Experimental Thermodynamics

Volume 7

By: Ron D. D. Weir (Editor), Theo W. W. de Loos (Editor)

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Hardcover | 1 October 2005

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450 Pages

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This volume is another in the series of IUPAC sponsored monographs that summarize the state of knowledge with respect to experimental techniques in thermochemistry and thermodynamics. Following volume VI, Measurement of Thermodynamic Properties of Single Phases, VI, this book contains descriptions of recent developments in the techniques for measurement of thermodynamic quantities for multiple phases of pure fluids as well mixtures over a wide range of conditions. The precision and accuracy of results obtained from each method was regarded as an essential element in each description. Throughout the text, the quantities, units and symbols are those defined by IUPAC for use in the international community. Measurement of Thermodynamic Properties of Multiple Phases, Volume VII is an invaluable reference source to researchers and graduate students.

Describes the latest techniques for studying multiple phases of pure component systems, using quantities, units and symbols as defined by IUPAC for use in the international community
Illustrates the measurement techniques to obtain activity coefficients, interfacial tension and critical parameters
An invaluable reference source to researchers and graduate students

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Non-Fiction Science Physics Thermodynamics & Heat Engineering & Technology Biochemical Engineering Materials & States of Matter Chemistry Physical Chemistry

List of Contributors	p. xi
Foreword	p. xiii
Introduction	p. 1
Phase Changes in Pure Component Systems: Liquids and Gases	p. 5
Static Measurements	p. 6
Ebulliometry	p. 7
Knudsen Effusion Methods for Vapour Pressure Measurement	p. 9
Conventional Mass-Loss Technique	p. 9
Torsion-Effusion Method	p. 9
Simultaneous Torsion and Mass-Loss Effusion Techniques	p. 11
Isothermal Knudsen Effusion Method in Thermogravimetric-Type Apparatus	p. 12
Non-Isothermal Knudsen Effusion Method in TG-Type Apparatus	p. 13
Mass-Loss Knudsen Technique with a Quartz Crystal Microbalance	p. 13
Mass-Loss Knudsen Technique by Heat-Conducting Calorimetry	p. 14
Mass-Loss Knudsen Technique with a Mass Spectrometry Method	p. 15
Knudsen Cell with Differential Scanning Calorimetry	p. 16
Langmuir Effusion Methods for Vapour Pressure Measurement	p. 17
The Transpiration Method	p. 19
Chromatographic Methods	p. 20
Headspace Analysis	p. 21
GC-Correlations with Retention Times and Vapour Pressures of Reference Compounds	p. 21
GC-Correlations with Net Retention Times	p. 22
Calorimetric Measurements of the Enthalpy of Vaporization	p. 24
Adiabatic Calorimeters	p. 24
Drop Calorimetry Method	p. 26
Differential Calorimetry	p. 26
Conclusions	p. 26
Phase Changes in Pure Component Systems: Liquids and Solids	p. 31
Thermal Methods and Calorimetry	p. 34
Measurements at Normal Pressure	p. 34
Measurements at High Pressure	p. 36
Density and Volume Changes	p. 38
Measurements at Normal Pressure	p. 38
Measurements at High Pressure	p. 39
Melting Curves at High Temperatures and Pressures	p. 41
Miscellaneous Methods	p. 42
Dielectric Measurements	p. 42
Ultrasonic Measurements	p. 42
Other Methods	p. 43
Pure Component Phase Changes: Solid and Solid	p. 49
Classification of Solid-Solid Phase Transitions	p. 50
Thermodynamics of Solid-Solid Phase Transitions	p. 52
