Comprehensive Handbook of Calorimetry and Thermal Analysis
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1 Comprehensive Handbook of Calorimetry and Thermal Analysis Michio Sorai Editor-in-Chief The Japan Society of Calorimetry and Thermal Analysis John Wiley & Sons, Ltd
2 Contents Preface xi Acknowledgements List of Contributors xiii xv Part I PRINCIPLES OF CALORIMETRY AND THERMAL ANALYSIS Calorimetry Overview Thermodynamic quantities characteristic of multi-component system Thermodynamic quantities characteristic of surface and interface Thermodynamic quantities in chemical reactions Thermodynamics of non-equilibrium states Biothermodynamics Thermal Analysis Overview Thermal analysis for chemical reactions Thermal analysis for mechanical properties Dynamic viscoelastic phenomena and thermal analysis Reaction kinetics in the solid State Periodic heating method 54 Part II EXPERIMENTAL METHODS Temperature Measurement in Thermal Study Principles and Methods of Calorimetry Classification and basic principles of calorimeters Adiabatic heat capacity calorimetry Heat capacity calorimetry by relaxation method AC calorimetry Laser-flash calorimetry High-temperature calorimetry 80
3 2.2.7 Low-temperature calorimetry Calorimetry under pressure Calorimetry under magnetic field Temperature jump calorimetry Calvet calorimeter Heat of vaporization and Sublimation Reaction calorimetry Heat of Solution and mixing Heat of immersion and adsorption Titration calorimetry Flow calorimetry Heat capacity spectroscopy Calorimetry at extremely high temperatures Adiabatic differential scanning calorimetry for biothermodynamics Principles and Methods of Thermal Analysis Thermogravimetry (TG) and controlled-rate TG Differential thermal analysis (DTA) and differential scanning calorimetry (DSC) Thermomechanical analysis (TMA) and dynamic mechanical analysis (DMA) Temperature-modulated DSC Temperature wave analysis Triple-cell DSC Simultaneous thermal analysis Micro thermal analysis by scanning probe microscopes Micromechanical calorimetry Other Experiments Determination of thermal expansivity Steady State method of determination of thermal conductivity/diffusivity Transient method for determination of thermal conductivity/diffusivity Mass spectrometry Determination of electromotive force Surface tension 183 Part III DATA ANALYSIS Data Analysis of Calorimetry Purity determination Phase transition and normal heat capacity 191
4 Contents vn Determination of partial molar quantities Statistical thermodynamic analysis in biocalorimetry Data analysis in titration calorimetry Techniques of Thermal Analysis and the Data Analysis Solid-state reaction kinetics by TG Baseline and thermal anomaly in DTA and DSC Heat capacity measurement by DSC and TM-DSC Analysis of isothermal crystallization by DSC Glass transition and relaxation phenomena Determination of phase diagrams by DTA/DSC Purity determination by DSC 241 Part IV HOW TO UTILIZE THE THERMODYNAMIC DATABASE Thermodynamic and Related Database Recent development of thermodynamic database Systems Phase diagram calculations Thermophysical property database Utilization of Thermodynamic Database Calculated phase diagram vs observed phase diagram Application of chemical equilibrium calculations Application of chemical potential diagram Thermodynamic Database for Biomolecules Proteins and mutants Protein-nucleic acid interactions 280 PartV ACTUAL APPLICATIONS Metals and Alloys Thermal analysis of amorphous alloys Thermal analysis of hydrogen-absorbing alloy Thermal analyses of heat-resistant type steels and alloys Thermodynamic analysis of liquid alloys by temperature-jump calorimetry EMF method with solid electrolyte for liquid alloys Construction of alloy phase diagrams Electronic density of states of quasicrystals Kinetics of oxidation in thin metal films Lattice-defect concentration in solids from thermal expansion 312
5 Vlll Contents 5.2 Inorganic Materials and Ceramics Heat capacity of U0 2 up to 8000K Battery materials: Spineis containing Mn for lithium secondary battery Thermal conductivity of diamond film Kinetic features of the thermal dehydration of inorganic hydrates Dehydration of inorganic salts under reduced pressure Thermal analysis of water-containing Silicate minerals Heat of adsorption and evaluation of active sites on the surface Nonstoichiometry of oxides by constant temperature TG Heat of hydration of zeolite Heat capacity of yttria-stabilized zirconia Acoustic emission and thermal analysis of phase transitions Pore-size distributions in silica gels Calorimetry for fast ion conducting glasses Negative thermal expansion of ZrW Calorimetry of high-pressure minerals Heat capacity of diamond and graphite Heat capacity anomaly in lead-based complex perovskite relaxors Organic Materials and Polymers Strain and resonance energies of fullerenes Heat capacity of molecular monolayers Entropy of transition of mixed crystals Glass transition and residual entropy Heat capacity of exotic superconductors Magnetic dimensionality and spin-wave excitation of molecule-based magnet Calorimetry of liquid crystals Alkyl-chain-length dependence of entropy of transition High-pressure DTA of liquid crystals Crystallization of polymers Melting of polymer crystals studied by temperature-modulated DSC Origin of double melting peaks of drawn nylon Glass transition and relaxation in polymers Thermal decomposition of polyurethanes containing natural Compounds Curing of epoxy resins containing plant components Phase transition in spin-crossover complex Frequency-dependent heat capacity near a glass transition 409
6 Contents ix Heat capacity of molecular magnets under magnetic field Micro thermal analysis of polymers by scanning probe microscopy Biomolecules Phase transition of lipid Thermal stability and function of Myb protein Thermal stability of mutant lysozymes Stepwise melting of plasmid DNA in the presence of Mg 2+ ion Volume and compressibility of proteins Enzyme activity Protein-DNA interaction Molecular recognition of antibody Glass transition of protein Medianes Purity determination of medicines by DSC Evaluation of Polymorphie transformation of drugs Determination of heat of hydration and hydration kinetics of theophylline hydrates Inclusion Compound formation between host material and medicinal molecules Estimation of initial dissolution rate of drug substances by thermal analysis Long-term stability Effect of drugs on microbial growth activities Drug interaction in human blood Foods and Biomaterials Phase transition of glycolipids Sol-gel transition in Polysaccharides Phase transition of Polysaccharide helix Interaction between starch and water Novel biomaterial-water interaction produced by heat treatment Nonfreezing water in food Quantitative evaluation of food putrefaction Thermal analysis of various plant materials Dynamic viscoelasticity of hair 494 APPENDIX 497 A.l The international temperature scale of 1990 (ITS-90) 499 A.2 Electromotive force of thermocouples 506
7 x Contents Index 523 A.3 Standard reference materials for thermal analysis 512 A.4 Symbols and notations for thermodynamic and related quantities and their printing 515 A.5 Guidelines for presentation of experimental results 518
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