Crystallization

Since the first publication of this definitive work nearly 40 years ago, this fourth edition has been completely rewritten. Crystallization is used at some stage in nearly all process industries as a method of production, purification or recovery of solid materials. Incorporating all the recent developments and applications of crystallization technology, Crystallization gives clear accounts of the underlying principles, a review of the past and current research themes and guidelines for equipment and process design. This new edition introduces and enlarges upon such subjects as: · Control and Separation of polymorphs and chiral crystals · Micro- and macro-mixing and the use of computer fluid dynamics · Seeding and secondary nucleation in batch crystallization processes · Incorporation of upstream and downstream requirements into design procedures for crystallization plant · Computer-aided molecular design and its use in crystal habit modifier selection Crystallization provides a comprehensive overview of the subject and will prove invaluable to all chemical engineers and industrial chemists in the process industries as well as crystallization workers and students in industry and academia. Crystallization is written with the precision and clarity of style that is John Mullin's hallmark - a special feature being the large number of appendices that provide relevant physical property data. Covers all new developments and trends in crystallization. Comprehensive coverage of subject area. Contents......Page 5 Preface to 4th edition......Page 8 Preface to 1st edition......Page 10 Nomenclature and units......Page 12 1.1 Liquid crystals......Page 17 1.2 Crystalline solids......Page 19 1.3 Crystal symmetry......Page 20 1.4 Crystal systems......Page 23 1.5 Miller indices......Page 26 1.6 Spare lattices......Page 29 1.7 Solid state bonding......Page 31 1.8 Isomorphs and polymorphs......Page 32 1.9 Enantiomorphs and chirality......Page 34 1.10 Crystal habit......Page 38 1.11 Dendrites......Page 40 1.12 Composite crystals and twins......Page 41 1.13 Imperfections in crystals......Page 43 2.1 Density......Page 48 2.2 Viscosity......Page 51 2.3 Surface tension......Page 55 2.4 Diffusivity......Page 57 2.5 Refractive index......Page 63 2.7 Crystal hardness......Page 64 2.8 Units of heat......Page 65 2.9 Heat capacity......Page 66 2.10 Thermal conductivity......Page 70 2.11 Boiling, freezing and melting points......Page 71 2.12 Enthalpies of phase change......Page 74 2.13 Heats of solution and cystallization......Page 78 2.14 Size classification of crystals......Page 80 3.2 Solvent selection......Page 102 3.3 Expression of solution composition......Page 106 3.4 Solubility correlations......Page 108 3.5 Theoretical crystal yield......Page 112 3.6 Ideal and non-ideal solutions......Page 114 3.7 Particle size and solubility......Page 124 3.8 Effect of impurities on solubility......Page 126 3.9 Measurement of solubility......Page 128 3.10 Prediction of solubility......Page 136 3.12 Supersolubility......Page 139 3.13 Solution structure......Page 148 4.1 The phase rule......Page 151 4.2 One-component systems......Page 152 4.3 Two-component systems......Page 155 4.4 Enthalpy-composition diagrams......Page 162 4.5 Phase change detection......Page 167 4.6 Three-component systems......Page 172 4.7 Four-component systems......Page 185 4.8 'Dynamic' phase diagrams......Page 195 5 Nucleation......Page 197 5.1 Primary nucleation......Page 198 5.2 Seconary nucleation......Page 211 5.3 Metastable zone widths......Page 217 5.4 Effect of impurities......Page 221 5.5 Induction and latent periods......Page 222 5.6 Interfacial tension (surface energy)......Page 226 5.7 Ostwald's rule of stages......Page 230 6.1 Crystal growth theories......Page 232 6.2 Growth rate measurements......Page 252 6.3 Crystal growth and dissolution......Page 276 6.4 Crystal habit modification......Page 285 6.5 Polymorphs and phase transformations......Page 296 6.6 Inclusions......Page 300 7.1 Recrystallization schemes......Page 305 7.2 Resolution of racemates......Page 311 7.3 Isolation of polymorphs......Page 316 7.4 Recrystallization from supercritical fluids......Page 318 7.5 Zone refining......Page 319 7.6 Single crystals......Page 325 8.1 Precipitation......Page 331 8.2 Crystallization from melts......Page 359 8.3 Sublimation......Page 374 8.4 Crystallization from solution......Page 384 9.1 Crystal size distribution (CSD)......Page 419 9.2 Kinetic data measurement and utilization......Page 446 9.3 Crystallizer specficiation......Page 450 