Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Thermodynamic Studies on the Structure of Binary Mixed Solvents(Ⅰ). Partial Molal Enthalpies of Alcohol-Cosolvent Mixtures

이성분 혼합용매의 구조에 대한 열역학적 연구(제1보). 알코올-Cosolvent 혼합물의 분몰랄엔탈피

  • Nah, Sang Moo (Department of Chemistry, College of Natural Sciences, Ajou University) ;
  • Park, Young Dong (Department of Chemistry, College of Natural Sciences, Ajou University)
  • 나상무 (아주대학교 자연과학대학 화학과) ;
  • 박영동 (아주대학교 자연과학대학 화학과)
  • Published : 19970200
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Abstract

Calorimetric measurements have been carried out for the binary mixture between protic, ROH (R=Me, Et) and dipolar aprotic solvents, MeCN,$Me_2CO,\;MeNO_2(or EtNO_2)$in order to investigate the molecular interaction and liquid structure of isodielectric solvents. From the measured partial molar enthalpies of the solutions, excess enthalpies for the mixing process were determined. The hydrogen bond strength between two components decreases in the order of$ROH-ROH>ROH-Me_2CO>ROH-MeCN>ROH-MeNO_2(or EtNO_2)$and the hydrogen bond donor acidity decreases in the order of MeOH>EtOH. From this result, we can conclude that the most important interaction for the formation of binary liquid mixture comes from the specific hydrogen bond.

등유전성 용매내에서 분자간 상호작용과 액체구조에 대한 정보를 얻기 위하여 양성자성 용매(protic solvent)인 ROH(R=Me, Et)와 양극성 비양성자성 용매(dipolar aprotic solvent)인 MeCN,$Me_2CO,\;MeNO_2(or EtNO_2)$간의 이성분 혼합물에서 각 성분의 분몰 용해엔탈피를 열량계법으로 측정하고 이를 이용하여 mixing과정에 대한 잉여엔탈피를 결정하였다. 이로부터 두 성분간의 수소결합 세기는$ROH-ROH>ROH-Me_2CO>ROH-MeCN>ROH-MeNO_2(or EtNO_2)$순으로 감소하며, ROH의 수소결합주게 산도(hydrogen bond donor acidity)는 MeOH>EtOH의 순으로 감소하며 이로부터 이성분 액체혼합물이 형성될 때의 에너지론(energetics)에 미치는 가장 강한 상호작용이 특별한 수소결합에 기인됨을 알 수 있었다.

Keywords

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