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.

References

  1. Schilt, A.A., Hoyle, W.C.: Improved sensitivity and selectivity in the spectrophotometric determination of iron by use of a new ferroin-type reagent. Anal. Chem. 39, 114-117 (1967)
  2. Diehl, H., Smith, G. F., Schilt, A. A, Mc Brid, L.: The copper reagents: cuproine, neocuproine bathocuproine. 2nd Ed., G. Frederick Smith Chemical Co., Columbus, Ohio. (1972)
  3. Traister, G.L., Schilt, A.A.: Water-soluble sulfonated chromogenic reagents of the ferroin type and determination of iron and copper in water, blood serum, and beer with the tetraammonium salt of 2, 4-bis (5, 6-diphenyl-1, 2, 4-triazin-3-yl) pyridinetetrasulfonic acid. Anal. Chem. 48, 1216-1220, (1976)
  4. Case, F.H.: The preparation of hydrazidines and as-triazines related to substituted 2-cyanopyridines1. J. Org. Chem. 30, 931-933, (1965)
  5. Carter, P.: Application of a new ferroin ligand to the automated determination of microgram serum iron and iron biniding capapcity. Microchim. Acta. 60, 410-419, (1972)
  6. White, J.M., Flashka, H. A.: An automated procedure, with use of ferrozine, for assay of serium iron and total iron-binding capacity. Clin.Chem. 19, 526-528, (1973)
  7. Stooky, L.L.: Ferrozine-a new spectrophotometirc reagent for iron. Anal. Chem. 42, 779-781, (1970)
  8. Kloster, M.B., Hach, C. C.: Simulatenous determination of sample concentration and reagent blank. Anal. Chem. 44, 1061-1064, (1972)
  9. Schilt, A.A., Hoyle, W. C.: Improved senestivity and selectivity in the spectrophotometric determination of iron by use of a new ferroin-type reagent. Anal. Chem. 38, 114-117, (1967)
  10. Smith, G.F., Richter, F.P.: Substituted 1, 10-phennthroline ferrous complex oxidation-reduction indicators potential determinations as a function of acid concentration. Ind. Eng. Chem. Anal. Ed. 16, 580-581, (1944)
  11. Ratnam, S., Anipindi, N. R.: Kinetic and mechanistic studies on the oxidation of hydroxylamine, semicarbazide, and thiosemicarbazide by iron(III) in the presence of triazines. Trans. Met. Chem. 37, 453-462, (2012)
  12. Kulakarni, S. D., Nandibewoor, S. T.: A kinetic and mechanistic study on oxidation of isoniazid drug by alkaline deiperiodatocuprate(III)-A free radical intervention. Trans. Met. Chem. 31, 1034-1039, (2006)
  13. Kulkarni, R.M., Bilehal, D.C., Nandibewoor, S.T.: Oxidation of isoniazid by quinilonium dichromate in an aqueous acid medium and kinetic determination of isoniazid in pure and pharmaceutical formulations. Anal.Sci. 20, 743-747 (2004)
  14. Varale, A., Hilage, N.: Oxidation of nicotinic acid hydrazide by thallium(III) in acidic medium: A kinetic and mechanistic study. Int.J.Chem.Sci. 7, 2173-2182, (2009)

International Journal of Scientific Research in Science, Engineering and Technology

Downloads

Published

2018-02-28

Issue

Volume 4, Issue 1, January-February-2018

Section

Research Articles

License

Copyright (c) IJSRSET

Creative Commons License

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

How to Cite

[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.