Chen The electron capture detector
.pdfTHE ELECTRON CAPTURE DETECTOR AND THE STUDY OF REACTIONS WITH THERMAL ELECTRONS
THE ELECTRON CAPTURE DETECTOR AND THE STUDY OF REACTIONS WITH THERMAL ELECTRONS
E. C. M. CHEN
E. S. D. CHEN
A JOHN WILEY & SONS, INC., PUBLICATION
Copyright # 2004 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
Published simultaneously in Canada.
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Library of Congress Cataloging-in-Publication Data:
Chen, E. C. M.
The electron capture detector and the study of reactions with thermal electrons /
E.C. M. Chen, E. S. D. Chen. p. cm.
Includes bibliographical references and index.
ISBN 0-471-32622-4 (Cloth)
1. Gas chromatography. 2. Electrons–Capture. I. Chen, E. S. D. II. Title. QD79.C45 C49 2004
5430 .85–dc22 |
2003023101 |
Printed in the United States of America |
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This book is dedicated to Professor Wayne E. Wenthworth who made it possible for the authors to become scientists. Without him the work in this book could not have been accomplished.
We also recognize the contributions of Dr. James. E. Lovelock, the inventor of the electron capture detector.
CONTENTS
FOREWORD |
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xiii |
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PREFACE |
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xv |
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1. Scope and History of the Electron |
1 |
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1.1 |
General Objectives and Organization |
1 |
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1.2 |
General Scope |
2 |
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1.3 |
History of the Electron |
4 |
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References |
|
6 |
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2. Definitions, Nomenclature, Reactions, and Equations |
8 |
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2.1 |
Introduction |
8 |
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2.2 |
Definition of Kinetic and Energetic Terms |
8 |
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2.3 |
Additional Gas Phase Ionic Reactions |
15 |
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2.4 |
Electron Affinities from Solution Data |
16 |
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2.5 |
Semi-Empirical Calculations of Energetic Quantities |
17 |
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2.6 |
Herschbach Ionic Morse Potential Energy Curves |
18 |
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2.7 |
Summary |
19 |
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References |
|
20 |
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3. Thermal Electron Reactions at the University of Houston |
22 |
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3.1 |
General Introduction |
22 |
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3.2 |
The First Half-Century, 1900 to 1950 |
23 |
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3.3 |
Fundamental Discovery, 1950 to 1960 |
25 |
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3.4 |
General Accomplishments, 1960 to 1970 |
27 |
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3.4.1 |
Introduction |
27 |
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3.4.2 |
The Wentworth Group |
28 |
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3.4.3 |
Stable Negative-Ion Formation |
28 |
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3.4.4 |
Dissociative Thermal Electron Attachment |
33 |
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3.4.5 |
Nonlinear Least Squares |
35 |
3.5Milestones in the Wentworth Laboratory and Complementary
Methods, 1970 to 1980 |
37 |
3.6Negative-Ion Mass Spectrometry and Morse Potential Energy
Curves, 1980 to 1990 |
40 |
3.7 Experimental and Theoretical Milestones, 1990 to 2000 |
41 |
vii
viii |
CONTENTS |
|
3.8 |
Summary of Contributions at the University of Houston |
42 |
References |
43 |
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4. Theoretical Basis of the Experimental Tools |
47 |
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4.1 |
Introduction |
47 |
4.2 |
The Kinetic Model of the ECD and NIMS |
47 |
4.3 |
Nondissociative Electron Capture |
50 |
4.4 |
Dissociative Electron Attachment |
59 |
4.5 |
Electron Affinities and Half-Wave Reduction Potentials |
64 |
4.6Electron Affinities and Ionization Potentials
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of Aromatic Hydrocarbons |
66 |
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4.7 |
Electron Affinities and Charge Transfer Complex Energies |
67 |
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4.8 |
Summary |
71 |
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References |
|
73 |
|
5. Experimental Procedures and Data Reduction |
75 |
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5.1 |
Introduction |
75 |
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5.2 |
Experimental ECD and NICI Procedures |
76 |
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5.3 |
Reduction of ECD Data to Fundamental Properties |
85 |
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5.3.1 |
Introduction |
85 |
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5.3.2 |
Acetophenone and Benzaldehyde |
86 |
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5.3.3 Benzanthracene, Benz[a]pyrene, and 1-Naphthaldehyde |
87 |
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5.3.4 |
Carbon Disulfide |
89 |
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5.3.5 |
Nitromethane |
90 |
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5.3.6 Consolidation of Electron Affinities for Molecular Oxygen |
91 |
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5.4 |
Reduction of Negative-Ion Mass Spectral Data |
93 |
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5.5 |
Precision and Accuracy |
96 |
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5.6 |
Evaluation of Experimental Results |
97 |
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5.7 |
Summary |
101 |
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References |
|
101 |
