Experimental Thermochemistry Volume IIPDF电子书下载

1．Combustion Calorimetry:Introductory＆GUY WADDINGTON 1

1．Reference to general principles 1

2．Moving-bomb calorimetry 2

(a) Limitations of classical bomb calorimetry 2

(b) Reasons for moving bombs 3

(c) Applications 5

(d) Comparison experiments 6

3．Fluorine as an oxidant 7

4．Machine computation of results 8

5．Future role of bomb calorimetry 10

6．Thermochemical compilations 12

2．Combustion in a Bomb of Organic Fluorine Compounds＆W．D．GOOD AND D．W．SCOTT 15

1．Introduction 15

2．Rotating-bomb calorimeter,bomb and fittings 16

3．Containers for volatile or sensitive samples 17

4．Chemistry of the bomb process 19

5．Experimental procedures 21

6．Comparison experiments 22

7．Reduction to standard states 24

(a) Initial state 24

(b) Final state 26

(c) Energy factors and calorimetric data 27

(d) Changes in internal energy 28

8．Factors influencing the accuracy 30

(a) Purity of samples 30

(b) CF4 as product 32

9．Reference substances for fluorine compounds 32

10．Publication of results 36

11．Illustrative results 38

3．Combustion in a Bomb of Organic Bromine Compounds＆LARS BJELLKRUP 41

1．Introduction 41

2．Apparatus 41

3．Experimental procedure 43

4．Calculation of results 44

5．Accuracy of resultant data 46

6．Summary 47

Appendix．Computation form for calculating standard heats of combustion from experimental data 48

(a) Initial and final states 48

(b) Energy factors and calorimetric data 52

(c) Changes in internal energy 54

4．Combustion in a Bomb of Organometallic Compounds＆W．D．GOOD AND D．W．SCOTT 57

1．Introduction 57

2．Limitations of static-bomb methods 58

3．Rotating-bomb methods 61

4．Corrections to standard states 63

5．Comparison experiments 65

6．Materials for the bomb,fittings and crucible 68

7．Containers for samples 70

8．Problem of incomplete combustion 71

9．Publication of results 73

5．Combustion in a Bomb of Metals＆ELMER J．HUBER,JR．,AND CHARLES E．HOLLEY,JR． 77

1．Introduction 77

2．Calorimetric considerations 77

3．Chemical considerations 78

(a) The metal 78

(b) The oxygen 80

(c) Ignition 81

(d) The container 82

(e) Getting the right reaction 83

(f) Determining the amount of reaction 84

(g) Side reactions 84

(h) The thermodynamic state of the reactants and the products 85

(i) Calculations 86

4．Some metals whose heats of combustion have been measured 87

6．Fluorine Bomb Calorimetry＆WARD N．HUBBARD 95

1．Introduction 95

(a) Problems involved 97

2．Experimental apparatus and procedure 98

(a) Materials of construction 98

(b) Safety 100

(c) The calorimeter and its calibration 101

(d) The bomb 101

(e) Support of the sample 102

(f) Exploratory reaction vessel 107

(g) Bomb charging and discharging apparatus 108

(h) Fluorine 110

(i) Experimental procedure 111

3．Thermodynamic states and appropriate thermal corrections 113

(a) Initial states 114

(b) Final states 116

(c) Energy factors and calorimetric data 117

(d) Changes in internal energy 117

4．Discussion 121

(a) Reproducibility of results 121

(b) Side reactions with construction materials 121

(c) Test substances 122

(d) Method of comparative measurements 123

(e) Exploratory studies 124

(f) Conclusion 125

7 Fluorine Flame Calorimetry＆GEORGE T．ARMSTRONG 129

1．Introduction 129

2．Basis of need for fluorine flame calorimetry 129

3．Technical problems in the use of fluorine in calorimetry 131

4．Apparatus and methods 133

(a) Burner and combustion chamber design 134

(b) Combustion gas-flow scheme 135

(c) Sample holders 138

(d) Analysis of fluorine 139

(e) Experimental procedure 139

(f) Energy equivalent of calorimeter 140

5．Verification of the amount of reaction 140

6．Correction of heat of reaction to standard state 142

7．Experimental results from fluorine flame calorimeter 142

8．Conclusion 144

8．Reaction Calorimetry:Introductory Chapter＆H．A．SKINNER 147

1．Heats of hydrogenation 149

2．Heats of hydrohalogenation and halogenation 150

3．Heats of hydrolysis 151

4．Solution calorimetry 151

5．Heats of polymerization 151

6．Heats of formation of co-ordination compounds 151

7．Miscellaneous reactions 152

8．Heats of mixing of liquids 154

9．The Design and Operation of Reaction Calorimeters＆H．A．SKINNER,JULIAN M．STURTEVANT AND STIG SUNNEB 157

1．Types of calorimeter:general considerations 157

(a) Constant-temperature-environment calorimeters 159

(b) Adiabatic calorimeters 160

(c) Twin calorimeter systems 160

(d) Isothermal phase-change calorimeters 161

(e) Heat-flow calorimeters 163

2．Temperature measurement 165

(a) Mercury-in-glass thermometers 166

(b) Platinum resistance thermometers 167

(c) Thermistors 168

(d) Thermocouples 170

3．Temperature control 173

(a) Control of thermostats 173

(b) Adiabatic control 175

4．Calibration of reaction calorimeters 177

(a) Electrical calibration 179

(b) Calibration by ＇standard＇ reactions 182

5．Mixing the reactants 183

6．Specific types of calorimeter 185

(a) Bomb calorimeters 185

(b) Rocking-bomb reaction calorimeter 186

(c) Glass Dewar-vessel calorimeters 188

(d) Vacuum-jacketed calorimeters 191

(e) Isothermal-jacket calorimeters 195

(f) Measuring the heats of slow reactions 196

(g) High-temperature reactions 202

Appendix 1．A thermistor control for thermostats 209

Appendix 2．A method for supplying constant power to a calorimeter heating circuit 211

