Time-resolved spectroscopic study of the reaction Cl + n-C5H12 --> HCl + C5H11 in solution

The Journal of Physical Chemistry. a
Leonid ShepsF Fleming Crim

Abstract

We study the hydrogen abstraction reaction from pentane by chlorine radicals using four different experimental approaches. We use two different solvents (CH2Cl2 and CCl4) and two different chlorine atom sources (photodissociation of dissolved Cl2 and two-photon photolysis of the solvent) to investigate their effects on the recombination and reactivity of the chlorine radical. All four experimental schemes involve direct probing of the transient chlorine population via a charge transfer transition with a solvent molecule. In one of the four approaches, photolysis of Cl2 in dichloromethane, we also monitor the nascent reaction products (HCl) by transient vibrational spectroscopy. Probing both the reactants and the products provides a comprehensive view of this bimolecular reaction in solution. Between one-third and two-thirds of the chlorine radicals that initially escape the solvent cage undergo diffusive geminate recombination with their partner radical (either another chlorine atom or the solvent radical). The rest react with pentane with the bimolecular rate constants k(bi) = (9.5 +/- 0.7) x 10(9) M(-1) s(-1) in CH2Cl2 and k(bi) = (7.4 +/- 2) x 10(9) M(-1) s(-1) in CCl4. The recombination yield phi(rec) depends on both the ch...Continue Reading

References

Oct 25, 2001·The Journal of Organic Chemistry·John E. Chateauneuf
Jul 13, 2006·The Journal of Physical Chemistry. a·Leonid ShepsF Fleming Crim

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Citations

Sep 4, 2008·Proceedings of the National Academy of Sciences of the United States of America·F Fleming Crim
Mar 13, 2014·The Journal of Chemical Physics·Andrew J Orr-Ewing
Jul 2, 2010·The Journal of Chemical Physics·Rebecca A RoseAndrew J Orr-Ewing
Jul 5, 2011·The Journal of Chemical Physics·Rebecca A RoseAndrew J Orr-Ewing
Apr 6, 2016·The Journal of Physical Chemistry. B·Jae-Yoon ShinF Fleming Crim
Apr 2, 2015·Annual Review of Physical Chemistry·Andrew J Orr-Ewing
Jun 12, 2014·The Journal of Physical Chemistry. a·Thomas J PrestonSaulo A Vázquez
Aug 24, 2013·The Journal of Physical Chemistry. a·Fawzi Abou-ChahineScott A Reid
Jul 7, 2017·Chemical Society Reviews·Andrew J Orr-Ewing
May 8, 2010·Physical Chemistry Chemical Physics : PCCP·Stuart J GreavesAndrew J Orr-Ewing
Apr 14, 2012·Physical Chemistry Chemical Physics : PCCP·R A RoseA J Orr-Ewing
Nov 7, 2008·The Journal of Physical Chemistry. a·Andrew C CrowtherF Fleming Crim
Sep 29, 2006·The Journal of Physical Chemistry. B·Marcin BroniatowskiPatrycja Dynarowicz-Łatka
Dec 9, 2009·The Journal of Physical Chemistry. a·Stacey L CarrierF Fleming Crim
Apr 18, 2009·The Journal of Physical Chemistry. a·Andrew C CrowtherF Fleming Crim
Sep 27, 2007·Langmuir : the ACS Journal of Surfaces and Colloids·Penglei ChenMinghua Liu
May 19, 2011·The Journal of Physical Chemistry Letters·Andrew J Orr-EwingRebecca A Rose
Apr 8, 2006·Annual Review of Physical Chemistry·Christopher G Elles, F Fleming Crim

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