Oxidation of the N,N–dimethylaniline by peroxynonanic acid in organic solvents

Abstract

The rate of oxidation reaction of the N,N–dimethylaniline with peroxynonanic acid in various organic solvents was studied. It has been found the effective rate constants ( k ) and the activation energy ( E akt ) of the studied process. Between the parameters of the transition state Δ Н ≠ and Δ Ѕ ≠ is some linear relationship, indicating the presence of the compensation effect in our series of experiments. The rate of oxidation and activation energy inflation of solvation peroxyacid and N,N–dimethylaniline. The reaction medium affects the rate of oxidation. Correlation equations between the rate constants of the reactions in the study and the physic-chemical parameters of the solvents were proposed. The correlation equation for effective rate constants and the basic physic-chemical parameters of solvents at 313 K has the form: lgk = 5 . 0118 – ( 8 . 8 421 ± 0.00 08 )f(n) + (0. 8624 ± 0.0001)f( ε ) – (0.003 9 ± 0.0000)B – (0.03 68 ± 0.0000)E T + (0.00 36 ± 0.0000) δ 2 – (0.00 32 ± 0.0000)V M . N =7; R =1.0; S =0.000; F =10.8537. The polarizability, basicity (B), E T , V M and δ 2 of solvent have effect on the oxidation process. Correlation equations for effective rate constants for other temperatures are similar. The correlation equation for effective energies of activation ( E akt ) and the basic physicochemical parameters of solvents has the form: l g Е а kt = 0 . 8844 + (0.0008 ± 0.0003) B + (0.0142 ± 0.0031) E T . N =7; R =0.9592; S =0.0409; F =86.3553. The basicity ( B ) and E T parameters of solvent have an effect on the energy of the activation process. The proposed correlation equations relate the parameters of the transition state of the oxidation process and the physic-chemical parameters of solvents. Keywords: N,N–dimethylaniline, oxidation reaction, peroxynonanic acid, rate constant, activation energy, correlation equation.