7572-29-4Relevant articles and documents
The C-Cl bond fissions from the photolysis of CHClCCl2 at 193 nm
Lee, Yu-Jinn,Lee, Ya-Rong,Chou, Chih-Chiang,Lin, Shen-Maw
, p. 346 - 347 (2007/10/03)
The photolysis of CHClCCl2 at 193 nm was investigated by translational spectroscopy. Two distinct product translational distributions were derived for the C-Cl bond fissions. The internally excited C2HCl2 fragment from the main dissociation channel is shown to decompose totally to produce the Cl+C2HCl products.
Hydrogen-Atom-Induced Decomposition of Trichloroethylene at High Temperatures
Tsang, Wing,Walker, James A.
, p. 3156 - 3161 (2007/10/02)
Mechanisms and rate constants for hydrogen atom attack on trichloroethylene have been determined in single-pulse shock tube experiments near 1050 K.Products from all the decomposition channels have been observed.The predominant process is the displacement of the chlorine at the least substituted site.The following rate expressions have been determined: k(H* + HClC=CCl2 -> H2C=CCl2 + Cl*) = 6 x 1E13 exp(-2439/T) cm3 mol-1 s-1; k(H* + HClC=CCl2 -> HClC=CClH (cis + trans) + Cl*) = 3.7 x 1E13 exp(-3946/T) cm3 mol-1 s-1; k(H* + HClC=CCl2 -> *HC=CCl2 or HClC=CCl* + HCl) = 3.8 x 1E14 exp(-6686/T) cm3 mol-1 s-1.An upper limit for the rate constant of the abstraction process H* + HClC=CCl2 -> *ClC=CCl2 + H2 is 6.5 x 1E10 cm3 mol-1 s-1 at 1050 K.Rate constants for chlorine attack on H2 at these temperatures are a factor of 13 smaller than those on mesitylene.The results are compared with those for hydrogen atom reactions with other unsaturated compounds.Some implications regarding the incineration of chlorinated organics will be discussed.
IR Laser-induced Chemistry of some Perhaloethene-Silane Mixtures at Different Single Irradiating Wavelengths
Pola, Josel,Simeonov, Sawa
, p. 101 - 108 (2007/10/02)
TEA CO2 laser-induced reactions in chlorotrifluoroethene-silane, 1,2-dichlorodifluoroethene-silane, 1,1-dichlorodifluoroethene-silane, and 1,2-dichlorodifluoroethene-trimethylsilane mixtures at medium (4-19 Torr) and in chlorotrifluoroethene-silane and 1,2-dichlorodifluoroethene-silane mixtures at low (1 Torr) pressures can be initiated by irradiation tuned to either perhaloethene or silane.The reaction progress at medium pressure and reaction products at low pressure depend on the particular wavelength employed.The former reactions are assumed to occur through reactive collision of both energized components in the mixture and have been shown to yield mostly tetrafluorosilane, trifluorosilane, hydrogen chloride, and other hydrocarbons.The latter are explained by multiphoton dissociation of the alkene into carbenes, subsequent reactions of these carbenes, and by 1,2-rearrangement of halogen in the transient CFCl=CF* radical produced upon C-Cl bond cleavage of the parent CFCl=CFCl compound.This reaction mechanism is in line with IR multiphoton decomposition of 1,2-dichlorodifluoroethene both in the absence and presence of chlorine and carbon monoxide.
Infrared Laser Multiphoton Dissociation of CF2ClCH2Cl
Yano, T.,Ozaki, S.,Ogura, H.,Tschuikow-Roux, E.
, p. 1108 - 1116 (2007/10/02)
The infrared multiphoton decomposition (IRMPD) of CF2ClCH2Cl was studied with focusing geometry using the P(34) line of the 9.6-μm CO2 band (1033.6 cm-1).The principal reaction product is CF2CHCl.Other products of significance include CFClCHCl, CF2CH2, and CFCH.It is concluded that the primary processes of photodecomposition involve the molecular elimination of HCl and HF and, to a very minor extent, C-C bond rupture.The relative importance of the primary steps is approximately 1000:30:1, respectively.From a series of diagnostic experiments in the presence of hydrogen donors and D2, it is shown that CF2CH2 derives from the secondary photolysis of CF2CHCl.The decomposition yield, the HF/HCl ratio, and the CF2CH2/CF2CHCl ratio were investigated as a function of reactant and argon pressure, the latter serving as a buffer gas.From the dependence of the decomposition yield on pulse number at different pulse energies, E0, the specific rate of decomposition, b, was found to be proportional to b E01.8, the power dependence being somewhat higher than the standard 3/2 power law for focusing geometry.These phenomena are interpreted in terms of a simple geometric fluence model which includes contributions from collisionally induced reactions in the outermost (lower fluence) irradiated region.The nonresonant photodecomposition of C2H6 and C2H4 at 1033.6 cm-1 observed in auxiliary, diagnostic experiments is interpreted in terms of photosensitization processes.
Infrared Spectra of Hydrogen-Bonded ? Complexes between Hydrogen Halides and Acetylene
McDonald, Stephen A.,Johnson, Gary L.,Keelan, Brian W.,Andrews, Lester
, p. 2892 - 2896 (2007/10/02)
Hydrogen-bonded ? complexes C2H2--H-X have been formed by codeposition of C2H2 and HX in excess argon at 15 K and by vacuum-UV photolysis of vinyl halides.The strength of the hydrogen bond, as measured by the displacement of the H-X vibrational fundamental below the isolated HX value, decreases in the series HF, HCl, and HBr as expected.Similar complexes made from di- and thichloroethylenes give slightly higher H-Cl vibrations which show minimal interaction between the halide and the acetylene substituent.The H-F fundamentals for C2H4 and C2H2 complexes at 3732 and 3747 cm-1, respectively, show that the ? electrons in double and triple bonds are comparable hydrogen-bond acceptors.
