Chemical Thermodynamics: Volume 2 (Specialist Periodical Reports),Used

Excerpt. Reprinted by permission. All rights reserved.Chemical Thermodynamics Volume 2A Review of the Recent LiteratureBy M. L. McGlashan The Royal Society of ChemistryCopyright 1978 The Chemical SocietyAll rights reserved.ISBN: 9780851862637ContentsChapter 1 The Measurement of Thermodynamic Excess Functions of Binary Liquid Mixtures By K. N. Marsh, 1,Chapter 2 Activity Coefficients at Infinite Dilution from GasLiquid Chromatography By T. M. Letcher, 46,Chapter 3 Experimental Methods for Studying Phase Behaviour of Mixtures at High Temperatures and Pressures By C. L. Young, 71,Chapter 4 Highpressure Phase Diagrams and Critical Properties of Fluid Mixtures By G. M. Schneider, 105,Chapter 5 Mixtures containing a Fluorocarbon By F. L. Swinton, 147,Chapter 6 Specific Interactions in Nonelectrolyte Mixtures By A. G. Williamson, 174,Chapter 7 Volumetric Properties of Gaseous Mixtures By C. M. Knobler, 199,Chapter 8 Critical Exponents for Binary Fluid Mixtures By R. L. Scott, 238,Chapter 9 A Bibliography of Thermodynamic Quantities for Binary Fluid Mixtures Edited by C. P. Hicks, 275,Author Index, 539,CHAPTER 1The Measurement of Thermodynamic Excess Functions of Binary Liquid MixturesBY K. N. MARSH1 IntroductionThis chapter deals with experimental methods for determining the thermodynamic excess functions of binary liquid mixtures of nonelectrolytes. Most of it is concerned with techniques suitable for measurements in the temperature range 250 to 400 K and the pressure range 0 to 100 kPa. Techniques suitable for lower temperatures will be briefly reviewed. Techniques for measuring the molar excess Gibbs function GEm the molar excess enthalpy HEm and the molar excess volume VEm will be discussed. The molar excess entropy SEm can only be determined indirectly from either measurements of GEm and HEm at a specific temperature [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII], or from the temperature dependence of [MATHEMATICAL EXPRESSION NOT REPRODUCIBLE IN ASCII]. The molar excess functions have been defined by McGlashan in the Introduction to Volume 1 of this series.Experimental excess functions of liquid mixtures are useful in that they provide data to test theories of liquid mixtures and provide a guide for the formulation of new theories. The data are also useful in the chemical and petroleum industries. This chapter does not contain a summary of experimental data since Chapter 9 of this volume consists of a bibliography of excess function and related measurements on binary mixtures of nonelectrolytes.To date there has been no comprehensive review written on experimental techniques. Williamson's survey 2 in 1967 is now out of date as a number of new techniques have since been published. Moreover, his survey did not include a detailed analysis of the accuracy of the various techniques.The excess Gibbs function, unlike the excess enthalpy and excess volumes, cannot be measured directly. The methods from which GE can be derived include: the simultaneous measurement of the total vapour pressure p, mole fraction y in the vapour phase and mole fraction x in the liquid phase at a fixed temperature, or any two of these three, in either a recirculating still or a static vapourpressure apparatus; gasliquid chromatography; isopiestic measurements; lightscattering measurements; and freezingtemperature determinations combined with excess enthalpies measured over a temperature range. In 1967 Hala et al. gave a detailed review of techniques suitable for vapourliquid equilibrium measurement but their review was confined mainly to recirculating stills. In recent years the dynamic method has been superseded by the static method for measuring isothermal vapourliquid equilibria data. The dynamic method is still commonly used to obtain isobaric data. This review will include only a limited discussion on recirculating stills and the reader is referred to ref. for further information on this method. Rec