Publication Type |
abstract |
School or College |
College of Engineering |
Department |
Chemical Engineering |
Creator |
Sarofim, Adel F.; Truong, Thanh |
Other Author |
Violi, Angela |
Title |
Kinetics of hydrogen abstraction reactions from polycyclic aromatic hydrocarbons by H atoms |
Date |
2004 |
Description |
An application of the Reaction Class Transition State Theory/Linear Energy Relationship (RC-TST/LER) is presented for the evaluation of the thermal rate constants of hydrogen abstraction reactions by H atoms from Polycyclic Aromatic Hydrocarbons (PAH). Two classes of reactions have been considered, namely hydrogen bonded to six- and five-membered rings, respectively, and twenty-two reactions have been used to develop the RC-TST/LER parameters. B3LYP and BH&HLYP density functional theory methods were used to calculate necessary potential energy surface information. Detailed analyses of RC-TST/LER reaction factors lead to the conclusion that rate constants for any reaction in these two classes can be approximated by those of its corresponding principal reaction corrected by the reaction symmetry factor. Specifically, for hydrogen abstraction from six-membered rings such as naphthalene and pyrene, k(T) = (?/?H+C6H6) kH+C6H6 = (?/6){1.42 × 108T1.77 exp(?6570/T)}(cm3/mol·s), and for hydrogen abstraction from five-membered rings such as acenaphthylene and acephenanthrylene, k(T) = (?/?H+C12H8) kH+C12H8 = (?/2){3.27 × 108T1.71 exp(?8170/T)} (cm3/mol·s), where ? is the reaction symmetry number. |
Type |
Text |
Publisher |
American Chemical Society |
Volume |
108 |
Issue |
22 |
First Page |
4846 |
Last Page |
4852 |
Subject |
Reaction Class Transition State Theory; Linear Energy Relationship; Hydrogen abstraction reactions |
Subject LCSH |
Polycyclic aromatic hydrocarbons |
Dissertation Institution |
University of Utah |
Language |
eng |
Bibliographic Citation |
Violi, A., Troung, T. N., & Sarofim, A. F. (2004). Kinetics of hydrogen abstraction reactions from polycyclic aromatic hydrocarbons by H atoms. Journal of Physical Chemistry A, 108(22), 4846-52. |
Rights Management |
(c)American Chemical Society http://dx.doi.org/10.1021/jp026557d |
Format Medium |
application/pdf |
Format Extent |
119,103 bytes |
Identifier |
ir-main,6930 |
ARK |
ark:/87278/s6n87vhw |
Setname |
ir_uspace |
ID |
707863 |
Reference URL |
https://collections.lib.utah.edu/ark:/87278/s6n87vhw |