We evaluated the absolute values of the heat capacity of polymer solids composed of polyesters and poly(oxide)s below the glass transition temperature. The frequencies of the skeletal and group-vibration modes were calculated by the Tarasov and Einstein equations, respectively. Furthermore, the estimated heat capacity was corrected by the difference between the heat capacities measured at constant pressure and at constant volume. The heat capacity contributing to the skeletal vibration can be expressed by one- and three-dimensional Tarasov equations, and the contribution of the group vibration can be determined by substituting the absorption frequency obtained from infrared absorption measurements for the frequency value in the Einstein equation. In this combination of equations, the absolute value of the heat capacity was obtained with only three fitting parameters. We thus reproduced the measured heat capacities of eight polyester and five poly(oxide) polymer solids with a carbon and oxygen backbone. The reproduced and experimental heat capacities of all samples except polycaprolactone and poly(3,3-bis(chloromethyl)oxetane) agreed within ±2.5%, and the errors for polycaprolactone and poly(3,3-bis(chloromethyl)oxetane) were within ±4.0%. To better understand the heat capacities of polymer solids and considering that more than a dozen types of data on the absolute heat-capacity values of polymer compounds already exist, we evaluated the heat capacities of eight polyesters and five poly(oxide)s polymer solids with a carbon and oxygen backbone. Our calculations combined the Tarasov equation, the Einstein equation, and the ( C p − C V ) correction term, accounting for the degrees of freedom of the monomer units. Using the combined Tarasov and Einstein equations, the heat capacities of the analyzed polymer solids were reproduced by only three fitting parameters. The reproduced and experimental heat capacities of all samples except polycaprolactone and poly(3,3-bis(chloromethyl)oxetane) agreed within ±2.5%, and the errors for polycaprolactone and poly(3,3-bis(chloromethyl)oxetane) were within ±4.0%.

中文翻译：

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由聚酯和聚（氧化物）组成的聚合物固体的热容量，在玻璃化转变温度以下评估

我们评估了低于玻璃化转变温度的由聚酯和聚（氧化物）组成的聚合物固体的热容量的绝对值。骨架和群振动模式的频率分别由塔拉索夫和爱因斯坦方程计算。此外，估计的热容量通过在恒定压力和恒定体积下测量的热容量之间的差异进行校正。对骨架振动有贡献的热容可以用一维和三维Tarasov方程表示，群振动的贡献可以通过用红外吸收测量获得的吸收频率代替爱因斯坦方程中的频率值来确定。在这个等式组合中，热容量的绝对值仅通过三个拟合参数获得。因此，我们再现了八种聚酯和五种具有碳和氧主链的聚（氧化物）聚合物固体的热容量。除聚己内酯和聚（3,3-双（氯甲基）氧杂环丁烷）外，所有样品的再现热容和实验热容均在±2.5%以内，聚己内酯和聚（3,3-双（氯甲基）氧杂环丁烷）的误差在±4.0%。为了更好地理解聚合物固体的热容，并考虑到已经存在十几种关于聚合物化合物绝对热容值的数据，我们评估了八种聚酯和五种聚（氧化物）聚合物固体的热容碳和氧的骨架。我们的计算结合了塔拉索夫方程、爱因斯坦方程、和 ( C p - CV ) 修正项，说明单体单元的自由度。使用组合的塔拉索夫和爱因斯坦方程，分析的聚合物固体的热容量仅通过三个拟合参数重现。除聚己内酯和聚（3,3-双（氯甲基）氧杂环丁烷）外，所有样品的再现热容和实验热容均在±2.5%以内，聚己内酯和聚（3,3-双（氯甲基）氧杂环丁烷）的误差在±4.0%。