Oxidation of Nicotinic Acid Hydrazide (NH) And Iso-Nicotinic Acid Hydrazide(INH) by Iron(III) in Presence of Triazines (PDTS & PPDTS): A Mechanistic Study

Authors

  • A. Vasudeva Rao  Department of Chemistry, A.M.A.L . College, Anakapalli, Andhra Pradesh,India
  • Ch. Nageswara Rao  Department of Chemistry, Dadi institute of Engineering & Technology, Visakhapatnam, Andhra Pradesh, India

Keywords:

Oxidation, Fe(III), PDTS, PPDTS, Hydrazides And Kinetics

Abstract

Oxidation of nicotinic acid hyrazide (NH) and iso-nicotinic acid hydrazide (INH) by iron(III) in presence of triazines (i.e. 3-((2-pyradyl)-5,6-bis(4-pehnyl sulphonic acid),-1,2,4 triazine (PDTS), 3-(4-(4-phenyl sulphonci)-2-pyridyl)-5,6-bis(4-phenylsulphonic acid)-1,2,4-triazine (PPDTS)) has been studied. These reactions enhanced in presence of triazines due to increase redox potential of Fe(III)/Fe(II) couple and also iron(III) acts as better oxidizing agent in presence of triazines. The oxidation of nicotinic acid hydrazide/ iso nicotinic hydrazide by iron(III) in the presence of PDTS is first order with respect to Fe(III). The reactions are accelerated by PDTS and plots of 1/kobs versus 1/[PDTS]2 are straight lines with positive slopes and positive intercepts on the ordinate indicating the formation of a 1:2 complex between Fe(III) and PDTS. It has also been observed that these reactions are decelerated by H+ ion. Iron(III) exists mainly as hexa aquoiron(III) under the present experimental conditions. Activation parameters have been computed. Specific rate constants (k) and equilibrium constants (K1 and K2) for iron(III)-PDTS-NH and iron(III)-PDTS-INH are nearly equal. This indicates that these two isomers show similar activity towards oxidation by iron(III). A similar trend is also noticed in the oxidation of NH/INH by iron(III) in the presence of PPDTS. The PDTS systems exhibit higher ΔH# values than the PPDTS systems. The entropies of activation, ΔS# for these reactions also fall in line with this analysis. ΔS# values are the lowest in the PPDTS systems which indicates that the transition states are highly ordered compared to those in the presence of PDTS.

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International Journal of Scientific Research in Science, Engineering and Technology

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Published

2018-02-28

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Volume 4, Issue 1, January-February-2018

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Research Articles

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[1]
A. Vasudeva Rao, Ch. Nageswara Rao "Oxidation of Nicotinic Acid Hydrazide (NH) And Iso-Nicotinic Acid Hydrazide(INH) by Iron(III) in Presence of Triazines (PDTS & PPDTS): A Mechanistic Study" International Journal of Scientific Research in Science, Engineering and Technology (IJSRSET), Print ISSN : 2395-1990, Online ISSN : 2394-4099, Volume 4, Issue 1, pp.582-591, January-February-2018.