Air pollution research report 40 - Organic peroxy radicals

Directorate-General For The Information Society And Media European Commission Directorate-General For Research And Innovation

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Kinetics, spectroscopy and tropospheric chemistry
Environment policy and protection of the environment
Environmental research

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• Publié par: DIRECTORATE-GENERAL-FOR-THE-INFORMATION-SOCIETY-AND-MEDIA-EUROPEAN-COMMISSION-DI
• Nombre de lectures: 8
• Langue: English
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ISSN 101B-5593
COMMISSION OF THE EUROPEAN COMMUNITIES
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Kinetics; spèctroseòpy and
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environment and
quality of life
Air pollution research report 40
ORGANIC PEROXY RADICALS
Kinetics, spectroscopy and tropospheric chemistry
1 2 3 1 P. D. Lightfoot, R. A. Cox, J. N. Crowley, M. Destriau,
4 4 3 5 G. D. Hayman, M. E. Jenkin, G. K. Moortgat, F. Zabel
1 Laboratoire de photophysique et photochimie moléculaire
Université de Bordeaux I
F-33405 Talence Cedex
2 Marine and Atmospheric Science Directorate
NERC HQ, Polaris House
North Star Avenue
Swindon SN2 1 EU
United Kingdom
3 Abt. Chemie der Atmosphäre
Max-Planck-Institut für Chemie
Postfach 3060
D-W-6500 Mainz
« AEA
Environment and Energy
Building B551
Harwell Laboratory
Didcot, Oxon 0X11 ORA
United Kingdom
5 Bergische Universität
Physikalische Chemie
Gauss-Straße 20
D-W-5600 Wuppertal 1
Directorate-General
Science, Research and Development
PARI ÉURÖP. ßibiioth. Environment research programme
N.C. EUR 14502 EN 1993
CM Published by the
COMMISSION OF THE EUROPEAN COMMUNITIES
Directorate-General XIII
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LEGAL NOTICE
Neither the Commission of the European Communities nor any person acting
on behalf of then is responsible for the use which might be made of
the following information.
Cataloguing data can be found at the end of this publication
Luxembourg: Office for Official Publications of the European Communities, 1993
ISBN 92-826-5681-0
© ECSC-EEC-EAEC, Brussels • Luxembourg, 1993
Printed in Belgium CONTENTS
Organic Peroxy Radicals: Kinetics, Spectroscopy and Tropospheric Chemistry
P.D. Lightfoot, R.A. Cox, J.N. Crowley, M. Destriau,
G.D. Hayman, M.E. Jenkin, G.K. Moortgat and F. Zabel
Preface v
I. Introduction 2
II. Laboratory experimental techniques 4
II. A. Methods of generating peroxy radicals S
II. A. 1. Generation of the organic fragment in the presence of Cs 5
II. A.2. Peroxy radical production in the absence of 0 10 2
II.B. Methods of detection 11
II.B.1. Peroxy radicals
II.B.2. Reaction products2
IET. Structure, spectroscopy and thermochemistry
m.A. Structure
EI. A.. Geometry of the ground state
ni.A.2. Electronic energy levels
and photolytic dissociation of peroxy radicals IS
m.B. Electronic (u.V.) spectroscopy 16
m.B.1. H08 2
m.B.2. Alkylperoxy radicals 20
III.B.3. Acylperoxys 32
m.B.4. Oxygen-substituted peroxy radicals 3
m.B.5. Halogen-substituted peroxys7
ni.B.6. Some comments regarding peroxy radical u.v. spectra 44
in.C. Near-i.r., i.r. and e.s.r. spectroscopy 46
III.C.l. Electronic (near i.r.) spectroscopy
ffl.C.2. Vibrational spectroscopy
ni.C.3. Electron spin resonance spectroscopy 51
ULD. Thermochemistry of peroxy radicals4
m.D.l. Alkylperoxy radicals 55
m.D.2. Acylperoxys6
m.D.3. Oxygen-substituted peroxy radicals7
m.D.4. Halogen-substituted peroxys
III.D.5. Unsaturated peroxy radicals8
III.D.6. Thermochemical parameters for the 0-(C)(0*) group 60
III.D.7. Summary 61
IV. Reactions of peroxy radicals
IV. A . Reactions between peroxy radicals
IV.A. 1. Alkylperoxy radicals6
IV.A.2. Acylperoxys 7
IV.A.3. Oxygen-substituted peroxy radicals 7IV.A.4. Halogen-substituted peroxy radicals 79
IV.A.5. Discussion 82
IV. B. Reactions of peroxy radicals with H0 87 2
IV.B.l. Alkylperoxys
IV.B.2. Acylperoxy radicals 91
IV.B.3. Oxygen-substituted peroxy radicals
IV.B.4. Discussion4
. IV.C. Reactions of peroxy radicals with NO
IV. C. 1. Alkylperoxy radicals7
IV.C.2. Acylperoxys 105
IV.C.3. Oxygen-substituted peroxy radicals
IV.C.4. Halogen-substituted peroxys6
IV.C.5. Aromatic peroxy radicals
IV.C.6. Discussion
IV.D. Reactions of peroxy radicals with N0 110 2
. rV.D.l. Alkylperoxys1
IV.D.2. Acylperoxy radicals4
IV.D.3. Oxygen-substituted peroxy radicals7
IV.D.4. Halogen-substituted peroxys
IV.D.5. Aromatic peroxy radicals 12
IV.D.6. Discussion0
IV.E. Reactions of peroxy radicals with other species
IV.E.1. Alkylperoxys
IV.E.2. Halogen-substituted peroxy radicals 13
IV.E.3. Summary 13
V. Peroxy radicals in the atmosphere
