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用Kretschmer-Wiebe模型结合Hildebrand-Scatchard公式处理含醇体系的活度系γ_i,得到醇类的自身缔合平衡常数K_A和氢键生成焓h_A。在烷烃溶剂中,K_A与烷烃的碳原子数关系不显著。在同一溶剂中,K_A依下列顺序减小: 甲醇>乙醇>正丙醇>正丁醇; 正丙醇>异丙醇; 正丁醇>异丁醇>仲丁醇>叔丁醇。所测醇类的h_A的平均值为:k_A=-24.3±0.6kJmol~(-1),与醇类的碳原子数及异构关系不显著计算出醇类-角鲨烯体系偏离Hildebrand-Scatchard公式的相互作用常数l_(AB),l_(AB)均为负值,|l_(AB)|依下列顺序减小: 甲醇>乙醇>正丙醇>正丁醇; 正丙醇>异丙醇; 正丁醇>异丁醇>仲丁醇>叔丁醇
The Krebschmer-Wiebe model combined with the Hildebrand-Scatchard equation was used to treat the alcoholic system γ_i. The self-association equilibrium constant K_A and the hydrogen-bonding enthalpy h_A were obtained. In the alkane solvent, K_A has no significant relationship with the number of carbon atoms in alkanes. In the same solvent, K_A decreases in the following order: methanol> ethanol> n-propanol> n-butanol; n-propanol> isopropanol; n-butanol> isobutanol> sec-butanol> t-butanol. The average value of h_A for the tested alcohols is: k_A = -24.3 ± 0.6kJmol -1, which is not significantly related to the number of carbon atoms and the isomerization of the alcohols. The Squalene system departs from Hildebrand-Scatchard The correlation coefficients l_ (AB) and l_ (AB) of the formula are all negative, | l_ (AB) | decreases in the following order: methanol> ethanol> n-propanol> n-butanol; n-propanol> isopropanol ; N-butanol> isobutanol> sec-butanol> tert-butanol