Introduction into Soft Modes and the Central Peak	p. 53
Phase Transitions in Plastic Crystals and Fullerenes	p. 54
Experimental Techniques	p. 56
Thermal Methods	p. 56
Optical Methods	p. 57
X-Ray and Neutron Scattering	p. 58
Ultrasonic Methods	p. 59
Magnetic Resonance	p. 59
Review of Recent Developments	p. 60
Inorganic Compounds	p. 60
Organic Compounds	p. 62
Fullerenes	p. 67
Advances in Experimental Techniques and Interpretation of Results	p. 68
Vapour-Liquid Equilibrium at Low Pressure	p. 71
Equipment and Procedures	p. 72
Static Methods	p. 73
Computations from Static Cell Data	p. 74
Semi-Micro Cells	p. 75
Data Reduction from P-x Measurements	p. 76
Sensitivity of Temperature and Pressure	p. 78
Dynamic Methods	p. 80
Attainment of Equilibrium	p. 81
Partial Condensation of Equilibrium Vapour	p. 82
Smooth Boiling	p. 83
Measurement and Control of Temperature and Pressure	p. 84
Measurement of Composition	p. 84
Conclusions	p. 86
Vapour-Liquid Equilibrium at High Pressure	p. 89
Closed-Circuit Methods	p. 90
Static-Analytic Methods	p. 90
Quasi-Static Method (Circulated Phases)	p. 99
Static-Synthetic Methods	p. 103
Open-Circuit Methods	p. 117
Forced Circulation of the Mixture	p. 117
Open Flow of the Gas Phase	p. 121
Conclusions	p. 133
Low-Pressure Solubility of Gases in Liquids	p. 137
Thermodynamics	p. 139
Fundamentals	p. 139
Practical Implementation	p. 149
Instruments, Experimental Techniques, Data Correlation and Selected Results	p. 156
Concluding Remarks	p. 168
Liquid-Liquid Equilibrium	p. 177
Liquid-Liquid Equilibrium in Binary Systems	p. 178
Direct Analytical Methods	p. 178
Synthetic or Turbidimetry Method	p. 180
Volumetric Method	p. 184
Indirect Methods	p. 186
Measurement of very Low Mutual Solubility	p. 186
Measurements in the Vicinity of the Critical Point	p. 188
Test System	p. 190
Liquid-Liquid Equilibrium in Ternary and Multi-Component Systems	p. 190
Determination of the Equilibrium Curves in a Ternary or Pseudo-Ternary System	p. 190
Direct Analytical Method	p. 192
Determination of the Tie Lines in a Ternary System using the Binodal Curve	p. 193
Determining of the Distribution (Partition) Coefficient	p. 194
Basic Monographs	p. 199
Condensed Phases of Organic Materials: Solid-Liquid and Solid-Solid Equilibrium	p. 201
Thermodynamic Treatment	p. 204
The Gibbs Energy Function	p. 204
The Lowest Possible Gibbs Energy	p. 205
Limiting Cases of Experimentation	p. 207
Analysis of the Phase Diagram	p. 208
Polymorphism	p. 212
Experimental	p. 213
Sample Preparation	p. 213
Microcalorimetry	p. 219
X-Ray Diffraction	p. 227
High-Order Phase Transitions	p. 236
Key Systems	p. 242
Naphthalene + 2-Naphthol	p. 242
Tricosane (C[subscript 23]H[subscript 48]) + Pentacosane (C[subscript 25]H[subscript 52])	p. 248
2,2-Dimethylpropane + Carbon Tetrachloride	p. 256
Empirical Relationships	p. 261
Enthalpy-Entropy Compensation	p. 261
Mismatch Parameters	p. 265
Concluding Remarks	p. 270
Condensed Phases of Inorganic Materials: Metallic Systems	p. 275
Solution Thermodynamics and Phase Diagram Development	p. 277
Experimental Methods	p. 284
Microscopic Phase Examination	p. 285
X-Ray Diffraction	p. 287
Emf Cells	p. 288
Vapour Pressure Techniques	p. 293
Thermal Methods	p. 295
Scanning Calorimetry	p. 296
Multi-Component Systems	p. 299
Conclusions	p. 303
Condensed Phases of Inorganic Materials: Ceramic Systems	p. 307
Techniques Yielding Formation Enthalpies	p. 309
Combustion Calorimetry	p. 309
Solution Calorimetry	p. 310
Techniques Yielding Heat Capacities and Entropies	p. 313