V. A. Production of peroxy radicals in the atmosphere1
V.B. Photochemical ozone formation
V.C. Reactions competing with photochemical ozone formation 132
V.D. Peroxy radicals in the boundary layer under low NO conditions6 x
V.E.ys in night-time oxidation chemistry 137
V.F. Peroxy radicals in halocarbonn9
V.G. Measurements of peroxy radical concentrations in the atmosphere 140
VI. Future work 143
VI. A. Laboratory experimental techniques
VLB. Structure, spectroscopy and thermochemistry 144
VI. C. Reactions of peroxy radicals
VI.C.l. Reactions between peroxy radicals
VI.C.2.s of peroxy radicals with H05 2
VI.C.3. Reactions of peroxys with NO and N0 146 2
VI.C.4.s of peroxy radicals with other species
VLD. Peroxy radicals in the atmosphere 14
VII. References 147
IV -PREFACE
P.D . LlGHTFOOT
Editor, Laboratoire de Photophysique et Photochimie Moleculaire, Université de Bordeaux I, Talence, France
Dagaut and Kurylo is restricted to the u.v. That the atmospheric degradation of organic
compounds is a complex process involving free spectroscopy and the kinetics and mechanisms
radicals is undisputed. In the atmosphere, of reactions of peroxy radicals, whereas we
organic molecules are transformed, after initial cover, in addition, the role of peroxy radicals in
free radical attack or photolysis, into peroxy the atmosphere and their detection in the field,
radicals, RO2. The important role thaty as well as their thermochemistry, electronic
radicals play as intermediates in the degradation structure and i.r. and e.s.r.spectroscopy.
of organic compounds has been recognised since The authors of this review have received
the early 1970's and has led to the development support for their research into peroxy radical
of a comprehensive theory of tropospheric chemistry from the Commission of the
photochemistry which is broadly consistent with European Communities, for example under the
observations of the distributions of relevant Science and Technology for Environmental
trace atmospheric constituents such as ozone, Protection (STEP) initiative, and also under the
hydrocarbons and nitrogen oxides. In recent former COST 611 programme. We are all very
years, a great deal of progress has been made grateful for this support, as well as the personal
towards an understanding of peroxy radical involvement of Dr. G. Angeletti of Directorate-
chemistry and a review of the situation seemed General XII of the CEC. The Commission
timely. In this review, we attempt to summarise provided the impetus for the preparation of the
the current knowledge of the chemistry and review and very generously provided funds for
physical properties of organic peroxy radicals, meetings of the review group.
with particular emphasis on their relevance to The review is being published both here,
tropospheric chemistry. We have tried to under the auspices of the CEC, and by the
include published literature and work in press journal Atmospheric Enviroment, where it will
thup to the end of 1991. The review team is made appear as the 10 issue of volume 26A in 1992.
up of representatives from several European The review closely follows the format of the
research groups which are active within the field review of the physics and chemistry of the
of peroxy radical chemistry. It has been an nitrate radical, edited by R.P. Wayne, which
honour to chair this group and to coordinate its appeared recently as a CEC publication and in
efforts, as well as to act as Editor for this Atmospheric Environment.
document that we have submitted to Much of the work reported in this review, by
Atmospheric Environment. the authors and by others, has been performed
as part of the LACTOZ (Laboratory Studies of Since undertaking this review, a second
Chemistry Related to Tropospheric Ozone) review of gas-phase peroxy radical chemistry,
subproject of the EUROTRAC programme. prepared by Drs. T.J. Wallington, P. Dagaut
and M.J. Kurylo, and which will be published Finally, I would like to take this opportunity
almost simultaneously with our own in to thank my co-authors for the enormous
Chemical Reviews, has come to our attention. amount of time and effort that they have
Although considerable overlap is of course devoted to the review, despite numerous other
unavoidable, the two reviews have somewhat commitments.
different goals. The review of Drs. Wallington,
V -ORGANIC PEROXY RADICALS: KINETICS,
SPECTROSCOPY AND TROPOSPHERIC CHEMISTRY
1P.D. LIGHTFOOT,*R.A. Cox, J.N. CROWLEY,* M. DESTRIAU,*
T G.D. HAYMAN,^ M.E. JENKIN,^ G.K. MOORTGAT* and F. ZABEL
»Laboratoire de Photophysique et Photochimie Moléculaire, Université de Bordeaux I, 33405
Talence Cedex, France. 1 Marine and Atmospheric Science Directorate,