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사슬길이가 다른 알킬벤젠술폰산 수용액에서 이소부틸렌의 반응성 흡수와 용해도

Reactive Absorption and Solubilities of Isobutylene in the Aqueous Solutions of Akylbenzenesulfonic Acids with Different Chain Lengths

HWAHAK KONGHAK, December 1990, 28(6), 712-719(8), NONE
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Abstract

p-Toluenesulfonic acid, ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, 황산 등 산용액에서 이소부틸렌의 용해도를 측정하고 균일 용액의 산 매체 중에서 산의 작용을 화학적 복합체 모델을 이용하여 설명하였다. 산의 농도의 증가에 따라 용해도는 급격히 증가하였는데 이는 산에 의한 산 복합체 혹은 화학적 반응에 의한 t-butyl alcohol이 생성되기 때문이다. 산의 알킬기의 사슬이 증가하면, 저 농도에서는 몰당 용해효율이 증가하나, 고농도에서는 그 효율이 감소하였다. 그러나 화학적 전환이 예상되는 농도 이상에서는 오히려 증가하여 전이 농도에서 최소치를 나타내었다. 이소부틸렌의 복합체 형성에 의한 평형반응과 Wilson 모델을 고려하여 활동도 계수를 계산하였는데 계산에 이용된 모든 산에서 화학 평형상수에 따른 영향이 크게 나타났다. 특히 p-toluenebenzenesulfonic acid의 경우 황산이나 ethylbenzenesulfonic acid의 경우보다 활동도 계수를 크게 저하시켜 같은 농도에서 산의 흡수효율이 증가하였다. 일정한 산 농도에서 p-toluenesulfonic acid와 dodecylbenzenesulfonic acid의 비를 조절하여 혼합용매를 만들어 이소부틸렌을 흡수시킨 결과 용해효율은 선형적으로 증감하고 있었다. 이는 흡수현상이 마이셀 등 내부구조에 의한 용해라기 보다는 산도에 의한 화학적 복합체의 형성이 주된 흡수기구이기 때문이다.
In the aqueous solutions of p-toluenesulfonic acid, ethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, and sulfuric acid, the solubilities of isobutylene were determined by the volumetric method at 33℃. Following the pseudobinary complexation model, the activities of isobutylene were determined for all acids, based on the Wilson model incorporated with the chemical theory. In solubilizing isobutylene, the significant increase of the equilibrium constant K, and the chemical conversion to tert-butyl alcohol suggested that the chemical complexation of isobutylene with acids might play a key role in the mechanism of the solubilization. By increasing the chain length of alkylbenzene-sulfonic acids, it is also found that the efficiencies of acids in solubilizing isobutylene were enhanced at lower concen-trations, but significantly reduced at higher concentrations. After a transition concentration where there appeared minima, the efficiencies of acids were greatly enhanced, indicating that the chemical conversion to t-butyl alcohol istriggered by acids. Further, the solubilizing efficiencies of mixed acids consisting of p-toluenseulfonic acid and dodecylbenzenesulfonic acid, linearly decreased depending on the effective chain hength at a fixed molar concentra-tion of acids, and it may be attributed to the formation of complex by acid rather than to the incorporation of isobutyl-ene into the micelles.

Keywords

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