Grenke Julia H, Elliott Janet A W
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9, Canada.
J Phys Chem B. 2025 Feb 20;129(7):1997-2012. doi: 10.1021/acs.jpcb.4c03909. Epub 2025 Feb 6.
Water is vital to all facets of life and is anomalously behaving in its condensed states, making it continually a substance of interest to researchers. Therefore, attempting to capture its properties via correlations and equations of state is extremely valuable. Liquid water has not been studied as extensively in the low-temperature and high-pressure region as in other regions. Some key applications for correlations in this region are cryopreservation (specifically in certain methods of cryopreservation such as hyperbaric (high-pressure) and isochoric (constant-volume) cryopreservation), deep oceans, hydrospheres, clouds, and precipitation. Although there are not nearly as many models for water at low temperatures and high pressures as there are in other temperature and pressure ranges, there are some models that do currently exist. However, these either do not extend to temperatures and pressures as extreme as the data that exist, or they are complex with large numbers of parameters making them more difficult for application. Herein, we present a new correlation for liquid water valid for the temperature range of 200-300 K (-73-27 °C) and pressure range of 0.1-400 MPa that can analytically calculate volume, isothermal compressibility, isobaric expansivity, constant pressure heat capacity, and speed of sound, using only 17 adjustable parameters. The analytical expressions that we derived, and the fitting method that we used can also be applied to other fluids of interest in the future.
水对生命的各个方面都至关重要,并且在其凝聚态下表现异常,这使得它一直是研究人员感兴趣的物质。因此,试图通过关联式和状态方程来描述其性质极具价值。液态水在低温高压区域的研究不如在其他区域广泛。该区域关联式的一些关键应用包括低温保存(特别是在某些低温保存方法中,如高压和等容低温保存)、深海、水圈、云层和降水。尽管低温高压下水的模型数量远不及其他温度和压力范围,但目前确实存在一些模型。然而,这些模型要么无法涵盖与现有数据一样极端的温度和压力范围,要么过于复杂,参数众多,难以应用。在此,我们提出了一种新的液态水关联式,适用于200 - 300 K(-73 - 27°C)的温度范围和0.1 - 400 MPa的压力范围,该关联式仅使用17个可调参数就能解析计算体积、等温压缩率、等压膨胀系数、定压热容和声速。我们推导的解析表达式以及所使用的拟合方法未来也可应用于其他感兴趣的流体。