Abstract
The kinetics and mechanism of cetyltrimethylammonium bromide catalyzed oxidation of triethylene glycol [2,2'-ethylene diqxybis(ethanol)] by chloramine-T in acidic acid medium have been investigated. The reaction is first order dependence on chloramine-T and fractional order for triethylene glycol with excess concentration of other reactants. The catalytic effect due to cetyletrimethylammonium bromide has been studied. The small salt effect and increase in the reaction rate with increasing dielectric constant suggest the involvement of neutral molecule in the rate-determining step. The addition ofp-toluene sulfonamide retards the reaction rate. The effect of chloride ion on the reaction also studied. The effect of temperature on the reaction has been investigated in the temperature range 313-333K and thermodynamic parameters were calculated from the Arrhenious plot. A tentative mechanism consistent with the experimental results has been proposed.
Highlights
Kinetics study is concerned with the rate of the reaction, the influence of various conditions on these rates and mechanisms by which a reaction occurs
Triethylene glycol (TEG) is characterized by two hydroxyl groups along with two ether linkages, which contribute to its high water solubility, hygroscopicity, solvent properties and reactivity with many organic compounds
Chloramine-T abbreviated as CAT, is a versatile oxidant[15,16,17,18,19].In continuation of our work[20,21,22] C16TAB: nC16TAB → (C16TAB) catalyzed oxidation of TEG by chloramine-T has been undertaken
Summary
Kinetics study is concerned with the rate of the reaction, the influence of various conditions on these rates and mechanisms by which a reaction occurs. In a typical kinetic run, for the reaction ([CAT] = 0.004 mol dm-3, [H+] = 0.05 mol dm-3 and [TEG] =0.08 mol dm-3), a plot of log (a-x) versus time (Figure 1) gave a straight line, which indicates that reaction under the chosen condition follows pseudo first order kinetics. On varying TEG concentration from 0.02 to 0.24 mol dm-3, there is an increase in rate of reaction.
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