Kinetics of the Bromine-exchange Reaction of Antimony(Ⅲ) Bromide with Organic Bromide in the Organic Solvents

Abstract

삼브롬화안티몬과 브롬화이소프로필 사이의 브롬 교환반응의 반응속도를 니트로벤젠과 1,2,4-트리클로로벤젠용매에서 측정하였다.

삼브롬화안티몬과 브롬화이소프로필 사이의 브롬 교환반응의 반응차수는 니트로벤젠 용매 및 1,2,4-트리클로로벤젠용매에서 모두 삼브롬화안티몬에 대해서는 1.4차이었으며 브롬화이소프로필에 대해서는 0차이었다. 이반응의 반응속도상수는 니트로벤젠 용매를 사용하였을 경우 22℃에서 3.3×10??(l/mole)??sec??이었으며 1,2,4-트리클로로벤젠 용매를 사용하였을 경우 22℃에서 4.1×10??(l/mole)??sec??이었다.

또 활성화에너지, 활성화엔트로피, 활성화엔탈피, 잦음율과 같은 열역학적 함수를 구하였으며 삼브롬화안티몬과 유기브롬화물 사이의 브롬 교환반응의 반응메카니즘도 제시하였다.

The rate of the bromine-exchange reaction between antimony(Ⅲ) bromide and isopropyl bromine in nitrobenzene and in 1,2,4-trichlorobenzene has been determined, utilizing antimony(Ⅲ) bromine labeled with radioactive bromine. The results indicate that the exchange reaction between antimony(Ⅲ) bromide and isopropyl bromide is 1.4th order with respect to antimony(Ⅲ) bromide and zero order with respect to isopropyl bromide in each of the two solvents. The reaction rate constants of these reatcion determined at 22˚are 3.3×10??(l/mole)??sec?? in nitrobenzene and 4.1×10??(l/mole)??sec?? in 1,2,4-trichlorobenzene.

The activation energy, the enthalphy of activation, and the entropy of activation for the exchange reaction have been determined. It has also been observed that antimony(Ⅲ) bromide exchanges bromine slower with isopropyl bromide than tert-butyl bromide and benzyl bromide. reaction mechanism for the bromine exchange is proposed.

The rate of the bromine-exchange reaction between antimony(Ⅲ) bromide and isopropyl bromine in nitrobenzene and in 1,2,4-trichlorobenzene has been determined, utilizing antimony(Ⅲ) bromine labeled with radioactive bromine. The results indicate that the exchange reaction between antimony(Ⅲ) bromide and isopropyl bromide is 1.4th order with respect to antimony(Ⅲ) bromide and zero order with respect to isopropyl bromide in each of the two solvents. The reaction rate constants of these reatcion determined at 22˚are 3.3×10??(l/mole)??sec?? in nitrobenzene and 4.1×10??(l/mole)??sec?? in 1,2,4-trichlorobenzene.

The activation energy, the enthalphy of activation, and the entropy of activation for the exchange reaction have been determined. It has also been observed that antimony(Ⅲ) bromide exchanges bromine slower with isopropyl bromide than tert-butyl bromide and benzyl bromide. reaction mechanism for the bromine exchange is proposed.