Experimental Thermochemistry Volume II2025|PDF|Epub|mobi|kindle电子书版本百度云盘下载

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1．Combustion Calorimetry:Introductory＆GUY WADDINGTON1

1．Reference to general principles1

2．Moving-bomb calorimetry2

(a) Limitations of classical bomb calorimetry2

(b) Reasons for moving bombs3

(c) Applications5

(d) Comparison experiments6

3．Fluorine as an oxidant7

4．Machine computation of results8

5．Future role of bomb calorimetry10

6．Thermochemical compilations12

2．Combustion in a Bomb of Organic Fluorine Compounds＆W．D．GOOD AND D．W．SCOTT15

1．Introduction15

2．Rotating-bomb calorimeter,bomb and fittings16

3．Containers for volatile or sensitive samples17

4．Chemistry of the bomb process19

5．Experimental procedures21

6．Comparison experiments22

7．Reduction to standard states24

(a) Initial state24

(b) Final state26

(c) Energy factors and calorimetric data27

(d) Changes in internal energy28

8．Factors influencing the accuracy30

(a) Purity of samples30

(b) CF4 as product32

9．Reference substances for fluorine compounds32

10．Publication of results36

11．Illustrative results38

3．Combustion in a Bomb of Organic Bromine Compounds＆LARS BJELLKRUP41

1．Introduction41

2．Apparatus41

3．Experimental procedure43

4．Calculation of results44

5．Accuracy of resultant data46

6．Summary47

Appendix．Computation form for calculating standard heats of combustion from experimental data48

(a) Initial and final states48

(b) Energy factors and calorimetric data52

(c) Changes in internal energy54

4．Combustion in a Bomb of Organometallic Compounds＆W．D．GOOD AND D．W．SCOTT57

1．Introduction57

2．Limitations of static-bomb methods58

3．Rotating-bomb methods61

4．Corrections to standard states63

5．Comparison experiments65

6．Materials for the bomb,fittings and crucible68

7．Containers for samples70

8．Problem of incomplete combustion71

9．Publication of results73

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

1．Introduction77

2．Calorimetric considerations77

3．Chemical considerations78

(a) The metal78

(b) The oxygen80

(c) Ignition81

(d) The container82

(e) Getting the right reaction83

(f) Determining the amount of reaction84

(g) Side reactions84

(h) The thermodynamic state of the reactants and the products85

(i) Calculations86

4．Some metals whose heats of combustion have been measured87

6．Fluorine Bomb Calorimetry＆WARD N．HUBBARD95

1．Introduction95

(a) Problems involved97

2．Experimental apparatus and procedure98

(a) Materials of construction98

(b) Safety100

(c) The calorimeter and its calibration101

(d) The bomb101

(e) Support of the sample102

(f) Exploratory reaction vessel107

(g) Bomb charging and discharging apparatus108

(h) Fluorine110

(i) Experimental procedure111

3．Thermodynamic states and appropriate thermal corrections113

(a) Initial states114

(b) Final states116

(c) Energy factors and calorimetric data117

(d) Changes in internal energy117

4．Discussion121

(a) Reproducibility of results121

(b) Side reactions with construction materials121

(c) Test substances122

(d) Method of comparative measurements123

(e) Exploratory studies124

(f) Conclusion125

7 Fluorine Flame Calorimetry＆GEORGE T．ARMSTRONG129

1．Introduction129

2．Basis of need for fluorine flame calorimetry129

3．Technical problems in the use of fluorine in calorimetry131

4．Apparatus and methods133

(a) Burner and combustion chamber design134

(b) Combustion gas-flow scheme135

(c) Sample holders138

(d) Analysis of fluorine139

(e) Experimental procedure139

(f) Energy equivalent of calorimeter140

5．Verification of the amount of reaction140

6．Correction of heat of reaction to standard state142

7．Experimental results from fluorine flame calorimeter142

8．Conclusion144

8．Reaction Calorimetry:Introductory Chapter＆H．A．SKINNER147

1．Heats of hydrogenation149

2．Heats of hydrohalogenation and halogenation150

3．Heats of hydrolysis151

4．Solution calorimetry151

5．Heats of polymerization151

6．Heats of formation of co-ordination compounds151

7．Miscellaneous reactions152

8．Heats of mixing of liquids154

9．The Design and Operation of Reaction Calorimeters＆H．A．SKINNER,JULIAN M．STURTEVANT AND STIG SUNNEB157

1．Types of calorimeter:general considerations157

(a) Constant-temperature-environment calorimeters159

(b) Adiabatic calorimeters160

(c) Twin calorimeter systems160

(d) Isothermal phase-change calorimeters161

(e) Heat-flow calorimeters163

2．Temperature measurement165

(a) Mercury-in-glass thermometers166

(b) Platinum resistance thermometers167

(c) Thermistors168

(d) Thermocouples170

3．Temperature control173

(a) Control of thermostats173

(b) Adiabatic control175

4．Calibration of reaction calorimeters177

(a) Electrical calibration179

(b) Calibration by ＇standard＇ reactions182

5．Mixing the reactants183

6．Specific types of calorimeter185

(a) Bomb calorimeters185

(b) Rocking-bomb reaction calorimeter186

(c) Glass Dewar-vessel calorimeters188

(d) Vacuum-jacketed calorimeters191

(e) Isothermal-jacket calorimeters195

(f) Measuring the heats of slow reactions196

(g) High-temperature reactions202

Appendix 1．A thermistor control for thermostats209

Appendix 2．A method for supplying constant power to a calorimeter heating circuit211

