Abstract Excess molar volumes, VE, for the binary mixtures of cyclohexanone with n-, sec-, or tert-butylbenzene were measured over the entire composition range at (298.15, 303.15, 308.15 and 313.15) K and 0.1 MPa, by means of a vibrating-tube densimeter. VE data are sigmoid shape for the studied mixtures of cyclohexanone + n-butylbenzene (with negative VE values at lower mole fractions of cyclohexanone) and negative for the mixtures of cyclohexanone + sec-butylbenzene, and cyclohexanone + tert-butylbenzene over the whole composition range. The absolute values of excess equimolar volumes vary in the order: tert-butylbenzene > sec-butylbenzene > n-butylbenzene. The VE in the studied systems increase as the rising temperature. The Redlich-Kister equation was applied to fit the experimental data. Using the coefficients of the Redlich–Kister equation, excess partial molar volumes at infinite dilution, V ¯ i E, ∞ were calculated for the three binary systems. Molecular non-bond energy, E for binary mixtures at the mole fraction of 0.5 and temperature of 298.15 K also were calculated by the MD simulations. The Prigogine–Flory–Patterson theory and Graph-theoretical approach were examined for the suitability by correlating experimental VE data with compositions.

中文翻译：

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环己酮与正、仲或叔丁基苯的摩尔体积过大：PFP 理论和图论方法的应用

摘要 在 (298.15、303.15、308.15 和 313.15) K 和 0.1 MPa 的整个组成范围内测量环己酮与正、仲或叔丁基苯的二元混合物的过量摩尔体积 VE振动管密度计。所研究的环己酮 + 正丁基苯混合物的 VE 数据为 S 形（环己酮摩尔分数较低时 VE 值为负），而环己酮 + 仲丁基苯和环己酮 + 叔丁基苯的混合物在整个组成范围内的 VE 数据为负. 过量等摩尔体积的绝对值按顺序变化：叔丁基苯 > 仲丁基苯 > 正丁基苯。所研究系统中的 VE 随着温度升高而增加。应用 Redlich-Kister 方程来拟合实验数据。使用 Redlich-Kister 方程的系数，计算了三个二元系统在无限稀释时的过量部分摩尔体积 V¯ i E, ∞。分子非键能 E 对于摩尔分数为 0.5 和温度为 298.15 K 的二元混合物也通过 MD 模拟计算。通过将实验 VE 数据与成分相关联，检查了 Prigogine-Flory-Patterson 理论和图论方法的适用性。