Advances in Mass Spectrometry (eBook)

Front Cover 1
Advances in Mass Spectrometry 4
Copyright Page 5
Table of Contents 6
FOREWORD 12
EDITOR'S NOTE 13
OPENING REMARKS 14
SESSION A: High Resolution Mass Spectrometry 16
CHAPTER 1. SOME NEW ATOMIC MASS DETERMINATIONS MADE WITH A LARGE SINGLE-FOCUSING MASS SPECTROMETER 18
INTRODUCTION 18
THE MASS SPECTROMETER 19
METHOD OF DETERMINING ATOMIC MASS DIFFERENCES 21
NEW MASS DIFFERENCE VALUES 23
DISCUSSION OF RESULTS 24
REFERENCES 26
CHAPTER 2. THE PERFORMANCE AND IMAGE ERROR CORRECTION OF THE NEW STIGMATIC FOCUSING MASS SPECTROGRAPH 27
NOTE ADDED IN PROOF 31
REFERENCES 31
CHAPTER 3. MASS SPECTROMETERS AND MASS SPECTROGRAPHS CORRECTED FORIMAGE DEFECTS 33
INTRODUCTION 33
THE DEFLECTION FIELDS 34
THE IMAGE DEFECTS 38
CORRECTION OF THE IMAGE DEFECTS 39
INSTRUMENTS WITH IMAGE-DEFECT CORRECTIONS 39
REFERENCES 52
CHAPTER 4. CORRECTION OF SECOND ORDER ABERRATIONSIN INHOMOGENEOUS MAGNETIC SECTOR FIELDS 53
APPENDIX: COEFFICIENTS IN THE SECOND ORDER APPROXIMATION OF THE ION TRAJECTORIES IN THE MEDIAN PLANE 58
REFERENCES 59
CHAPTER 5. THEORETICAL AND EXPERIMENTAL STUDY OF HIGH-MASS HIGH-RESOLUTION MASS SPECTROMETERS 61
INTRODUCTION 61
PART I.THEORETICAL CONSIDERATIONS RESOLUTION 62
ION CURRENTS OBTAINABLE 66
PART IIDESCRIPTION OF EXPERIMENTAL INSTRUMENTS 67
COINCIDENT FIELD SECTOR MASS SPECTROMETER 67
TANDEM SECTOR MASS SPECTROMETER 71
COINCIDENT FIELD CYCLOID MASS SPECTROMETER 77
REFERENCES 81
CHAPTER 6. DESIGN AND PERFORMANCE OF A DOUBLE-FOCUSING MASS SPECTROMETER FOR ANALYTICAL WORK 83
INTRODUCTION 83
DESCRIPTION OF INSTRUMENT 84
REFERENCES 101
SESSION B: Mass Spectrometry of Solids 104
CHAPTER 7. HIGH SENSITIVITY SOLID SOURCE MASS SPECTROMETRY 106
INTRODUCTION 106
THE THERMAL EMISSION ION SOURCE 106
THE ELECTRON MULTIPLIER 110
LIMITATIONS OF THE METHOD 112
COMPARISON OF RESULTS 117
REFERENCES 118
CHAPTER 8. ISOTOPE DILUTION ANALYSIS 120
INTRODUCTION 120
DESCRIPTION OF THE METHOD 120
DISCUSSION OF THE METHOD 122
APPLICATIONS 130
REFERENCES 134
CHAPTER 9. IONIZATION OF SILVER AND COPPER IN A TRIPLE-FILAMENT ION SOURCE 137
APPARATUS 137
EXPERIMENTAL METHODS 137
RESULTS 139
REFERENCES 141
CHAPTER 10. INVESTIGATION OF THE TIME VARIATION OF ALKALI ION EMISSION FROM SOLID SPECIMENS ON GLOWING METAL SURFACES 142
INTRODUCTION 142
APPARATUS 143
EXPERIMENTAL METHODS AND ACCURACY 144
RESULTS 144
INTERPRETATION OF THE IM-IMAGES 150
REFERENCES 152
CHAPTER 11. DETERMINATION OF IMPURITIES IN SOLIDS BY SPARK SOURCE MASS SPECTROMETRY 153
