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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

Published by John Wiley & Sons, Inc., Hoboken, New Jersey.

Published simultaneously in Canada.

No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400, fax 978-646-8600, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008.

Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and speciﬁcally disclaim any implied warranties of merchantability or ﬁtness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of proﬁt or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.

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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

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			xiii
PREFACE			xv
1. Scope and History of the Electron			1
1.1	General Objectives and Organization		1
1.2	General Scope		2
1.3	History of the Electron		4
References			6
2. Deﬁnitions, Nomenclature, Reactions, and Equations			8
2.1	Introduction		8
2.2	Deﬁnition of Kinetic and Energetic Terms		8
2.3	Additional Gas Phase Ionic Reactions		15
2.4	Electron Afﬁnities from Solution Data		16
2.5	Semi-Empirical Calculations of Energetic Quantities		17
2.6	Herschbach Ionic Morse Potential Energy Curves		18
2.7	Summary		19
References			20
3. Thermal Electron Reactions at the University of Houston			22
3.1	General Introduction		22
3.2	The First Half-Century, 1900 to 1950		23
3.3	Fundamental Discovery, 1950 to 1960		25
3.4	General Accomplishments, 1960 to 1970		27
	3.4.1	Introduction	27
	3.4.2	The Wentworth Group	28
	3.4.3	Stable Negative-Ion Formation	28
	3.4.4	Dissociative Thermal Electron Attachment	33
	3.4.5	Nonlinear Least Squares	35

3.5Milestones in the Wentworth Laboratory and Complementary

Methods, 1970 to 1980

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
4. Theoretical Basis of the Experimental Tools		47
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

	of Aromatic Hydrocarbons		66
4.7	Electron Afﬁnities and Charge Transfer Complex Energies		67
4.8	Summary		71
References			73
5. Experimental Procedures and Data Reduction			75
5.1	Introduction		75
5.2	Experimental ECD and NICI Procedures		76
5.3	Reduction of ECD Data to Fundamental Properties		85
	5.3.1	Introduction	85
	5.3.2	Acetophenone and Benzaldehyde	86
	5.3.3 Benzanthracene, Benz[a]pyrene, and 1-Naphthaldehyde		87
	5.3.4	Carbon Disulﬁde	89
	5.3.5	Nitromethane	90
	5.3.6 Consolidation of Electron Afﬁnities for Molecular Oxygen		91
5.4	Reduction of Negative-Ion Mass Spectral Data		93
5.5	Precision and Accuracy		96
5.6	Evaluation of Experimental Results		97
5.7	Summary		101
References			101
6. Complementary Experimental and Theoretical Procedures			103
6.1	Introduction		103
6.2	Equilibrium Methods for Determining Electron Afﬁnities		105
6.3	Photon Techniques		110
6.4	Thermal Charge Transfer Methods		116
6.5	Electron and Particle Beam Techniques		121
6.6	Condensed Phase Measurements of Electron Afﬁnities		124
6.7	Complementary Theoretical Calculations		125
	6.7.1	Atomic Electron Afﬁnities	126
	6.7.2	Polyatomic Molecules	128
6.8	Rate Constants for Attachment, Detachment, and Recombination		132

	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
	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
Electron Afﬁnities		168
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
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
10. Negative Ions of Organic Molecules			234
	10.1	Introduction	234
	10.2	Electron Afﬁnities and Potential Energy Curves for
		Nitrobenzene and Nitromethane	235

10.3Electron Afﬁnities Determined Using the Magnetron, Alkali Metal Beam, Photon, and Collisional

