Sb Post Graduate College

Barāgaon, India

Sb Post Graduate College

Barāgaon, India
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Kumar A.,Sb Post Graduate College | Pratap B.,Sb Post Graduate College
Asian Journal of Chemistry | Year: 2012

The kinetics of Pd(II) catalyzed oxidation of methyl amine by alkaline solution of N-bromosuccinimide (NBS) in the presence of mercuric acetate as scavenger is investigated in the temperature range 30-45 °C. First order kinetics in the lower concentration range of N-bromosuccinimide was observed to tend to zero order at its higher concentrations. The reaction follow identical kinetics, being zero order in substrate and [OH-]. A positive effect of variation of palladous chloride was observed while addition of succinimide and mercuric acetate did not affect the rate constant of reaction. The variation of ionic strength of the medium and [Cl-] showed zero effect on the reaction rate. The oxidation product formed formaldehyde formed was detected by spot test and 2,4-dinitrophenyl hydrazine test. Various thermodynamic parameters have been computed. A suitable mechanism, consistent with the kinetic observation has been proposed.


Kumar A.,Sb Post Graduate College | Pratap B.,Sb Post Graduate College
Asian Journal of Chemistry | Year: 2012

The kinetics of oxidation of ethyl amine by N-bromosuccinimide in the presence of alkaline solution of palladium(II) chloride as homogeneous catalyst has been investigated at 303 K. A1:1 stoichiometry has been observed. The reaction exhibits a zero order rate dependence with respect to amine and first order at low concentration of N-bromosuccinimide tending to zero order at high concentration of N-bromosuccinimide. A positive fractional order is observed in the case of Pd(II) whereas ionic strength, [OH-] and Hg(OAc)2 do not influence the oxidation rate. The reaction follows negligible effect on addition succinimide and chloride ion. The activation parameters have been evaluated from the Arrhenius plot. Mechanistic steps are discussed and the rate law derived was found to confirm the observed kinetic results.

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