Appendix 3．Representative sample of literature references on calorimeter design214

10．Heats of Hydrogenation and Halogenation＆JOHN R．LACHER221

1．Introduction221

2．Vapour-phase heats of hydrogenation222

3．Liquid-phase heats of hydrogenation224

4．Vapour-phase heats of halogenation and hydrohalogenation229

5．Experimental results232

11．Heats of Hydrolysis＆STIG SUNNER AND I．WADSO239

1．Introduction239

2．Class of reactions240

(a) Boron compounds240

(b) Halides242

(c) Anhydrides244

(d) Metal alkyls244

(e) Amides245

(f) Esters and related substances246

(g) Hydrides246

(h) Amide and peptide bonds247

(i) Phosphates247

12．Heats of Polymerization＆F．S．DAINTON AND K．J．IVIN251

1．Introduction and definitions251

2．Combustion methods255

3．Direct calorimetry256

(a) Some problems of technique256

(b) Non-isothermal methods256

(c) Vaporization calorimetric method259

(d) Fusion calorimetric method262

4．Other methods266

(a) Thermodynamic method266

(b) Semi-empirical methods267

5．Heats of solution of polymers267

6．Tables of data268

7．Structural effects and their interpretation275

(a) Ethylene derivatives275

(b) Ring compounds276

(c) Copolymerization276

13．High-temperature Reaction Calorimetry＆WILLIAM H．EVANS281

1．Introduction281

2．The heat of decomposition of diborane282

3．The heat of decomposition of decaborane288

4．The heats of formation of BC13,TiCl4,and TiBr4290

5．Conclusions290

14．Solution Calorimetry and Silicate Thermochemistry＆JAMES P．COUGHLIN293

1．Introduction293

2．Evaluation of heats of formation294

3．The glass-Dewar calorimeter296

4．Silicate thermochemistry303

(a) The calorimeter304

(b) Electrical calibrations307

(c) Determination of final equilibrium308

(d) Minimization of heat interchange corrections310

(e) Importance of exact stoichiometry312

5．Problem areas313

(a) Substances soluble with difficulty313

(b) Precipitate formation316

(c) Corrosion317

(d) Gas evolution317

(e) Oxidizing agents318

15．Heats of Mixing＆M．L．MCGIASHAN321

1．Introduction321

2．Measurement of ？mH322

3．The effect of vapour spaces325

4．Review of published mixing vessels328

5．Behaviour of heats of mixing337

16．Metallurgical and Alloy Thermochemistry＆O．KUBASCHEWSKI AND R．HULTGREN343

1．Introduction343

2．Selection of methods346

3．Calorimeters351

(a) General351

(b) Common parts of calorimeters351

(c) Drop calorimetry356

4．Types of calorimeter359

(a) Transformation calorimeters359

(b) Adiabatic calorimeters361

(c) Heat-flow calorimeters365

(d) Isoperibol calorimeters367

(e) Liquid-metals reaction calorimeters375

(f) Heats of precipitation and transformation377

5．Sources of error379

17．Recent Progress in Microcalorimetry＆EDOUARD CALVET385

1．Refinements to the apparatus385

(a) The microcalorimetric elements385

(b) Positioning of the microcalorimetric elements386

(c) The thermostat387

(d) Electrical circuits387

(e) Compensation of thermal effects387

2．Transforming the recorded thermograms into true thermogenesis curves388

(a) Nature of the problem388

(b) Examples of recorded curves389

(c) Solution of the transformation problem392

(d) Experimental verification of the transformation equations399

3．A micro-combustion bomb for use in the Calvet microcalorimeter399

4．Studies in catalysis402

(a) Description of the microcalorimeter for operation at moderately high temperatures403

(b) Microcalorimetric study of the controlled oxidation of methane404

(c) Microcalorimetric study of the controlled oxidation of ethylene408

18．Biochemical and Zoological Thermogenesis＆HENRI PRAT411

1．Introduction411

2．Plants411

3．Micro-organisms414

4．Poikilotherms (cold-blooded animals)417

(a) Insects417

(b) Snakes419

5．Homeotherms (warm-blooded animals)419

6．Summary423

19．Heats of Biochemical Reactions＆JULIAN M．STURTEVANT427

1．Introduction427

2．The hydrolysis of amide and peptide bonds429

3．The hydrolysis of phosphate compounds430

4．Reactions involving carbohydrates432

5．Methyl transfer reactions433

6．Heats of ionization434

7．The hydration of fumaric acid436

8．The denaturation of proteins436

9．The denaturation of desoxyribosenucleic acid438

10．The polymerization of fibrin monomer438

11．Antigen-antibody reactions438

12．Protein-protein interactions439

13．Enzyme—substrate interaction439

14．The calorimetric determination of reaction rates439

15．The calorimetric evaluation of equilibrium constants439

16．The calorimetric determination of molecular weights440

Author Index443

Subject Index453