Neau S H, Flynn G L
University of Michigan, College of Pharmacy, Ann Arbor 48109.
Pharm Res. 1990 Nov;7(11):1157-62. doi: 10.1023/a:1015984310068.
The expression that relates the ideal mole fraction solubility of a crystalline compound to physicochemical properties of the compound includes a term involving the difference in the heat capacities of the solid and liquid forms of the solute, delta Cp. There are two alternate conventions which are employed to eliminate this term. The first assumes that the term involving delta Cp, or delta Cp itself, is zero. The alternate assumption assigns the value of the entropy of fusion to the differential heat capacity. The relative validity of these two assumptions was evaluated using the straight-chain alkyl para-aminobenzoates as test compounds. The heat capacities of the solid and liquid forms of each of the para-aminobenzoates, near the respective melting point, were determined by differential scanning calorimetry. The data lead one to conclude that the assumption that the differential heat capacity is not usually negligible and is better approximated by the entropy of fusion.
将晶体化合物的理想摩尔分数溶解度与其物理化学性质相关联的表达式包含一个涉及溶质固态和液态热容差(ΔCp)的项。有两种替代惯例用于消除该项。第一种假设涉及ΔCp的项或ΔCp本身为零。另一种假设将熔化熵值赋予微分热容。使用直链烷基对氨基苯甲酸酯作为测试化合物评估了这两种假设的相对有效性。通过差示扫描量热法测定了各对氨基苯甲酸酯在各自熔点附近的固态和液态热容。数据使人们得出结论,即微分热容通常不可忽略且用熔化熵来近似更好这一假设。