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6. Complementary Experimental and Theoretical Procedures |
103 |
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6.1 |
Introduction |
103 |
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6.2 |
Equilibrium Methods for Determining Electron Affinities |
105 |
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6.3 |
Photon Techniques |
110 |
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6.4 |
Thermal Charge Transfer Methods |
116 |
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6.5 |
Electron and Particle Beam Techniques |
121 |
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6.6 |
Condensed Phase Measurements of Electron Affinities |
124 |
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6.7 |
Complementary Theoretical Calculations |
125 |
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6.7.1 |
Atomic Electron Affinities |
126 |
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6.7.2 |
Polyatomic Molecules |
128 |
6.8 |
Rate Constants for Attachment, Detachment, and Recombination |
132 |
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CONTENTS |
ix |
6.9 |
Summary |
134 |
References |
134 |
|
7. Consolidating Experimental, Theoretical, and Empirical Data |
139 |
|
7.1 |
Introduction |
139 |
7.2 |
Semi-Empirical Quantum Mechanical Calculations |
140 |
7.3 |
Morse Potential Energy Curves |
150 |
|
7.3.1 Classification of Negative-Ion Morse Potentials |
151 |
|
7.3.2 The Negative-Ion States of H2 |
153 |
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7.3.3 The Negative-Ion States of I2 |
156 |
|
7.3.4 The Negative-Ion States of Benzene and Naphthalene |
157 |
7.4 |
Empirical Correlations |
161 |
7.5 |
Summary |
165 |
References |
166 |
|
8. Selection, Assignment, and Correlations of Atomic |
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Electron Affinities |
168 |
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8.1 |
Introduction |
168 |
8.2 |
Evaluation of Atomic Electron Affinities |
169 |
8.3 |
Mulliken Electronegativities |
178 |
8.4 |
Electron Affinities of Atomic Clusters |
184 |
8.5 |
Summary |
189 |
References |
190 |
|
9. Diatomic and Triatomic Molecules and Sulfur Fluorides |
193 |
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9.1 |
Introduction |
193 |
9.2 |
Diatomic Molecules |
194 |
9.2.1Electron Affinities and Periodic Trends of
Homonuclear Diatomic Molecules |
194 |
9.2.2Electron Affinities and Morse Potential Energy Curves:
Group VII Diatomic Molecules and Anions |
197 |
9.2.3Electron Affinities and Morse Potential Energy Curves:
Group VI Diatomic Molecules and Anions |
205 |
9.2.4Electron Affinities and Morse Potential Energy Curves: Group IA and IB Homonuclear Diatomic Molecules
and Anions |
209 |
9.2.5Electron Affinities and Morse Potential Energy Curves:
NO and NO( ) |
214 |
9.3 Triatomic Molecules and Anions |
216 |
9.4Electron Affinities and Morse Potential Energy Curves:
Sulfur Fluorides and Anions |
224 |
9.5 Summary |
229 |
References |
229 |
x |
CONTENTS |
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10. Negative Ions of Organic Molecules |
234 |
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10.1 |
Introduction |
234 |
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10.2 |
Electron Affinities and Potential Energy Curves for |
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|
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Nitrobenzene and Nitromethane |
235 |
10.3Electron Affinities Determined Using the Magnetron, Alkali Metal Beam, Photon, and Collisional
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Ionization Methods |
238 |
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10.3.1 Electron Affinities Determined Using the |
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Magnetron Method |
238 |
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10.3.2 Electron Affinities Determined Using the |
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AMB Method |
240 |
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10.3.3 Electron Affinities Determined Using |
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Photon Methods |
241 |
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10.3.4 Electron Affinities Determined Using Collisional |
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Ionization Methods |
243 |
10.4 |
Electron Affinities Determined Using the ECD, NIMS, |
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and TCT Methods |
244 |
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10.4.1 Electron Affinities of Aromatic Hydrocarbons |
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by the ECD Method |
244 |
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10.4.2 Electron Affinities of Organic Carbonyl Compounds |
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by the ECD Method |
246 |
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10.4.3 Electron Affinities of Organic Nitro Compounds |
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the ECD and TCT Methods |
253 |
10.5 |
Electron Affinities of Charge Transfer Complex Acceptors |
257 |
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10.6 |
Substituent Effect |
261 |
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10.7 |
Summary |
263 |
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References |
|
263 |
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11. Thermal Electrons and Environmental Pollutants |
266 |
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11.1 |
Introduction |
266 |
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11.2 |
Alkyl Halides |
267 |
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11.2.1 |
Morse Potential Energy Curves |
267 |
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11.2.2 |
Experimental Activation Energies |
269 |
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11.2.3 |
Alkyl Fluorocompounds |
272 |
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11.2.4 Electron Affinities of the Alkyl Halides |
274 |
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11.3 |
Aromatic Halides |
276 |
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11.3.1 Electron Affinities of Fluoroand Chlorobenzenes |
