Journal ArticleDOI
Reactions of ground state chlorine atoms with fluorinated methanes and ethanes
TLDR
In this article, the reactions of photochemically generated Cl(2PJ) atoms with a number of fluorohydrocarbons have been investigated in the temperature range 8-95°C by the competitive photochlorination technique using CH4 as a primary standard.Abstract:
The reactions of photochemically generated Cl(2PJ) atoms with a number of fluorohydrocarbons have been investigated in the temperature range 8–95 °C by the competitive photochlorination technique using CH4 as a primary standard. Relative and absolute rate parameters are reported for CH3F, CH2F2, CH3CH2F, CH2FCH2F, CH3CHF2, CH3CF3, CH2FCHF2, CHF2CHF2, and several auxiliary reactions including CH3Cl, C2H6, and C3H8. The internal competition for hydrogen abstraction in asymmetric fluorethanes is examined in detail. The reactivity trends are discussed and it is found that the activation energies in the fluoromethane series correlate with the known C–H bond dissociation energies. The hydrogen reactivity in the fluoroethane series for which a sufficient data base of DH°(C–H) values is not available is best rationalized in terms of inductive effects and resonance interactions.read more
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Book ChapterDOI
Characteristics of C-F Systems
TL;DR: The physical properties and chemical reactivities of organic molecules can be dramatically affected by fluorination as discussed by the authors, and the numerous ways in which industry has taken practical advantage of these effects are the subjects of the following chapters in this book.
Journal ArticleDOI
Detection of Cl atoms and HCl molecules by resonantly enhanced multiphoton ionization
TL;DR: In this article, the authors used an enhanced multiphoton ionization (EMI) to detect Cl(3p 2P 3 2 o) and Cl* via the pumping of two-photon-allowed transitions in the wavelength region of 230-245 nm.
Journal ArticleDOI
Kinetics and mechanisms of the reactions of chlorine atoms with ethane, propane, and n‐butane
TL;DR: In this article, absolute (flash photolysis) and relative (FTIR-smog chamber and GC) rate techniques were used to study the gas-phase reactions of Cl atoms with C2H6 (k1), C3H8 (k3), and n-C4H10 (k2) at 297 ± 1 K and 10−700 torr of N2 diluent, respectively.
Journal ArticleDOI
A kinetic study of the reaction of chlorine atoms with CF3CHCl2, CF3CH2F, CFCl2CH3, CF2ClCH3, CHF2CH3, CH3D, CH2D2, CHD3, CD4, and CD3Cl at 295±2 K
TL;DR: In this article, a rate constant of 1.0×10 −13 cm 3 molecule −1 s −1 for the reaction of CHCl 2 atoms with methane was derived.
References
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Journal ArticleDOI
Hydrocarbon Bond Dissociation Energies
TL;DR: The best available values for homolytic bond dissociation energies (BDEs) of various classes of neutral compounds are considered in a review as mentioned in this paper, focusing on prototypical radicals whose heats of formation, formerly thought to be well in hand, have recently been called into serious question.
Journal ArticleDOI
Electronegativity values from thermochemical data
TL;DR: In this paper, the electronegativities of sixtynine elements have been calculated from the most recent thermochemical data, and the mean deviation of the calculated electronegativity difference, 0·208 √ †, from the difference of the average electrone-gativities is 0·046 units.
Journal ArticleDOI
Inertia and driving force of chemical reactions
Journal ArticleDOI
Chlorofluoromethanes in the Environment
F. S. Rowland,Mario J. Molina +1 more
TL;DR: In this article, the photoprocesses of atmospheric chlorofluoromethanes, including their ultimate sinks, are studied. Butt et al. present a detailed study of the photodissociation process of chlorofluromethane.
Journal ArticleDOI
Stratospheric Chlorine: a Possible Sink for Ozone
TL;DR: In this article, a photochemical scheme is devised which includes two catalytic cycles through which the oxides of chlorine, ClOx, may constitute an important sink for stratospheric ozone.