Contents ....................................................... 3
Preface ......................................................... 7
Chapter 1 Outline of the history of calorimetry development ... 13
Chapter 2 Heat transfer in calorimetry ........................ 41
2.1 Fourier Law and Fourier-Kirchhoff Equation ................ 41
2.2 Heat transfer. Conduction, convection and radiation ....... 46
2.3 Cooling and heating processes of thermally passive body ... 57
2.4 Heat balance equation of simple body. Newton Law of
Cooling ................................................... 59
2.5 Relation between α and β .................................. 64
2.6 Application of Newton's Law of Cooling for the
determination of heat effects. The static-dynamic
method .................................................... 67
Chapter 3 Analysis of heat effects courses occurring in
the calorimeters. Dynamic properties of calorimeters ........... 73
3.1 Thermal - electrical analogy method ....................... 73
3.2 Thermal and dynamic properties of the calorimeters.
Thermal-dynamic analogy method ............................ 75
3.3 The influence of the thermostat disturbances on
temperature changes in a calorimeter ...................... 89
3.4 Determination of the effect of the disturbances on the
course of the function T(t) in a differential and twin
calorimeters .............................................. 98
3.5 Multi-body theory ........................................ 103
3.5.1 Postulates of the multi-body theory ............... 103
3.5.2 Equations of dynamics ............................. 108
3.5.3 Elaboration of the mathematical, dynamic model
of calorimeter based on physical parameters ....... 117
Chapter 4 Classification of calorimeters. Method of
determination of heat effects ................................. 121
4.1 Classification of calorimeters ........................... 121
4.2 Method of determination of heat effects .................. 132
4.2.1 Dynamic method .................................... 133
4.2.2 Flux method ....................................... 136
4.2.3 Steady-state method ............................... 138
4.2.4 Modulating method ................................. 141
4.2.5 Method of corrected temperature rise .............. 143
4.3 Calibration and test reactions ........................... 148
Chapter 5 Adiabatic calorimeters ............................. 151
5.1 Adiabatic calorimeters (adiabatic-nonisothermal
calorimeters) ............................................ 151
5.2 Adiabatic-isothermal calorimeters ........................ 164
5.2.1 Adiabatic-isothermal titration microcalorimeter ... 164
5.3 Scanning adiabatic calorimeters .......................... 172
5.4 Photoacoustic (quasi-adiabatic) calorimeters ............. 185
Chapter 6 Isoperibol, batch nonadiabatic-nonisothermal
calorimeters .................................................. 189
6.1 The KRM calorimeter. Ordinary calorimeters ............... 190
6.2 Microcalorimeter for determination of heat of
chemisorption on gases on vacuum evaporated metal
films .................................................... 193
6.3 Combustion calorimetry ................................... 195
6.3.1 Static and rotating oxygen calorimetric bombs ..... 195
6.3.2 Fluorine combustion bomb .......................... 200
6.4 Solution calorimetry ..................................... 203
6.4.1 Definitions of the enthalpy of solution ........... 204
6.4.2 Solution calorimeters ............................. 206
6.4.3 Solute-solvent interactions of hydrophobic
compounds ......................................... 211
6.4.4 H.F. Solution calorimetry ......................... 223
6.4.5 High temperature solution calorimetry ............. 224
Chapter 7 Enthalpy of sublimation. Calorimetric and
indirect methods .............................................. 227
7.1 Knudsen cell mass-loss effusion method ................... 228
7.2 Calorimetric and TG/DTG methods .......................... 232
7.3 Transpiration method ..................................... 235
7.4 Quartz resonator method .................................. 239
Chapter 8 Batch displacement and flow calorimeters.
Measurements of heats of dilution and mixing .................. 241
8.1 Measurements of heats of dilution and mixing ............. 241
8.2 Isothermal displacement calorimeters ..................... 244
8.3 The Mönk and Wadsö flow calorimeter. The LKB 10711
calorimeter and its modifications ........................ 245
8.4 The Picker flow calorimeter .............................. 246
8.5 High-pressure, high-temperature calorimeters ............. 248
Chapter 9 Conduction calorimeters. The E. Calvet
microcalorimeter .............................................. 251
9.1 The E. Calvet microcalorimeter ........................... 251
9.2 Conduction microcalorimeters ............................. 253
9.3 Determination of kinetic parameters ...................... 258
9.4 Fast reaction calorimeters ............................... 266
9.5 Photocalorimetry ......................................... 269
9.6 Methods of the determination of heat effects and
thermokinetics in conduction calorimetry ................. 272
9.6.1 Heat flux method and dynamic method ............... 272
9.6.2 N-body method ..................................... 273
9.6.3 Numerical and analogue methods of reconstruction
of thermokinetics ................................. 274
Chapter 10 Nonisothermal-nonadiabatic scanning calorimeters.
Thermal analysis. Differential scanning calorimetry (DSC) ..... 283
Chapter 11 Pressure scanning calorimeters. Transistometry ..... 295
Final Remarks ................................................. 299
References .................................................... 301
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