276 |
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11.3.2 Electron Affinities from Reduction Potentials |
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and CURES-EC |
283 |
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11.3.3 Negative-Ion Mass Spectra and Electron Affinities |
284 |
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11.4 |
Negative-Ion Mass Spectrometry |
287 |
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11.5 |
Calculation of the ECD and NIMS Temperature Dependence |
291 |
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CONTENTS |
xi |
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11.6 |
Summary |
|
293 |
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References |
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|
293 |
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12. |
Biologically Significant Molecules |
296 |
|||
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12.1 |
Introduction |
|
296 |
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12.2 |
Electron Affinities of Purines and Pyrimidines |
299 |
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12.2.1 Predictions of Electron Affinities |
299 |
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12.2.2 Electron Affinities from Reduction Potentials |
300 |
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12.2.3 Gas Phase Measurements of Electron Affinities |
302 |
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12.2.4 |
Theoretical Electron Affinities |
305 |
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12.3 |
Electron Affinities of Biological Molecules from |
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Reduction Potentials |
307 |
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12.4 |
Gas Phase Acidities of Nucleic Acids |
310 |
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12.5 |
Morse Potential Energy Curves for Thymine and Cytosine |
311 |
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12.6 |
Gas Phase Acidities and Electron Affinities of the Amino Acids |
315 |
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|
12.7 |
The Calculation of the ECD and NIMS Temperature |
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Dependence |
|
316 |
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12.8 |
Electron Affinities of AT AU and GC |
318 |
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12.9 |
Radiation Damage in DNA |
320 |
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12.10 |
Summary |
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326 |
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References |
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|
327 |
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APPENDICES |
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|
329 |
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I Glossary of Terms, Acronyms, and Symbols |
331 |
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II Structures of Organic Molecules |
336 |
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III |
General Least Squares |
339 |
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IV |
Tables of Evaluated Electron Affinities |
349 |
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Table A1.1 |
Atoms |
|
349 |
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Table A1.2 Main Group Homonuclear Diatomic Molecules |
351 |
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References |
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|
352 |
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Table A2.1 and A2.2 |
CH Molecules |
355 |
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References |
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|
357 |
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Table A2.3 and A2.4 |
CHX Molecules |
357 |
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References |
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|
359 |
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Table A3.1 and A3.2 |
CHNX Molecules |
360 |
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References |
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|
361 |
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Table A4.1 and A4.2 |
CHO Molecules |
362 |
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Table A4.3 and A4.4 |
CHOX Molecules |
366 |
xii |
CONTENTS |
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|
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References |
|
369 |
|
Table A5.1 and A5.2 |
CHON Molecules |
370 |
|
Table A5.3 and A5.4 |
CHONX Molecules |
375 |
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References |
|
376 |
|
Table A6.1 Bergman Dewar set |
377 |
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Table A6.2 Values Different from NIST Values |
|
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(from Tables A2.1 to A5.4) |
378 |
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Table A6.3 Unpublished or Updated Gas Phase Values not |
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|
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in NIST Tables |
380 |
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Table A6.4 Values for Adenine, Guanine, Cytosine, Uracil, |
|
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Thymine, and Their Hydrates |
382 |
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Table A6.5 Values for Charge Transfer Complex Acceptors |
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not in NIST Tables |
382 |
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Table A6.6 Values for Chlorinated Hydrocarbons from |
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Reduction Potentials and CURES-EC |
383 |
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Table A6.7 Values for Biological Compounds from |
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Reduction Potentials |
383 |
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AUTHOR INDEX |
|
387 |
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SUBJECT INDEX |
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395 |