2011); doi:10.4061/2011/346043.

M.A. Henderson, Y. Zhou, J.M. White and C.A. Mims, J. Phys. Chem., 93, 3688 (1989); doi:10.1021/j100346a063.

J.T. Hupp, H.Y. Liu, J.K. Farmer, T. Gennett and M.J. Weaver, J. Electroanal. Chem. Interfacial Electrochem., 168, 313 (1984); doi:10.1016/0368-1874(84)87107-5.

K.A. Conner, T. Gennett, M.J. Weaver and R.A. Walton, J. Electroanal. Chem., 196, 69 (1985); doi:10.1016/0022-0728(85)85081-6.

M. Mohammad and M. Aslam, J. Chem. Soc. Pak., 33, 12 (2011).

M.D. Newton and N. Sutin, Annu. Rev. Phys. Chem., 35, 437 (1984); doi:10.1146/annurev.pc.35.100184.002253.

D.D. Perrin, Purification of Laboratory Chemicals, Pergamon Press, Oxford, edn 1, p. 58 (1966).

J.W. Ross, R.D. DeMars and I. Shain, Anal. Chem., 28, 1768 (1956); doi:10.1021/ac60119a039.

D.O. Wipf and R.M. Wightman, Anal. Chem., 60, 2460 (1988); doi:10.1021/ac00173a005.

R.S. Nicholson and I. Shain, Anal. Chem., 36, 706 (1964); doi:10.1021/ac60210a007.

D.H. Evans, Chem. Rev., 108, 2113 (2008); doi:10.1021/cr068066l.

Z.V. Todres, Ion-Radical Organic Chemistry: Principles and Applications, CRC Press, Taylor & Francis Group, Boca Raton, Fla, USA, edn 2 (2009).

A.S. Mendkovich, M.A. Syroeshkin, L.V. Mikhalchenko, A.I. Rusakov and V.P. Gultyai, Russ. Chem. Bull., 57, 1492 (2008); doi:10.1007/s11172-008-0193-6.

M.-J. Huang and J. Leszczynski, J. Mol. Struct., 592, 105 (2002); doi:10.1016/S0166-1280(02)00231-2.

A.J. Bard and L.R. Faulkner, Electrochemical Methods, John Wiley & Sons, New York, edn 2 (2001).

D. Britz, Digital Simulation in Electrochemistry, Springer, Berlin (1981).

D.K. Gosser and P.H. Rieger, Anal. Chem., 60, 1159 (1988); doi:10.1021/ac00162a014.

D.K. Gosser Jr., Cyclic Voltammetry, VCH, New York and Weinheim, Germany, p. 275 (1993).

Issue

Vol. 26 No. 16 (2014): Vol 26 Issue 16

Thermodynamic and Kinetic Study for Protonation Reaction of Anion Radicals of Some Dinitroaromatics in Acetonitrile

Corresponding Author(s) : Ghazala Yasmeen

Abstract

Keywords

Full Article

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