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Updated Principle of Corresponding States

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Dor Ben-Amotz and Alan D. Gift

Department of Chemistry, Purdue University, West Lafayette, IN 47907-1393

R. D. Levine

Fritz-Haber Research Center, Hebrew University, Jerusalem 91904, Israel

J. Chem. Educ., 2004, 81 (1), p 142

DOI: 10.1021/ed081p142

Publication Date (Web): January 1, 2004

Section:

History, Education, and Documentation

Abstract

Demonstrating the principle of corresponding states is often the first encounter that a beginning student of physical chemistry has with the analysis of real data. This remarkable reduced representation of fluid thermodynamic properties points to a fundamental link between observable macroscopic behavior and molecular properties. Recently compiled experimental measurements and computer simulations offer an opportunity to demonstrate and explain this intriguing connection. In particular, we show how experimental and theoretical equation of state results may be combined to better illustrate the scaling relationship of real rare gases, diatomics, and methane. We demonstrate the connection between thermodynamic properties and the intermolecular interaction potential and establish a link to gas non-idealities, as expressed by the compressibility factor, Z (= PV/nRT), the second virial coefficient, B(T), and the Boyle temperature, T_Boyle (at which the vapor behaves nearly ideally). Conversely, the fact that other fluids, such as He, CO₂, HO, and n-butane, do not globally follow the same reduced behavior implies that these molecules have intermolecular interaction potentials of fundamentally different form. Web-based tables and graphs available from the NIST Chemistry WebBook (accessed Aug 2003) offer ample opportunities to reinforce key concepts using numerical examples and homework problems.

Keywords (Audience):

Upper-Division Undergraduate

Keywords (Domain):

Physical Chemistry

Keywords (Feature):

Research: Science and Education

Keywords (Subject):

Gases

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This article has been cited by 1 ACS Journal articles (1 most recent appear below).

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- The Analysis of Spontaneous Processes Using Equilibrium Thermodynamics
  J. M. Honig and Dor Ben-Amotz
  Journal of Chemical Education2006 83 (1), 132
  We present a pedagogical tool that facilitates the derivation of wide-ranging thermodynamic implications of the second law and, particularly, the consequences of irreversible processes, including a number of important results that are not described in ...
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