Kinetic and theoretical studies of the reactions CH sub 3 C(O)O sub 2 + NO sub 2 + M r reversible CH sub 3 C(O)O sub 2 NO sub 2 + M between 248 and 393 K and between 30 and 760 Torr

Journal Article · Thu May 02 04:00:00 EDT 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100162a031· OSTI ID:5885818

Bridier, I; Caralp, F; Loirat, H; Lesclaux, R; Veyret, B ^[1]; Becker, K H; Reimer, A; Zabel, F ^[2]

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1. Univ. de Bordeaux 1, Talence (France)
2. Bergische Univ.-Gesamthochschule Wuppertal (West Germany)

The kinetics of the thermal decomposition and formation reactions of acetyl peroxynitrate (PAN) CH{sub 3}C(O)O{sub 2} + NO{sub 2} + M {leftrightarrow} CH{sub 3}C(O)O{sub 2}NO{sub 2} + M (1, {minus}1) was studied as a function of temperature and pressure by two groups. In one set of experiments, the decomposition of the peroxynitrate formed in the photolysis of CH{sub 3}CHO/Cl{sub 2}/O{sub 2}/N{sub 2}/NO{sub 2} mixtures was followed by in situ FTIR spectrometry. In the second set of experiments, the decay of the acetylperoxy radical formed in the flash photolysis of Cl{sub 2}/CH{sub 3}CHO/NO{sub 2}/air mixtures was monitored by UV absorption. From the two independent kinetic determinations of k{sub 1} and k{sup {minus}1}, the equilibrium constant K{sub 1}(T) was calculated to be 0.9 {times} 10{sup {minus}28} exp((14,000 {plus minus} 200)/T) cm{sup 3} molecule{sup {minus}1}. Quantum chemical and RRKM calculations were performed to obtain accurate and predictive representations of the data. In Troe's notation, the RRKM curves corresponding to the experimental results are represented by the following expressions for the limiting low- and high-pressure rate constants, with F{sub c} = 0.30: k{sub 0}({minus}1) = 4.9 {times} 10{sup {minus}3} exp({minus}(12,100 {plus minus} 500)/T) cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}; k{sub {infinity}}({minus}1) = 4.0 {times} 10{sup 16} exp({minus}(13,600 {plus minus} 350)/T) s{sup {minus}1}; k{sub 0}(1) = 2.7 {times} 10{sup {minus}28}(T/298){sup {minus}7.1{plus minus}1.7} cm{sup 6} molecule{sup {minus}2} s{sup {minus}1}; k{sub {infinity}}(1) = (12.1 {plus minus} 0.5) {times} 10{sup {minus}12}(T/298){sup {minus}0.9{plus minus}0.15} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The thermochemistry of reactions 1 and {minus}1 and the atmospheric implications of the thermal stability of PAN are briefly discussed.

• OSTI ID: 5885818
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:9; ISSN JPCHA; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
54 ENVIRONMENTAL SCIENCES
540120* -- Environment
Atmospheric-- Chemicals Monitoring & Transport-- (1990-)
ABSORPTION SPECTROSCOPY
ARRHENIUS EQUATION
ATMOSPHERIC CHEMISTRY
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
EQUATIONS
EQUILIBRIUM
ESTERS
EXPERIMENTAL DATA
FOURIER TRANSFORM SPECTROMETERS
INFORMATION
INFRARED RADIATION
KINETICS
LOW PRESSURE
MATHEMATICAL MODELS
MEASURING INSTRUMENTS
NITRATES
NITRIC ACID ESTERS
NITROGEN COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PEROXYACETYL NITRATE
PHYSICAL PROPERTIES
PRESSURE DEPENDENCE
PYROLYSIS
RADIATIONS
REACTION KINETICS
SPECTROMETERS
SPECTROSCOPY
SYNTHESIS
TEMPERATURE RANGE
TEMPERATURE RANGE 0273-0400 K
THEORETICAL DATA
THERMOCHEMICAL PROCESSES
THERMODYNAMIC PROPERTIES
ULTRAVIOLET RADIATION