9.4 Fluid-particle suspensions......Page 467 9.5 Encrustation......Page 475 9.6 Caking of crystals......Page 479 9.7 Downstream processes......Page 483 Appendix......Page 494 References......Page 552 Author index......Page 593 Subject index......Page 603 Contents 5 Preface to 4th edition 8 Preface to 1st edition 10 Nomenclature and units 12 1 The crystalline state 17 1.1 Liquid crystals 17 1.2 Crystalline solids 19 1.3 Crystal symmetry 20 1.4 Crystal systems 23 1.5 Miller indices 26 1.6 Spare lattices 29 1.7 Solid state bonding 31 1.8 Isomorphs and polymorphs 32 1.9 Enantiomorphs and chirality 34 1.10 Crystal habit 38 1.11 Dendrites 40 1.12 Composite crystals and twins 41 1.13 Imperfections in crystals 43 2 Physical and thermal properties 48 2.1 Density 48 2.2 Viscosity 51 2.3 Surface tension 55 2.4 Diffusivity 57 2.5 Refractive index 63 2.6 Electrolytic conductivity 64 2.7 Crystal hardness 64 2.8 Units of heat 65 2.9 Heat capacity 66 2.10 Thermal conductivity 70 2.11 Boiling, freezing and melting points 71 2.12 Enthalpies of phase change 74 2.13 Heats of solution and cystallization 78 2.14 Size classification of crystals 80 3 Solutions and solubility 102 3.1 Solutions and melts 102 3.2 Solvent selection 102 3.3 Expression of solution composition 106 3.4 Solubility correlations 108 3.5 Theoretical crystal yield 112 3.6 Ideal and non-ideal solutions 114 3.7 Particle size and solubility 124 3.8 Effect of impurities on solubility 126 3.9 Measurement of solubility 128 3.10 Prediction of solubility 136 3.11 Solubility data sources 139 3.12 Supersolubility 139 3.13 Solution structure 148 4 Phase equilibria 151 4.1 The phase rule 151 4.2 One-component systems 152 4.3 Two-component systems 155 4.4 Enthalpy-composition diagrams 162 4.5 Phase change detection 167 4.6 Three-component systems 172 4.7 Four-component systems 185 4.8 'Dynamic' phase diagrams 195 5 Nucleation 197 5.1 Primary nucleation 198 5.2 Seconary nucleation 211 5.3 Metastable zone widths 217 5.4 Effect of impurities 221 5.5 Induction and latent periods 222 5.6 Interfacial tension (surface energy) 226 5.7 Ostwald's rule of stages 230 6 Crystal growth 232 6.1 Crystal growth theories 232 6.2 Growth rate measurements 252 6.3 Crystal growth and dissolution 276 6.4 Crystal habit modification 285 6.5 Polymorphs and phase transformations 296 6.6 Inclusions 300 7 Recrystallization 305 7.1 Recrystallization schemes 305 7.2 Resolution of racemates 311 7.3 Isolation of polymorphs 316 7.4 Recrystallization from supercritical fluids 318 7.5 Zone refining 319 7.6 Single crystals 325 8 Industrial techniques and equipment 331 8.1 Precipitation 331 8.2 Crystallization from melts 359 8.3 Sublimation 374 8.4 Crystallization from solution 384 9 Crystallizer design and operation 419 9.1 Crystal size distribution (CSD) 419 9.2 Kinetic data measurement and utilization 446 9.3 Crystallizer specficiation 450 9.4 Fluid-particle suspensions 467 9.5 Encrustation 475 9.6 Caking of crystals 479 9.7 Downstream processes 483 Appendix 494 References 552 Author index 593 Subject index 603 Since the first publication of this definitive work nearly 40 years ago, this fourth edition has been completely rewritten.


Crystallization is used at some stage in nearly all process industries as a method of production, purification or recovery of solid materials.

Incorporating all the recent developments and applications of crystallization technology, Crystallization gives clear accounts of the underlying principles, a review of the past and current research themes and guidelines for equipment and process design. This new edition introduces and enlarges upon such subjects as:

· Control and Separation of polymorphs and chiral crystals
· Micro- and macro-mixing and the use of computer fluid dynamics
· Seeding and secondary nucleation in batch crystallization processes
· Incorporation of upstream and downstream requirements into design procedures for crystallization plant
· Computer-aided molecular design and its use in crystal habit modifier selection

Crystallization provides a comprehensive overview of the subject and will prove invaluable to all chemical engineers and industrial chemists in the process industries as well as crystallization workers and students in industry and academia.

Crystallization is written with the precision and clarity of style that is John Mullin's hallmark - a special feature being the large number of appendices that provide relevant physical property data.

Covers all new developments and trends in crystallization.

Comprehensive coverage of subject area.