Appendix 3．Representative sample of literature references on calorimeter design 214

10．Heats of Hydrogenation and Halogenation＆JOHN R．LACHER 221

1．Introduction 221

2．Vapour-phase heats of hydrogenation 222

3．Liquid-phase heats of hydrogenation 224

4．Vapour-phase heats of halogenation and hydrohalogenation 229

5．Experimental results 232

11．Heats of Hydrolysis＆STIG SUNNER AND I．WADSO 239

1．Introduction 239

2．Class of reactions 240

(a) Boron compounds 240

(b) Halides 242

(c) Anhydrides 244

(d) Metal alkyls 244

(e) Amides 245

(f) Esters and related substances 246

(g) Hydrides 246

(h) Amide and peptide bonds 247

(i) Phosphates 247

12．Heats of Polymerization＆F．S．DAINTON AND K．J．IVIN 251

1．Introduction and definitions 251

2．Combustion methods 255

3．Direct calorimetry 256

(a) Some problems of technique 256

(b) Non-isothermal methods 256

(c) Vaporization calorimetric method 259

(d) Fusion calorimetric method 262

4．Other methods 266

(a) Thermodynamic method 266

(b) Semi-empirical methods 267

5．Heats of solution of polymers 267

6．Tables of data 268

7．Structural effects and their interpretation 275

(a) Ethylene derivatives 275

(b) Ring compounds 276

(c) Copolymerization 276

13．High-temperature Reaction Calorimetry＆WILLIAM H．EVANS 281

1．Introduction 281

2．The heat of decomposition of diborane 282

3．The heat of decomposition of decaborane 288

4．The heats of formation of BC13,TiCl4,and TiBr4 290

5．Conclusions 290

14．Solution Calorimetry and Silicate Thermochemistry＆JAMES P．COUGHLIN 293

1．Introduction 293

2．Evaluation of heats of formation 294

3．The glass-Dewar calorimeter 296

4．Silicate thermochemistry 303

(a) The calorimeter 304

(b) Electrical calibrations 307

(c) Determination of final equilibrium 308

(d) Minimization of heat interchange corrections 310

(e) Importance of exact stoichiometry 312

5．Problem areas 313

(a) Substances soluble with difficulty 313

(b) Precipitate formation 316

(c) Corrosion 317

(d) Gas evolution 317

(e) Oxidizing agents 318

15．Heats of Mixing＆M．L．MCGIASHAN 321

1．Introduction 321

2．Measurement of ？mH 322

3．The effect of vapour spaces 325

4．Review of published mixing vessels 328

5．Behaviour of heats of mixing 337

16．Metallurgical and Alloy Thermochemistry＆O．KUBASCHEWSKI AND R．HULTGREN 343

1．Introduction 343

2．Selection of methods 346

3．Calorimeters 351

(a) General 351

(b) Common parts of calorimeters 351

(c) Drop calorimetry 356

4．Types of calorimeter 359

(a) Transformation calorimeters 359

(b) Adiabatic calorimeters 361

(c) Heat-flow calorimeters 365

(d) Isoperibol calorimeters 367

(e) Liquid-metals reaction calorimeters 375

(f) Heats of precipitation and transformation 377

5．Sources of error 379

17．Recent Progress in Microcalorimetry＆EDOUARD CALVET 385

1．Refinements to the apparatus 385

(a) The microcalorimetric elements 385

(b) Positioning of the microcalorimetric elements 386

(c) The thermostat 387

(d) Electrical circuits 387

(e) Compensation of thermal effects 387

2．Transforming the recorded thermograms into true thermogenesis curves 388

(a) Nature of the problem 388

(b) Examples of recorded curves 389

(c) Solution of the transformation problem 392

(d) Experimental verification of the transformation equations 399

3．A micro-combustion bomb for use in the Calvet microcalorimeter 399

4．Studies in catalysis 402

(a) Description of the microcalorimeter for operation at moderately high temperatures 403

(b) Microcalorimetric study of the controlled oxidation of methane 404

(c) Microcalorimetric study of the controlled oxidation of ethylene 408

18．Biochemical and Zoological Thermogenesis＆HENRI PRAT 411

1．Introduction 411

2．Plants 411

3．Micro-organisms 414

4．Poikilotherms (cold-blooded animals) 417

(a) Insects 417

(b) Snakes 419

5．Homeotherms (warm-blooded animals) 419

6．Summary 423

19．Heats of Biochemical Reactions＆JULIAN M．STURTEVANT 427

1．Introduction 427

2．The hydrolysis of amide and peptide bonds 429

3．The hydrolysis of phosphate compounds 430

4．Reactions involving carbohydrates 432

5．Methyl transfer reactions 433

6．Heats of ionization 434

7．The hydration of fumaric acid 436

8．The denaturation of proteins 436

9．The denaturation of desoxyribosenucleic acid 438

10．The polymerization of fibrin monomer 438

11．Antigen-antibody reactions 438

12．Protein-protein interactions 439

13．Enzyme—substrate interaction 439

14．The calorimetric determination of reaction rates 439

15．The calorimetric evaluation of equilibrium constants 439

16．The calorimetric determination of molecular weights 440

Author Index 443

Subject Index 453