Oxidation of hydrazine by Cr(VI) oxide. kinetic and mechanistic studies in the presence of complexing agents

V-M Ramanujam, S. Sundaram, N. Venkatasubramanian

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The kinetics of the Cr(VI) oxidation of hydrazine sulphate have been investigated both in the presence and absence of aqueous sulphuric acid. At low concentrations of hydrazine sulphate (< 0.02 M), the reaction exhibits a total second order dependence being first with respect to the gross [Cr(VI)] and also first with respect to [hydrazine sulphate]. But a plot of 1/k1 versus 1/[substrate] is linear with an intercept when [N2H4·H2SO4] is > 0.02 M pointing to the formation of an equilibrium complex between the reactants prior to the main reaction. The effect of added H2SO4, sulphate, bisulphate and chloride ions has been analysed. A stoichiometry of [Cr(VI]: [N2H4] = 4:3 and the absence of ammonia in the reaction product (nitrogen being the only product) indicate that Cr(VI) behaves as a two-electron oxidant. Effect of added EDTA on this system is quite interesting and has been investigated thoroughly. A study of the UV spectrum of Cr(VI) solution in the presence of EDTA indicates the formation of mono and binuclear complexes of Cr(VI) with EDTA. Suitable mechanisms have been proposed to account for these observations.

Original languageEnglish (US)
Pages (from-to)133-139
Number of pages7
JournalInorganica Chimica Acta
Volume13
Issue numberC
DOIs
StatePublished - 1975
Externally publishedYes

Fingerprint

hydrazine
ethylenediaminetetraacetic acids
Hydrazine
Ethylenediaminetetraacetic acid
hydrazines
Oxides
sulfates
Oxidation
oxidation
Kinetics
oxides
Edetic Acid
kinetics
Reaction products
Oxidants
Stoichiometry
reaction products
ammonia
low concentrations
stoichiometry

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Oxidation of hydrazine by Cr(VI) oxide. kinetic and mechanistic studies in the presence of complexing agents. / Ramanujam, V-M; Sundaram, S.; Venkatasubramanian, N.

In: Inorganica Chimica Acta, Vol. 13, No. C, 1975, p. 133-139.

Research output: Contribution to journalArticle

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AB - The kinetics of the Cr(VI) oxidation of hydrazine sulphate have been investigated both in the presence and absence of aqueous sulphuric acid. At low concentrations of hydrazine sulphate (< 0.02 M), the reaction exhibits a total second order dependence being first with respect to the gross [Cr(VI)] and also first with respect to [hydrazine sulphate]. But a plot of 1/k1 versus 1/[substrate] is linear with an intercept when [N2H4·H2SO4] is > 0.02 M pointing to the formation of an equilibrium complex between the reactants prior to the main reaction. The effect of added H2SO4, sulphate, bisulphate and chloride ions has been analysed. A stoichiometry of [Cr(VI]: [N2H4] = 4:3 and the absence of ammonia in the reaction product (nitrogen being the only product) indicate that Cr(VI) behaves as a two-electron oxidant. Effect of added EDTA on this system is quite interesting and has been investigated thoroughly. A study of the UV spectrum of Cr(VI) solution in the presence of EDTA indicates the formation of mono and binuclear complexes of Cr(VI) with EDTA. Suitable mechanisms have been proposed to account for these observations.

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