Kinetics and Mechanism of Oxidation of Diethyl Ether by Chloramine-T in Acidic Medium

Y I Hassan,N H M Saeed

doi:10.1155/2012/957405

Abstract

The kinetics of oxidation of diethyl ether (DE) with sodium N-chloro-p-toluenesulphonamide (CAT) in hydrochloric acid solution has been studied at (313°K).The reaction rate show a first order dependence on [CAT] and fractional order dependence on each [DE] and [H+] .The variation of ionic strength of the medium has no significant effect on the reaction rate , addition of p-toluenesulphonamide (p-TSA) affects the reaction rate marginally the rate increased with decreasing dielectric constant of the medium , the stochiometry of the reaction was found to be 1:2 and oxidation products were identified , A Michaelis – Menten type mechanism has been suggested to explain the results.The equilibrium and the decomposition constants of CAT – diethyl ether complex have been evaluated. Thermodynamic parameters were computed by studying reaction at temperatures range ( 308 – 323°K) for the rate limiting step and for the observed first order constants by the linear Arrhenius plot. The mechanism proposed and the derived rate law are consistent with observed kinetics.

Highlights

The versatile nature of aromatic sulphonyl haloaminesis due to their ability to act as sources of halonium cations, hypohalite species and nitrogen anion which act as both bases and nucleophilies .Sodium-N-chloro-P-toluenesulphonamide (p-CH3-C6H4SO2NClNa.3H2O), well known as chloramine-T (CAT, R'NClNa), is a very important member of this class of compounds and has received a considerable attention as an oxidizing agent for a wide range of functional groups in both acidic and alkaline media
The kinetics of oxidation of diethyl ether (DE), by chloramine-T was investigated at several initial concentration of reactants in acid medium
The reaction rate will increase with increase in [H+], Table 1

Summary

Introduction

The versatile nature of aromatic sulphonyl haloaminesis due to their ability to act as sources of halonium cations, hypohalite species and nitrogen anion which act as both bases and nucleophilies .Sodium-N-chloro-P-toluenesulphonamide (p-CH3-C6H4SO2NClNa.3H2O), well known as chloramine-T (CAT, R'NClNa), is a very important member of this class of compounds and has received a considerable attention as an oxidizing agent for a wide range of functional groups in both acidic and alkaline media. R'NCl - and OCl- in alkaline medium .Free chlorine has been detected in medium in the presence of chloride ion[3] This reagent has been widely ulitized for the quantitative determination of a large number of inorganic and organic compoundsin solution[4,5], only a few kinetic studies have been carried out .Mention may be made about the oxidation of hydrogen peroxide[6], P-cresols7,8 ,phenols[9], aldehyde[10], ketones[11], aldoses[12,13], primary[14] and secondary alcohols[15], α-hydroxy acid16 ,formic acid[17], furan-2-carboxic acid[18], amino acid[19,20], aniline[21], toluene[22], acetanilide[23] catecholamines[24], sulphoxides[25,26], cyanide[27] and thiocynat[28] by CAT. HASSAN acid produced was identified by conversion to hydro –oximic acid derivative[34] which give violate color with ferric ion .or formation of deep-red coloration on reaction with practically neutral or basic solution of ferric chloride[35]

Results and Discussion

H CH3 CH3 C

Conclusion