气液色谱法测量醇类在惰性溶剂中的无限稀热力学函数

用气液色谱法测量了在不同温度下C_1～C_4醇类的各种异构物在C_(16)～C_(23)正构烷烃、角鲨烷,和角鲨烯中的无限稀活度系数γ_i,偏摩尔过量焓、偏摩尔过量熵。在各种溶剂中γ_i、均大于1,在同一溶剂中γ_i依下列次序减小: 甲醇>乙醇>正丙醇>正丁醇; 正丙醇>异丙醇; 正丙醇>异丁醇>仲丁醇>叔丁醇同一种醇在角鲨烯中的γ_i较在角鲨烷中为低。异构醇类的低于正构醇类。所测的有随的增加而增加的趋势。

INFINITZ DILUTE THERMODYNAMIC QUANTITIES OF ALCOHOLS IN INERT SOLVENTS BY GAS-IQUID CHROMATOGRAPHY

The infinite dilution activity coefficients γ_i, partial molar excess enthalpies H_i~E and entropies S_i~E of C_1—C_4 alcohols have been measured in C_(16)—C_(23) normal alkanes, squalane and squalene by gas-liquid chromatography。 The obtained infinite dilution activity coefficients are all greater than unity. In the same stationary Iiquid, the values of γ_i follow the order: methanol>ethanol>n-propanol>n-butanol; n-propanol>isopropanol; n-butanol>isobutano>sec-butanol>tert-butanol. It has been found that the activity coefficient of the same alcohol in squalane is greater than in squalene. The excess enthalpy of normal alcohols is greater than isomeric alcohols about 1.5 kJ.mol~(-1). The measured partial molar excess enthalpies and entropies are all positive. A linear relationship have been observed between the H_i~E and S_i~E values of the alcohols in the aliphatic hydrocarbon solvents, the results of which can be represented asH_i~E-431 S_i~E+1620 (J.mol~(-1))