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Atmospheric Photochemical Oxidation of Benzene:  Benzene + OH and the Benzene−OH Adduct (Hydroxyl-2,4-cyclohexadienyl) + O_2

Lay, Tsan H. and Bozzelli, Joseph W. and Seinfeld, John H. (1996) Atmospheric Photochemical Oxidation of Benzene:  Benzene + OH and the Benzene−OH Adduct (Hydroxyl-2,4-cyclohexadienyl) + O_2. Journal of Physical Chemistry, 100 (16). pp. 6543-6554. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20180720-152513589

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Abstract

The addition of hydroxyl radical to benzene leading to the formation of the hydroxyl-2,4-cyclohexadienyl radical (benzene−OH adduct, BOH) initiates the atmospheric oxidation of benzene. This reaction and subsequent reactions of the BOH adduct with O_2 are chemically activated reactions. Rate constants of these chemically activated bimolecular reactions and unimolecular decompositions are analyzed using a quantum version of Rice−Ramsperger−Kassel theory (QRRK) for k(E) and a modified strong collision approach for falloff. Results of QRRK analyses show that stabilization channels of energized BOH and benzene−OH−O_2 (BOHO_2) adducts are dominant in chemically activated reaction systems under atmospheric condition. Unimolecular reactions of stabilized adducts to products are also important. Thermodynamic parameters (ΔH_f^°_(298), S^°_(298), and C_p(T)s) are calculated using group additivity techniques with evaluated bond energies (for ΔH_f^°_(298)) and semiempirical PM3 molecular orbital calculations (for S6°_(298) and C_p(T)s). A limited elementary reaction mechanism that includes 29 reactions and 26 species is developed with reverse reaction rates determined from species thermodynamic parameters and microscopic reversibility for each step. Simulation results of three reaction systems indicate that pseudo-equilibrium is attained and that equilibrium levels of the important BOH and BOHO_2 adducts are controlled by thermodynamic properties. The most important bicyclic intermediate leading to ring cleavage products is adduct III. Rate constants of important bimolecular reactions are (k = A(T/K)^n exp(−E_a/RT), A in cm^3/(mol s), Ea in kcal/mol): k^4, (4.65 × 10^(15))(T/K)^(-1.18) e^(-1.23/RT) for C)6H)6 + OH ⇒ BOH; k_7, (3.55 × 10^(36))(T/K)^(-8.86) e^(-3.79/RT) for BOH + O_2 ⇒ BOHO_2; k_8, (1.73 × 10^(10))(T/K)^(-0.26) e^(-8.28/RT) for BOH + O_2 ⇒ hexadienedial + OH; k_9, (7.06 × 10^(14))(T/K)^(-1.83) e^(-5.36/RT) for BOH + O_2 ⇒ phenol + HO_2; k_(10), (2.14 × 10^(15))(T/K)^(-2.05) e^(-4.69/RT) for BOH + O_2 ⇒ adduct III. Rate constants of important unimolecular reactions are (A in s^(-1)): k_6, (2.04 × 10^(25))(T/K)^(-4.2) e^(-24.5/RT) for BOH ⇒ phenol + H; k_(15), (6.30 × 10^(40))(T/K)^(-10.86) e^(-19.4/RT) for BOHO)2 ⇒ phenol + HO)2; k_(16), (1.43 × 10^(42))(T/K)^(-11.34) e^(-18.8/RT) for BOHO_2 ⇒ adduct III.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/jp951726yDOIArticle
ORCID:
AuthorORCID
Seinfeld, John H.0000-0003-1344-4068
Alternate Title:Atmospheric Photochemical Oxidation of Benzene:  Benzene + OH and the Benzene−OH Adduct (Hydroxyl-2,4-cyclohexadienyl) + O2
Additional Information:© 1996 American Chemical Society. Received: June 20, 1995; In Final Form: January 15, 1996. The authors gratefully acknowledge funding from the NJIT-MIT USEPA Northeast Research Center and the USEPA MIT-CALTECH-NJIT Research Center on Airborne Organics.
Funders:
Funding AgencyGrant Number
NJIT-MIT USEPA Northeast Research CenterUNSPECIFIED
USEPA MIT-CALTECH-NJIT Research Center on Airborne OrganicsUNSPECIFIED
Record Number:CaltechAUTHORS:20180720-152513589
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180720-152513589
Official Citation:Atmospheric Photochemical Oxidation of Benzene:  Benzene + OH and the Benzene−OH Adduct (Hydroxyl-2,4-cyclohexadienyl) + O2 Tsan H. Lay, Joseph W. Bozzelli, and John H. Seinfeld The Journal of Physical Chemistry 1996 100 (16), 6543-6554 DOI: 10.1021/jp951726y
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88094
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:23 Jul 2018 21:20
Last Modified:23 Jul 2018 21:20

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