{"title":"临界点现象学理论和物理变量的基本状态方程","authors":"I. V. Kudryavtseva, S. V. Rykov","doi":"10.1134/S0036024424701632","DOIUrl":null,"url":null,"abstract":"<p>The linear Scofield–Litster–Ho (LM) model is used to obtain a representation of the scaling hypothesis (SH) similar in structure to the SH representation. The new representation follows from the phenomenological theory of the Migdal critical point and allows the construction of an equation of state in physical variables, in accordance with the requirements of the scale theory. As in the Berestov critical point model, isochoric heat capacity reduced to absolute temperature (<span>\\({{C}_{{v}}}\\)</span>/<i>T</i>) is used as a scale factor in the proposed critical point model. Based on Benedek’s hypothesis, scale functions of Helmholtz free energy in density–temperature variables not inferior to the corresponding LM scale functions can be calculated using the proposed SH model. In contrast to scale functions calculated on the basis of Migdal’s SH representations, free energy scale functions calculated within the proposed critical point model do not contain integrals of differential binomials. A unified fundamental equation of state in the context of the new SH concept is proposed and tested by describing the equilibrium properties of methane in the 90.6941–620 K range of temperatures at pressures up to 600 MPa.</p>","PeriodicalId":767,"journal":{"name":"Russian Journal of Physical Chemistry A","volume":"98 11","pages":"2461 - 2474"},"PeriodicalIF":0.7000,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Phenomenological Theory of the Critical Point and the Fundamental Equation of State in Physical Variables\",\"authors\":\"I. V. Kudryavtseva, S. V. Rykov\",\"doi\":\"10.1134/S0036024424701632\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The linear Scofield–Litster–Ho (LM) model is used to obtain a representation of the scaling hypothesis (SH) similar in structure to the SH representation. The new representation follows from the phenomenological theory of the Migdal critical point and allows the construction of an equation of state in physical variables, in accordance with the requirements of the scale theory. As in the Berestov critical point model, isochoric heat capacity reduced to absolute temperature (<span>\\\\({{C}_{{v}}}\\\\)</span>/<i>T</i>) is used as a scale factor in the proposed critical point model. Based on Benedek’s hypothesis, scale functions of Helmholtz free energy in density–temperature variables not inferior to the corresponding LM scale functions can be calculated using the proposed SH model. In contrast to scale functions calculated on the basis of Migdal’s SH representations, free energy scale functions calculated within the proposed critical point model do not contain integrals of differential binomials. A unified fundamental equation of state in the context of the new SH concept is proposed and tested by describing the equilibrium properties of methane in the 90.6941–620 K range of temperatures at pressures up to 600 MPa.</p>\",\"PeriodicalId\":767,\"journal\":{\"name\":\"Russian Journal of Physical Chemistry A\",\"volume\":\"98 11\",\"pages\":\"2461 - 2474\"},\"PeriodicalIF\":0.7000,\"publicationDate\":\"2024-10-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Russian Journal of Physical Chemistry A\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S0036024424701632\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Journal of Physical Chemistry A","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S0036024424701632","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
斯科菲尔德-利特斯特-霍(LM)线性模型被用来获得一种结构上类似于标度假说(SH)的表征。新的表示法源自米格达尔临界点的现象学理论,可以根据尺度理论的要求构建物理变量状态方程。与别列斯托夫临界点模型一样,等时热容还原为绝对温度(\({{C}_{v}}}\)/T)在拟议的临界点模型中被用作比例因子。根据贝内德克的假设,可以利用所提出的 SH 模型计算出密度-温度变量中的亥姆霍兹自由能尺度函数,其数值不小于相应的 LM 尺度函数。与根据 Migdal 的 SH 表示法计算的标度函数不同,在拟议的临界点模型中计算的自由能标度函数不包含微分二项式的积分。通过描述甲烷在 90.6941-620 K 温度范围内、最高 600 MPa 压力下的平衡特性,提出并测试了新 SH 概念下的统一基本状态方程。
Phenomenological Theory of the Critical Point and the Fundamental Equation of State in Physical Variables
The linear Scofield–Litster–Ho (LM) model is used to obtain a representation of the scaling hypothesis (SH) similar in structure to the SH representation. The new representation follows from the phenomenological theory of the Migdal critical point and allows the construction of an equation of state in physical variables, in accordance with the requirements of the scale theory. As in the Berestov critical point model, isochoric heat capacity reduced to absolute temperature (\({{C}_{{v}}}\)/T) is used as a scale factor in the proposed critical point model. Based on Benedek’s hypothesis, scale functions of Helmholtz free energy in density–temperature variables not inferior to the corresponding LM scale functions can be calculated using the proposed SH model. In contrast to scale functions calculated on the basis of Migdal’s SH representations, free energy scale functions calculated within the proposed critical point model do not contain integrals of differential binomials. A unified fundamental equation of state in the context of the new SH concept is proposed and tested by describing the equilibrium properties of methane in the 90.6941–620 K range of temperatures at pressures up to 600 MPa.
期刊介绍:
Russian Journal of Physical Chemistry A. Focus on Chemistry (Zhurnal Fizicheskoi Khimii), founded in 1930, offers a comprehensive review of theoretical and experimental research from the Russian Academy of Sciences, leading research and academic centers from Russia and from all over the world.
Articles are devoted to chemical thermodynamics and thermochemistry, biophysical chemistry, photochemistry and magnetochemistry, materials structure, quantum chemistry, physical chemistry of nanomaterials and solutions, surface phenomena and adsorption, and methods and techniques of physicochemical studies.