Kinetic and mechanistic aspects of the NO oxidation by O<sub>2</sub> in aqueous phase

International Journal of Chemical Kinetics - Tập 26 Số 12 - Trang 1207-1227 - 1994
Marçlal Pires1, Michel J. Rossi1, David S. Ross2
1Laboratoire de Pollution Atmosphérique et Sol (LPAS), Ecole Polytechnique Fédérale de Lausanne (EPFL), CH‐1015, Lausanne, Switzerland
2Department of Physical Organic Chemistry, Physical Sciences Division, SRI International, Menlo Park California

Tóm tắt

AbstractThe oxidation kinetics of NO by O2 in aqueous solution was observed using a stopped flow apparatus. The kinetics follows a third order rate law of the form k · [NO]2 · [O2] in analogy to gas‐phase results. The rate constant at 296 K was measured as (6.4 ± 0.8) · 106 M−2 s−1 with an activation energy of 2.3 kcal/mol and a preexponential factor of (4.0 ± 0.5) · 108 M−2 s−1. The rate constant displays a very slight pH dependence corresponding to less than a factor of three over the range 0 to 12. The system NO/O2 in aqueous solution is an efficient nitrosating agent which has been tested using phenol as a substrate over the pH range 0 to 12. The rate limiting step leading to formation of 4‐nitrosophenol is the formation of the reactive intermediate whose competitive hydrolysis yields HONO or NO2−. The absence of NO3− in the autoxidation of NO, the exclusive presence of NO2− as a product of the nitrosation reaction of phenol, and the kinetic results of the N3− trapping experiments point towards N2O3 as the reactive intermediate. © 1994 John Wiley & Sons, Inc.

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Tài liệu tham khảo

10.1016/0968-0004(89)90181-3

10.1039/tf9635902323

10.1021/je60060a013

Pogrebnaya V. L., 1975, J. Appl. Chem. USSR, 48, 1004

10.1252/kakoronbunshu.15.1115

10.1021/tx00031a003

10.1002/kin.550250506

10.1029/92JD01222

Young C. L., 1982, Oxides of Nitrogen

1981, Oxygen and Ozone

1967, UV Atlas of Organic Compounds

Williams D. L. H., 1988, Nitrosation

Benson S. W., 1960, The Foundations of Chemical Kinetics, 21

Schwartz S. E., 1983, 1

B. C.ChallisandR. J.Higgins J. Chem. Soc. Perkin Trans. II 1597(1973).

10.1002/kin.550181107

10.1016/0301-0104(78)87004-9

10.1021/j100461a024

10.1021/i160053a010

10.1016/0014-5793(93)81748-O

D. S.Ross D.Hendry andC. L.Gu NOx Aerosol Chemistry in the Atmosphere SRI Report to the National Science Foundation August1983 p.C‐6 (Project 2015).

Pogrebnaya V. L., 1976, J. Appl. Chem. USSR, 49, 757

B. C.ChallisandS. A.Kyrtopoulos J. Chem. Soc. Perkin II 1296 (1987).

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International Journal of Chemical Kinetics

Tập 26 Số 12

1207-1227

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