INTRODUCTION 153
NATURE OF THE MASS SPECTRUM PRODUCED BY THE SPARK IONIZATION SOURCE 157
DETERMINATION OF IMPURITY CONCENTRATION 160
RESULTS AND APPLICATIONS 164
FACTORS AFFECTING THE LIMIT OF DETECTION OF IMPURITIES 168
REFERENCES 172
CHAPTER 12. THE ANALYSIS OF NON-CONDUCTING SOLIDS BY THE MASS SPECTROMETER 174
REFERENCES 177
CHAPTER 13. THE APPLICATION OF MASS SPECTROMETRY TO THE STUDY OF SURFACES BY SPUTTERING 179
INTRODUCTION 179
EXPERIMENTAL 179
RESULTS 182
REFERENCES 187
SESSION C: Application of the Mass Spectrometer in Organic Chemistry 190
CHAPTER 14. STATUS OF APPLICATION OF MASS SPECTROMETRY TO HEAVY OIL ANALYSIS 192
INTRODUCTION 192
PRODUCTION OF MASS SPECTRA 192
ANALYTICAL METHODS 193
RECENT APPLICATIONS 204
CONCLUSION 206
REFERENCES 207
CHAPTER 15. USE OF RHENIUM FILAMENTS AND LOW IONIZING VOLTAGES FOR ANALYSING LIQUID PRODUCTS FROM COAL HYDROGENATION BY MASS SPECTROMETRY 210
INTRODUCTION 210
COMPARISON OF TUNGSTEN AND RHENIUM FILAMENTS 211
ANALYSIS OF NEUTRAL AND TAR ACID FRACTIONS OF LIQUID PRODUCTS FROM COAL HYDROGENATION 213
REFERENCES 224
CHAPTER 16. THE ANALYSIS OF CORROSIVE GASES WITH A MASS SPECTROMETER 226
INTRODUCTION 226
MASS SPECTROMETER FOR THE ANALYSIS OF CORROSIVE GASES 226
FACTORS INFLUENCING THE ANALYSIS OF HF AND C1F3 231
CONCLUSION 236
REFERENCES 237
CHAPTER 17. MASS SPECTROMETRIC IDENTIFICATION OF IMPURITIES IN ORGANIC SUBSTANCES BY MEANS OF ADDITIONAL FRACTIONATION AT THE INLET SYSTEM 239
INTRODUCTION 239
EXPERIMENTAL 239
RESULTS 241
DISCUSSION 247
REFERENCES 248
CHAPTER 18. DIGITIZATION OF MASS SPECTRA 249
INTRODUCTION 249
THE SPECTRO-SADIC 249
GALVANOMETER DIGITIZER 251
THE MASCOT DIGITIZER 254
COMPUTATION OF ANALYTICAL RESULTS USING PUNCHED CARD MASS SPECTROMETER DATA 259
REFERENCES 264
CHAPTER 19. THE TIME-OF-FLIGHT MASS SPECTROMETER 266
REFERENCES 281
CHAPTER 20. A HIGH-SPEED CYCLOIDAL MASS SPECTROMETER 283
INTRODUCTION 283
CYCLOIDAL INSTRUMENT 284
ELECTRONICS 287
PERFORMANCE 287
SUMMARY AND CONCLUSIONS 289
REFERENCES 289
CHAPTER 21. ION DISSOCIATION REACTIONS IN THE MASS SPECTROMETER 291
REFERENCES 301
CHAPTER 22. THEORETICAL ASPECTS OF THE MASS SPECTRA OF POLYATOMIC MOLECULES 304
INTRODUCTION 304
BASIS OF THE THEORETICAL TREATMENT: FUNDAMENTAL KINETICS AND THE SIGNIFICANCE OF DISSOCIATION ENERGIES 305
THE ELECTRON DENSITY DISTRIBUTION IN THE PARENT ION 306
ENERGETICS OF THE FRAGMENTATION PROCESS 309
