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Thermodynamic Properties of Fluids and Fluid Mixtures

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Thermodynamic Properties of Fluids and Fluid Mixtures

I. M. Abdulagatov
National Institute of Standards and Technology, Boulder

V. A. Rabinovich
All-Russian Research Center of Standardization, Information and Certification of Raw and Processed Materials and Substances of the Russian State Standards Committee, Russian Metrological Academy, Moscow, Russia

V. I. Dvoryanchikov
Institute of Problems in Geothermy, Makhachkala, Russia


This book considers various methods of experimental study of thermal and caloric properties of pure substances and binary mixtures in wide ranges of the variation of independent variables, including the near critical region. Its 350 pages contain the results of experiments that are the principal source of information for the great majority of properties of the most common substances and materials. Experimental methods of determining thermodynamic properties of pure substances and binary mixtures in wide parameters' ranges including near-critical regions are considered. A brief survey of equipment designed in various laboratories in the former Soviet Union is given; the main units of the equipment, their characteristics, and the experimental procedures are described. Containing over 100 tables and figures, and exhaustively researched (over 500 references are listed), this monograph is addressed to both theorists and experimenters working in the fields of molecular physics, chemical technology, and power engineering, as well as researchers, lecturers, postgraduates, and students.

350 pages, © 1999


1 Methods of Studying (p, V, T, x) Properties of Fluids and Fluid Mixtures: Experimental Results
1.1 Method of Hydrostatic Weighing
1.2 Method of Variable-Volume Piezometer
1.3 Method of Constant-Volume Piezometer
2 Methods of Studying Constant-Volume Heat Capacity of Fluids and Fluid Mixtures: Experimental Results
2.1 Classical Method of Adiabatic Calorimetry
2.2 Method of High-Temperature High-Pressure Integrating Adiabatic Calorimeter
2.2.1 Main Principles Underlying the Method
2.2.2 Construction of the Calorimeter
2.2.3 Heat Capacity of Empty Calorimeter
2.2.4 Measurement of the Working Volume of the Calorimeter
2.2.5 Preparation of the Calorimeter and the Technique of Measurements
2.2.6 Errors in Measuring Cv
2.2.7 Measurements of Isochoric Heat Capacity Cv near the Coexistence Curve
3 Compensation-Relaxation Method for Simultaneously Measuring Isochoric Heat Capacity Cv and (p, V, T) Properties of Liquids and Gases
3.1 General Description of the Apparatus and the Main Principles of its Operation
3.2 Construction of Piezocalorimeter Vessel
3.3 Construction of the Isothermal Shield
3.4 System of Measuring Pressure and Mass
3.5 Power-Supply and Control Unit (PSCU)
3.6 Some Specific Features of the Calorimeter Functioning in the Relaxation-Compensation Regime
3.7 Quantitative Estimation of Disturbing Factors
3.7.1 Thermal Expansion of the Calorimeter Vessel
3.7.2 Pressure Effects on the Calorimeter-Vessel Volume
3.7.3 Error of Measuring Heat Capacity of Empty Calorimeter
3.7.4 Corrections for Nonideal Isochoricity of the Process
3.8 Equations for Calculating Cc, Cv, and Cp
3.9 Equations for Calculating Pressure, Density, and the Derivatives (∂p/∂T)v and (∂p/∂V)T
3.10 Calibration of the Experimental Apparatus
3.11 Measuring Heat Capacity of the Calorimetric System
3.12 Estimation of Corrections and Measurement Accuracy
3.13 Experimental Results
3.13.1 Measuring (p, ρ, T) Properties of Propanol
3.13.2 Measuring Heat Capacities Cv and Cp
3.13.3 Measuring Temperature Coefficient of Pressure
4 Equations of State for Pure Fluids and Fluid Mixtures
4.1 Potential Functions of Intermolecular Interactions and Virial Coefficients
4.1.1 Hard-Sphere Equation of State [299]
4.1.2 PHCT Model of the Equation of State
4.1.3 SPHCT Model of the Equation of State
4.1.4 Hole Quasichemical Model
4.2 Classical Equations of State
4.2.1 Van der Waals-Type Equations of State
4.2.2 Cubic Equations of State
4.2.3 Virial Equations of State
4.2.4 Calculation of Mixture Properties
4.3 Non-Classical Equations of State. Crossover Models