Abstract Kinetics of oxidation of aniline by chromic acid has been studied in
10 % aqueous acetic acid and N-methylaniline, while the kinetics of
oxidation of N,N'-dimethylaniline have been studied by chromic acid
in 1 % aqueous acetic acid. The order with respect to oxidant for aniline,
N-methylaniline, N,N'-dimethylaniline is one, zero, zero, respectively.
The order with respect to substrate is one in each case. The rates constant
were found to depend upon the concentration of HCl and H2SO4. The
primary salt effect on the rate of oxidation is negligible. The reaction
rate increases with the decrease of the dielectric constant of the medium
in each case. An addition of Cu2+ and Ag+ ions have marked accelerating
effect on all the three reactions, while in case of Mn2+ ions the rate is found
to decrease in case of aniline and N,N'-dimethylaniline, but increase in
case of N-methyl aniline. Thermodynamic parameters were evaluated
and mechanisms for the reactions have been proposed. The isokinetic
temperature has also been evaluated. |