	Ionization Methods		238
	10.3.1 Electron Afﬁnities Determined Using the
		Magnetron Method	238
	10.3.2 Electron Afﬁnities Determined Using the
		AMB Method	240
	10.3.3 Electron Afﬁnities Determined Using
		Photon Methods	241
	10.3.4 Electron Afﬁnities Determined Using Collisional
		Ionization Methods	243
10.4	Electron Afﬁnities Determined Using the ECD, NIMS,
	and TCT Methods		244
	10.4.1 Electron Afﬁnities of Aromatic Hydrocarbons
		by the ECD Method	244
	10.4.2 Electron Afﬁnities of Organic Carbonyl Compounds
		by the ECD Method	246
	10.4.3 Electron Afﬁnities of Organic Nitro Compounds
		the ECD and TCT Methods	253
10.5	Electron Afﬁnities of Charge Transfer Complex Acceptors		257
10.6	Substituent Effect		261
10.7	Summary		263
References			263
11. Thermal Electrons and Environmental Pollutants			266
11.1	Introduction		266
11.2	Alkyl Halides		267
	11.2.1	Morse Potential Energy Curves	267
	11.2.2	Experimental Activation Energies	269
	11.2.3	Alkyl Fluorocompounds	272
	11.2.4 Electron Afﬁnities of the Alkyl Halides		274
11.3	Aromatic Halides		276
	11.3.1 Electron Afﬁnities of Fluoroand Chlorobenzenes		276
	11.3.2 Electron Afﬁnities from Reduction Potentials
		and CURES-EC	283
	11.3.3 Negative-Ion Mass Spectra and Electron Afﬁnities		284
11.4	Negative-Ion Mass Spectrometry		287
11.5	Calculation of the ECD and NIMS Temperature Dependence		291

				CONTENTS	xi
	11.6	Summary			293
	References				293
12.	Biologically Signiﬁcant Molecules				296
	12.1	Introduction			296
	12.2	Electron Afﬁnities of Purines and Pyrimidines			299
		12.2.1 Predictions of Electron Afﬁnities			299
		12.2.2 Electron Afﬁnities from Reduction Potentials			300
		12.2.3 Gas Phase Measurements of Electron Afﬁnities			302
		12.2.4	Theoretical Electron Afﬁnities		305
	12.3	Electron Afﬁnities of Biological Molecules from
		Reduction Potentials			307
	12.4	Gas Phase Acidities of Nucleic Acids			310
	12.5	Morse Potential Energy Curves for Thymine and Cytosine			311
	12.6	Gas Phase Acidities and Electron Afﬁnities of the Amino Acids			315
	12.7	The Calculation of the ECD and NIMS Temperature
		Dependence			316
	12.8	Electron Afﬁnities of AT AU and GC			318
	12.9	Radiation Damage in DNA			320
	12.10	Summary			326
	References				327
APPENDICES					329
I Glossary of Terms, Acronyms, and Symbols					331
II Structures of Organic Molecules					336
III	General Least Squares				339
IV	Tables of Evaluated Electron Afﬁnities				349
	Table A1.1		Atoms		349
	Table A1.2 Main Group Homonuclear Diatomic Molecules				351
	References				352
	Table A2.1 and A2.2			CH Molecules	355
	References				357
	Table A2.3 and A2.4			CHX Molecules	357
	References				359
	Table A3.1 and A3.2			CHNX Molecules	360
	References				361
	Table A4.1 and A4.2			CHO Molecules	362
	Table A4.3 and A4.4			CHOX Molecules	366

xii	CONTENTS
	References		369
	Table A5.1 and A5.2	CHON Molecules	370
	Table A5.3 and A5.4	CHONX Molecules	375
	References		376
	Table A6.1 Bergman Dewar set		377
	Table A6.2 Values Different from NIST Values
	(from Tables A2.1 to A5.4)		378
	Table A6.3 Unpublished or Updated Gas Phase Values not
	in NIST Tables		380
	Table A6.4 Values for Adenine, Guanine, Cytosine, Uracil,
	Thymine, and Their Hydrates		382
	Table A6.5 Values for Charge Transfer Complex Acceptors
	not in NIST Tables		382
	Table A6.6 Values for Chlorinated Hydrocarbons from
	Reduction Potentials and CURES-EC		383
	Table A6.7 Values for Biological Compounds from
	Reduction Potentials		383
AUTHOR INDEX			387
SUBJECT INDEX			395

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