COMPLETE MOLECULAR ORBITAL EVALUATION OF IONIZATION POTENTIALS AND ELECTRON DENSITIES FOR BRANCHED CHAIN HYDROCARBONS 309
THE DISSOCIATION ENERGIES DÌ 311
OTHER FEATURES OF FRAGMENTATION PROCESSES AND THE HIGH ABUNDANCE OF IONS OF MASS 43 AND MASS 57 315
HYDROGEN ABSTRACTION PROCESSES 316
EFFECT OF A DOUBLE BOND 317
MASS SPECTRA OF FUSED RING HYDROCARBONS 317
POSSIBILITIES OF APPLICATIONS TOOTHER ORGANIC SYSTEMS 322
REFERENCES 323
CHAPTER 23. ION-MOLECULE REACTIONS IN THE GAS PHASE 325
INTRODUCTION 325
IDENTIFICATION OF THE REACTION 326
REACTION RATE STUDIES 327
RATE THEORY 331
DECOMPOSITION OF THE COMPLEX 336
ION-MOLECULE REACTIONS IN MIXTURES OF GASES 338
REFERENCES 343
CHAPTER 24. HIGH RESOLUTION MASS SPECTROMETRY OF ORGANIC MATERIALS 345
INTRODUCTION 345
MULTIPLET PEAKS PRODUCED BY ORGANIC MATERIALS 346
MASS MEASUREMENT USING HIGH MASS DOUBLETS 352
CONSIDERATIONS OF RESOLVING POWER 354
OPERATING EXPERIENCE 357
SOME EXAMPLES 361
REFERENCES 370
CHAPTER 25. INTERPRETATION OF MASS SPECTRA OF ORGANIC MOLECULES 372
INTRODUCTION 372
QUALITATIVE EFFECTS OF FUNCTIONAL GROUPS 372
QUANTITATIVE EFFECTS OF FUNCTIONAL GROUPS 375
CONCLUSION 379
REFERENCES 380
CHAPTER 26. THE MASS SPECTRA OF SOME ORGANIC PHOSPHATES 382
INTRODUCTION 382
EXPERIMENTAL 383
DISCUSSION 386
CONCLUSIONS 399
REFERENCES 400
CHAPTER 27. STUDY OF THE REARRANGEMENT PROCESSES IN MASS SPECTROMETRY BY MEANS OF LABELLED COMPOUNDS 401
INTRODUCTION 401
REARRANGEMENTS IN ETHYLAMINE—2d2 404
CONCLUSIONS 408
REFERENCES 408
SESSION D: Ionization and Electron Impact Studies 412
CHAPTER 28. STUDY OF MULTIPLE IONIZATION IN HELIUM AND XENON BY ELECTRON IMPACT 414
INTRODUCTION 414
DESCRIPTION OF APPARATUS 415
DISCUSSION 425
REFERENCES 427
CHAPTER 29. RECENT ELECTRON IMPACT STUDIES ON SIMPLE MOLECULES (02, Cl2, I2)* 430
INTRODUCTION 430
EXPERIMENTAL 431
RESULTS AND DISCUSSION 431
REFERENCES 446
CHAPTER 30. IONIZATION POTENTIALS OF ALKYL AND HALOGENATED ALKYL FREE RADICALS 448
INTRODUCTION 448
EXPERIMENTAL 451
PRODUCTION OF RADICALS 451
MEASUREMENT OF THE IONIZATION POTENTIALS 452
RESULTS AND DISCUSSION 454
REFERENCES 458
CHAPTER 31. ELECTRON IMPACT STUDIES OF HYDRAZINE AND THE METHYL-SUBSTITUTED HYDRAZINES 460
INTRODUCTION 460
EXPERIMENTAL 460
RESULTS 461
DISCUSSION 464
REFERENCES 474
CHAPTER 32. NEGATIVE ION FORMATION AND ELECTRIC BREAKDOWN IN SOME HALOGENATED GASES 475
INTRODUCTION 475
EXPERIMENTAL PROCEDURE 476
RESULTS AND DISCUSSION 476
REFERENCES 488
CHAPTER 33. A MODIFICATION OF THE R.P.D. METHOD FOR MEASURING APPEARANCE POTENTIALS 490
