Jasiok Bernadeta, Postnikov Eugene B, Chorążewski Mirosław
Institute of Chemistry, Department of Physical Chemistry, University of Silesia in Katowice, Szkolna 9, 40-006 Katowice, Poland.
Department of Theoretical Physics, Kursk State University, Radishcheva St., 33, 305000 Kursk, Russia.
Phys Chem Chem Phys. 2019 Jul 24;21(29):15966-15973. doi: 10.1039/c9cp02448d.
In this work, we argue that the volumetric properties of liquids cannot be reproduced by a single isothermal equation of state derived by the compressibility route for the whole pressure region extended up to a GPa pressure but require the consideration of two states associated with qualitatively different molecular packing properties. This is confirmed by examples of polar and non-polar substances within the range of temperatures from 203.15 K to 491.48 K and pressures up to 1200 MPa. The proposed two states model is truly predictive for the high-pressure density and isothermal compressibility using several easily measurable physico-chemical quantities: the density, the isobaric heat capacity, and the speed of sound at atmospheric pressure only. The experimental data on the density for 15 different compressed liquids, given in the literature as a function of temperature and very high-pressures, were used for the comparison and its analysis. The relative absolute average deviation for 2138 experimental data points by a two states model is close to 0.17%.
在这项工作中,我们认为,对于整个压力范围扩展至1吉帕斯卡压力的情况,液体的体积性质无法通过由压缩率路径推导出的单一等温状态方程来再现,而是需要考虑与性质上不同的分子堆积性质相关的两种状态。这在203.15 K至491.48 K温度范围以及高达1200兆帕压力范围内的极性和非极性物质的例子中得到了证实。所提出的双状态模型仅使用几个易于测量的物理化学量:密度、等压热容和常压下的声速,就能对高压密度和等温压缩率进行真正的预测。文献中给出的15种不同压缩液体的密度随温度和极高压力变化的实验数据被用于比较和分析。双状态模型对2138个实验数据点的相对绝对平均偏差接近0.17%。