HPMBP与N_(1923)协萃钯(Ⅱ)的性能和动力学研究

STUDY ON THE BEHAVIOUR AND KINETICS OF SYNERGISTIC EXTRACTION OF Pd(Ⅱ)WITH HPMBP AND N_(1(?)23)

本文研究了 HPMBP 与 N_(1923)的氯仿溶液从硝酸介质中协萃钯(Ⅱ)的性能和动力学,结果表明:当[N_(1923)](o)>1.5×10^(-2)mol·1^(-1)时,HPMBP—N_(1923)—CHCl_3体系对 Pd(Ⅱ)出现反协萃效应,应用对应溶液法原理,测得了 HPMBP 与 N_(1923)间的缔合比,计算了缔合物 HPMBP·N_(1923)反应平衡常数β=5.90;HPMBP 与 N_(1923)协萃Pd(Ⅱ)是一级反应,测得了协萃反应的表观活化能 E_f=4.56kJ·mol^(-1),E_b=34.8kJ·mol^(-1),协萃反应的焓变△H=-30.3kJ·mol^(-1).

In the paper,the behaviour of synergistic extraction of P d(Ⅱ) from nitric acid solution with HPMBP(1-phenyl-3-methyl-4-benzoyl- pyrazole-5-one) and primary amine N_(1923) in CHCl_3 is studied.The results show that when[N_(1923)]>1.5×10^(-2) mol.1^(-1) the anti-synergistic extraction effect emerges in this system due to interaction between HPMBP and N_(1923). According to the theory of the correspondence solution the reactron of asso- ciation is determined to be best represented by HPMBP_(0)+N_(1923(0))——HPMBP.N_(1923(0)) and the equilibrium constant of association reaction is calculated to be equal to 5.90. The kinetics of synergistic extraction of Pd(Ⅱ)from nitric acid solution with HPMBP and N_(1923) in CHCl_3 were investigated.The experimental results show that the aforementioned synergistic extraction reaction for Pd(Ⅱ)is a first order reaction.The values of apparent activation energy of the positive and counter synergistic extraction reaction at 25±1℃ are determined as follows: E_f=4.56 kJ·mol^(-1) E_b=34.80 kJ·mol^(-1) The enthalpy change of the synergistic extraction reaction is H=E_f-E_h=-30.3 kJ·mol^(-1)