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 00:00:00 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), Vol. 95:9; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

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