Drop Calorimetry	p. 313
Differential Thermal Methods	p. 314
Adiabatic Calorimetry	p. 314
Techniques Yielding Partial Molar Quantities	p. 315
Gas Equilibration Techniques	p. 315
Knudsen Cell Methods	p. 317
Electrochemical Techniques	p. 320
Conclusions	p. 323
Condensed Phases of Inorganic Materials: Molten Salts	p. 327
Structure of Molten Salts	p. 328
Experimental Determination of Thermodynamic Properties	p. 329
Calorimetric Measurements	p. 330
Incorporation of Calorimetric Data into a Thermodynamic Model for Molten Salts	p. 330
Vapour Pressure Methods	p. 332
Electrochemical Methods	p. 332
Solubility Measurements	p. 335
Cryoscopy	p. 335
Thermodynamic Properties from Phase Diagrams	p. 335
Solid and Gas Phases	p. 336
Differential Thermal Analysis (DTA)	p. 336
Mass Spectroscopy	p. 336
Conclusions	p. 337
Measurement of Limiting Activity Coefficients: Non-Analytical Tools	p. 339
Experimental Methods	p. 340
Differential Ebulliometry and Equipment	p. 342
Characterization of an Ebulliometer	p. 344
Principal Ebulliometer Equation	p. 345
Evaluation of E Parameter	p. 346
Evaluation of Holdups (R'/S') and (V'/S')	p. 347
Determination of the Vaporization Ratio [phi]	p. 348
Static Differential Methods	p. 351
Calculation of Equilibrium Liquid Composition, x[subscript 1]	p. 352
Calculation of Activity Coefficient at Infinite Dilution [gamma superscript infinity subscript i]	p. 354
Inert Gas Stripping	p. 355
Attainment of Equilibrium	p. 355
Calculation of Activity Coefficient at Infinite Dilution [gamma superscript infinity subscript 1]	p. 356
Conclusions	p. 356
Measurement of Limiting Activity Coefficients Using Analytical Tools	p. 359
Retention Measurements in GLC	p. 362
Conventional GLC	p. 362
Relative GLC	p. 363
Non-Steady-State GLC	p. 364
Headspace Method of Analysis	p. 366
Static Mass Balance Methods	p. 368
Equilibrium Partitioning in Closed Systems	p. 368
Phase Ratio Variation (PRV) Method	p. 369
Headspace Stepwise Extraction Methods	p. 370
Rate Measurements on Continuous Gas-Liquid Separation Processes	p. 370
Inert Gas Stripping	p. 370
Exponential Saturator Method	p. 373
Distillation Methods	p. 375
Rayleigh Distillation Method (RDIST)	p. 375
Differential Distillation	p. 376
Measurements by Circulation Stills	p. 376
Concluding Remarks	p. 377
Measurement of Surface and Interfacial Tension	p. 383
Terminology	p. 386
Static Methods	p. 387
Capillary Rise and Related Methods	p. 387
Drop and Bubble Shape Methods	p. 389
Spinning Drop Method	p. 392
Oscillating Drop Method	p. 393
Quasi-Static ("Detachment") Methods	p. 393
Drop Volume-Weight	p. 394
du Nouy Ring	p. 396
Wilhelmy Plate	p. 398
Maximum Bubble Pressure	p. 399
Dynamic Surface and Interfacial Tension	p. 400
Oscillating Jet Method	p. 401
Capillary Wave Methods	p. 402
Oscillating Drop and Bubble Methods	p. 403
Maximum Bubble Pressure Method	p. 404
Capillary Pressure and Related Methods	p. 404
Critical Parameters	p. 409
Experimental Techniques	p. 410
Sealed Ampoule Method	p. 410
Flow Method	p. 414
Spontaneous Boiling Methods	p. 416
Open Tube Methods	p. 418
Methods Based on the PvT Behaviour of a Substance	p. 419
Other Methods	p. 420
Note on Experimental Errors	p. 422
Extrapolation Techniques	p. 422
Subject Index	p. 427
Chemical Substance Index	p. 433
Table of Contents provided by Ingram. All Rights Reserved.

Experimental Thermodynamics

Volume 7

At a Glance

Hardcover

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How to return your order

Defective items

You Can Find This Book In

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