The rate coefficients for the reactions of O(P-3) with CF3I (1) and CH3I (2) were measured between 213 and 364 K to be: k(1)(T) = (7.9 +/- 0.8) x 10(-12) exp-(175 +/- 40)/T and k(2)(T) = (1.0 +/- 0.2) x 10(-11) exp(160 +/- 50)/T cm(3) molecule(-1) s(-1). The rate coefficients for the reaction of O(P-3) with CD3I, (CH3)(2)CHCH2I,(CH3)(2)CHI, CF3CH2I, CF3CHFI, and CF3CF2I at 298 K were also measured. The yields of the IO and CF3O products in reaction 1 at 298 K were found to be 0.83 +/- 0.09 and <0.01, respectively. Product yields of reaction 2 at 298 K were measured to be IO (0.44 +/- 0.04), OH (0.16 +/- 0.05), H (0.07 +/- 0.02), CH3O (<0.03), and HI (<0.05). IO, OH, and CH3O were detected via laser-induced fluorescence, O and H atoms via resonance fluorescence, and IO, CF3O, and HI by chemical ionization mass spectrometry. The IO yield from reactions 1 and 2 showed a slight positive temperature dependence. Within our experimental error the OH yield from reaction 2 was temperature independent. An upper limit for the enthalpy of formation of IO, Delta(f)H(o)(298.15 K)(IO) <28.8 kcal mol(-1), was obtained from an interpretation of our data.
%0 Journal Article
%1 Gilles:1996p2240
%A Gilles, MK
%A Turnipseed, AA
%A Talukdar, RK
%A Rudich, Y
%A Villalta, PW
%A Huey, LG
%A Burkholder, JB
%A Ravishankara, A. R
%D 1996
%J Journal of Physical Chemistry
%K 222 Absorption Cf3I, Cross-Sections, Depletion, Fluorescence, Kinetics, Laser-Induced Nm, Ozone Photochemistry Photolysis, Quantum Rate-Constant, Yields,
%N 33
%P 14005--14015
%T Reactions of O(P-3) with alkyl iodides: Rate coefficients and reaction products
%U http://www.google.com/search?client=safari&rls=en-us&q=Reactions+of+O(P-3)+with+alkyl+iodides:+Rate+coefficients+and+reaction+products&ie=UTF-8&oe=UTF-8
%V 100
%X The rate coefficients for the reactions of O(P-3) with CF3I (1) and CH3I (2) were measured between 213 and 364 K to be: k(1)(T) = (7.9 +/- 0.8) x 10(-12) exp-(175 +/- 40)/T and k(2)(T) = (1.0 +/- 0.2) x 10(-11) exp(160 +/- 50)/T cm(3) molecule(-1) s(-1). The rate coefficients for the reaction of O(P-3) with CD3I, (CH3)(2)CHCH2I,(CH3)(2)CHI, CF3CH2I, CF3CHFI, and CF3CF2I at 298 K were also measured. The yields of the IO and CF3O products in reaction 1 at 298 K were found to be 0.83 +/- 0.09 and <0.01, respectively. Product yields of reaction 2 at 298 K were measured to be IO (0.44 +/- 0.04), OH (0.16 +/- 0.05), H (0.07 +/- 0.02), CH3O (<0.03), and HI (<0.05). IO, OH, and CH3O were detected via laser-induced fluorescence, O and H atoms via resonance fluorescence, and IO, CF3O, and HI by chemical ionization mass spectrometry. The IO yield from reactions 1 and 2 showed a slight positive temperature dependence. Within our experimental error the OH yield from reaction 2 was temperature independent. An upper limit for the enthalpy of formation of IO, Delta(f)H(o)(298.15 K)(IO) <28.8 kcal mol(-1), was obtained from an interpretation of our data.
@article{Gilles:1996p2240,
abstract = {The rate coefficients for the reactions of O(P-3) with CF3I (1) and CH3I (2) were measured between 213 and 364 K to be: k(1)(T) = (7.9 +/- 0.8) x 10(-12) exp[-(175 +/- 40)/T] and k(2)(T) = (1.0 +/- 0.2) x 10(-11) exp[(160 +/- 50)/T] cm(3) molecule(-1) s(-1). The rate coefficients for the reaction of O(P-3) with CD3I, (CH3)(2)CHCH2I,(CH3)(2)CHI, CF3CH2I, CF3CHFI, and CF3CF2I at 298 K were also measured. The yields of the IO and CF3O products in reaction 1 at 298 K were found to be 0.83 +/- 0.09 and <0.01, respectively. Product yields of reaction 2 at 298 K were measured to be IO (0.44 +/- 0.04), OH (0.16 +/- 0.05), H (0.07 +/- 0.02), CH3O (<0.03), and HI (<0.05). IO, OH, and CH3O were detected via laser-induced fluorescence, O and H atoms via resonance fluorescence, and IO, CF3O, and HI by chemical ionization mass spectrometry. The IO yield from reactions 1 and 2 showed a slight positive temperature dependence. Within our experimental error the OH yield from reaction 2 was temperature independent. An upper limit for the enthalpy of formation of IO, Delta(f)H(o)(298.15 K)(IO) <28.8 kcal mol(-1), was obtained from an interpretation of our data.},
added-at = {2010-06-22T19:38:37.000+0200},
affiliation = {NOAA,AERON LAB,BOULDER,CO 80303},
author = {Gilles, MK and Turnipseed, AA and Talukdar, RK and Rudich, Y and Villalta, PW and Huey, LG and Burkholder, JB and Ravishankara, A. R},
biburl = {https://www.bibsonomy.org/bibtex/2dff1de40d0ca2013655306357530427f/gsmith},
date-added = {2010-03-23 14:40:45 -0400},
date-modified = {2010-05-07 17:09:40 -0400},
interhash = {9740eb8b693b784fd6f1b8325290e6c2},
intrahash = {dff1de40d0ca2013655306357530427f},
journal = {Journal of Physical Chemistry},
keywords = {222 Absorption Cf3I, Cross-Sections, Depletion, Fluorescence, Kinetics, Laser-Induced Nm, Ozone Photochemistry Photolysis, Quantum Rate-Constant, Yields,},
language = {English},
local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Journal%20of%20Physical%20Chemistry/1996/Journal%20of%20Physical%20Chemistry,%20100,%2014005-14015%201996-1.pdf},
month = Jan,
number = 33,
pages = {14005--14015},
pmid = {A1996VC55000020},
rating = {0},
timestamp = {2010-06-22T19:39:20.000+0200},
title = {Reactions of O(P-3) with alkyl iodides: Rate coefficients and reaction products},
uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p2240},
url = {http://www.google.com/search?client=safari&rls=en-us&q=Reactions+of+O(P-3)+with+alkyl+iodides:+Rate+coefficients+and+reaction+products&ie=UTF-8&oe=UTF-8},
volume = 100,
year = 1996
}