INTRODUCTION 490
PRINCIPLE OF OPERATION 490
EXPERIMENTAL 494
PERFORMANCE OF THE ION SOURCE 497
FIELD PENETRATION INTO THE ION SOURCE 500
APPEARANCE POTENTIALS OF N2+ IONS FROM N2 504
CONCLUSION 504
REFERENCES 504
CHAPTER 34. KINETIC ENERGY OF FRAGMENT IONS 506
INTRODUCTION 506
EXPERIMENTAL 506
RESULTS 514
REFERENCES 520
SESSION E: Use of the Mass Spectrometer in Fundamental Research 522
CHAPTER 35. ISOTOPIC ANALYSIS OF TRACE QUANTITIES OF RARE GASES 524
DOUBLE-FOCUSING MASS SPECTROMETER FOR HELIUM ANALYSIS 525
SINGLE-FOCUSING ALL METAL MASS SPECTROMETER FOR ULTRA HIGH VACUUM WORK 527
REFERENCES 530
CHAPTER 36. MASS SPECTROMETRY ANALYSIS OF SIMPLE HYDROGEN COMPOUNDS 532
INTRODUCTION 532
DESCRIPTION OF THE SPECTROMETER 532
METHOD OF REDUCTION OF WATER AND HYDROGEN COMPOUNDS 535
ABSOLUTE STANDARDIZATION OF THEMASS SPECTROMETER 537
CHAPTER 37. THE MASS SPECTROMETER AS A GEOLOGICAL INSTRUMENT 543
CHAPTER 38. MASS SPECTROMETRIC STUDIES OF THE THERMODYNAMIC PROPERTIES OF GROUP III-V AND II-VI COMPOUNDS AND THE GROUP V AND VI ELEMENTS 551
INTRODUCTION 551
EXPERIMENTAL 552
RESULTS 553
DISCUSSION 558
REFERENCES 561
CHAPTER 39. ADSORPTION AND DESORPTION OF GASES IN THE IONIZED STATE ON METAL AND GLASS SURFACES 564
INTRODUCTION 564
APPARATUS 565
EXPERIMENTAL PROCEDURE AND RESULTS 567
DISCUSSION OF RESULTS 572
CONCLUSIONS 574
REFERENCES 574
CHAPTER 40. THE INVESTIGATION OF CERTAIN SURFACE PROCESSES BY MASS SPECTROMETRY 576
INTRODUCTION 576
EXPERIMENTAL METHODS WITH THE. MASS SPECTROMETER 577
SOME REACTIONS ON PLATINUM FILAMENTS 581
SOME REACTIONS ON TUNGSTEN FILAMENTS 582
REACTIONS OF RADICALS IN THE ION SOURCE 584
THE LIFETIME OF ADSORBED MOLECULES 585
REFERENCES 585
CHAPTER 41. A MASS SPECTROMETER WITH A LOW TEMPERATURE IONIZATION CHAMBER TO STUDY HETEROGENEOUS REACTIONS OF ATOMS AND FREE RADICALS 587
INTRODUCTION 587
DESCRIPTION OF THE INSTRUMENT 589
THE FLOW AND PRESSURE OF GAS IN THE IONIZATION CHAMBER 594
EXPERIMENTAL RESULTS 598
REFERENCES 605
BIBLIOGRAPHY ON MASS SPECTROMETRY 1938-1957 inclusive 608
INTRODUCTION 610
Section A. INSTRUMENT DESIGN 612
Section B. OPERATING TECHNIQUES 637
Section C. APPLICATIONS TO ISOTOPIC PROBLEMS 647
Section C. APPLICATIONS TO ISOTOPIC PROBLEMS 666
Section D. APPLICATIONS TO ORGANIC CHEMISTRY 668
Section E. IONIZATION AND DISSOCIATION OF MOLECULES 682
Section F. GENERAL APPLICATIONS IN ENGINEERING AND PHYSICS 694
Section G. APPLICATIONS TO SOLIDS 704
NAME INDEX OF BIBLIOGRAPHY 707