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Abstract
Broadband transient infra-red absorption measurements are reported that contrast the dynamics of reaction of Cl atoms with 2,3-dimethylbut-2-ene and n-pentane in chlorinated solvents. In both cases, H-atom transfer produces HCl and a hydrocarbon radical, but the energy release in the former reaction is greater because of the formation of a resonance-stabilized allylic radical. The reaction of Cl atoms with n-pentane in solution in CH2Cl2 forms HCl exclusively in its lowest vibrational level (v = 0), and our measured rate coefficient agrees with a prior report by Sheps et al., J. Phys. Chem. A, 2006, 110, 3087. The time-dependence of the growth of intensity in the HCl fundamental absorption band shows two domains of reaction: a prompt rise is associated with reaction of the photolytically generated Cl atoms with n-pentane molecules lying within the first solvent shell, whereas a slower further rise is attributed to reaction following diffusion through the solution. For the reaction of Cl atoms with 2,3-dimethylbut-2-ene, these two domains of reaction are also observed, and fitting to a kinetic model incorporating these components gives bimolecular rate coefficients for formation of HCl of (1.7 +/- 1.4) x 10(10) M-1 s(-1) in CDCl3 and (3.4 +/- 1.2) x 10(10) M-1 s(-1) in CCl4. However, an additional transient absorption is observed similar to 115 cm(-1) lower in wavenumber than the fundamental HCl absorption band and is assigned to the v = 2...
Original language | English |
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Pages (from-to) | 226-237 |
Number of pages | 12 |
Journal | Chemical Science |
Volume | 4 |
Issue number | 1 |
Early online date | 15 Oct 2012 |
DOIs | |
Publication status | Published - 1 Jan 2013 |
Keywords
- DIATOMIC POLAR-MOLECULES
- INFRARED-ABSORPTION
- LIQUID SOLUTIONS
- HYDROGEN ABSTRACTION
- ORGANIC-MOLECULES
- ROTATION SPECTRA
- DIMETHYL ETHER
- METHYL HALIDES
- HCL PRODUCTS
- METHANOL
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Dive into the research topics of 'Vibrationally resolved dynamics of the reaction of Cl atoms with 2,3-dimethylbut-2-ene in chlorinated solvents'. Together they form a unique fingerprint.Projects
- 3 Finished
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Dynamics of Gas-Liquid Reactions; The Pseudo-Surface Approach
Greaves, S. J. (Principal Investigator)
1/10/11 → 1/10/16
Project: Research
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NEW HORIZONS IN CHEMICAL AND PHOTOCHEMICAL DYNAMICS
Orr-Ewing, A. J. (Principal Investigator) & Ashfold, M. N. R. (Co-Principal Investigator)
1/10/08 → 1/04/14
Project: Research
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NEW FRONTIERS IN QUANTITATIVE INFRA RED TO ULTRAVIOLET SPECTROSCOPY
Orr-Ewing, A. J. (Principal Investigator)
1/01/07 → 1/07/12
Project: Research