scholarly journals Erratum: Doppler spectroscopy of chlorine atoms generated from photodissociation of hydrogen chloride and methyl chloride at 157 and 193 nm [J. Chem. Phys. 92, 1696 (1990)]

1992 ◽  
Vol 97 (7) ◽  
pp. 5261-5261 ◽  
Author(s):  
Yutaka Matsumi ◽  
Puspendu Kumar Das ◽  
Masahiro Kawasaki
Keyword(s):  
Hydrogen Chloride ◽  
Methyl Chloride ◽  
Chem Phys ◽  
Chlorine Atoms ◽  
Doppler Spectroscopy ◽  
193 Nm

Fine structure branching ratios and Doppler spectroscopy of chlorine atoms from the photodissociation of alkyl chlorides and chlorofluoromethanes at 157 and 193 nm

1991 ◽  
Vol 94 (4) ◽  
pp. 2669-2674 ◽  
Author(s):  
Yutaka Matsumi ◽  
Kenichi Tonokura ◽  
Masahiro Kawasaki ◽  
Gen Inoue ◽  
Sunita Satyapal ◽  
...  
Keyword(s):  
Fine Structure ◽  
Branching Ratios ◽  
Chlorine Atoms ◽  
Doppler Spectroscopy ◽  
193 Nm

Reaction of adamantanone, diamantanone, and their derivatives with thionyl chloride

1987 ◽  
Vol 52 (8) ◽  
pp. 2028-2034 ◽  
Author(s):  
Josef Janků ◽  
Jiří Burkhard ◽  
Luděk Vodička
Keyword(s):  
Hydrogen Chloride ◽  
Carbonyl Group ◽  
Chlorine Atom ◽  
Thionyl Chloride ◽  
Reaction Rate ◽  
Axial Position ◽  
Chlorine Atoms

In reaction of adamantanone, diamantanone, and their chloro or oxo derivatives with thionyl chloride the oxo group is replaced with two chlorine atoms under formation of geminal dichloro derivatives. The presence of a chlorine atom or an oxo group in both ketones reduces the reaction rate. The reaction rate decreases with decreasing distance between the substituent and the carbonyl group. Ketones with chlorine atom in α- or β-axial position do not react with thionyl chloride. The reaction is accelerated by hydrogen chloride whereas in the presence of pyridine no reaction was observed.

The thermal decomposition of methylene chloride

1959 ◽  
Vol 250 (1261) ◽  
pp. 180-196 ◽  
Keyword(s):  
Thermal Decomposition ◽  
Hydrogen Chloride ◽  
Methylene Chloride ◽  
Flow System ◽  
Vessel Diameter ◽  
Chlorine Atoms ◽  
System A ◽  
Pressure Time ◽  
A Chain ◽  
Kinetic Features

The thermal decomposition of methylene chloride has been studied in the temperature range 500 to 650 °C by both the static technique of pressure-time measurement and the use of a flow system in conjunction with gas chromatographic analysis. The reaction, which leads principally to carbon and hydrogen chloride is characterized by a slow acceleration, the rate of which decreases with the vessel diameter. In vessels of diameter less than 5 mm the reaction is almost completely inhibited. The reaction rate is increased by the addition of inert gas, nitric oxide and, particularly, by dichlorethylene. Using the flow system a number of chlorinated hydrocarbons were detected as minor products of the reaction and their rate of formation relative to the major products was followed in detail. By identifying some of these as radical recombination products and one, dichlorethylene, as a degenerate branching agent, a delayed branching mechanism has been deduced which explains most of the kinetic features of the reaction as well as the formation of the observed minor products. This involves the production of the intermediate, dichlor­ethylene, in a chain carried by chlorine atoms and dichlormethyl radicals, and the conversion of this to carbon and hydrogen chloride by a coupled chain also involving chlorine atoms. The average primary chain length has been estimated as fifteen by measurement of the rate of formation of the supposed recombination products, but this figure is uncertain since the termination products appear to be destroyed in turn by chlorine atoms generated in the main chain.

PRIMARY PROCESSES IN REACTIONS INITIATED BY PHOTOEXCITED MERCURY ISOTOPES

1958 ◽  
Vol 36 (1) ◽  
pp. 89-95 ◽  
Author(s):  
Harry E. Gunning
Keyword(s):  
Water Vapor ◽  
Hydrogen Chloride ◽  
Methylene Chloride ◽  
Methyl Chloride ◽  
Mercury Vapor ◽  
Enrichment Factors ◽  
Exchange Reactions ◽  
Boron Trichloride ◽  
Mercury Compounds ◽  
Similar Enrichment

A study has been made of the reaction of Hg2026(3P1) atoms, photoexcited in natural mercury vapor; with a number of substrates which form solid mercury compounds in mercury photo-sensitization. Some data are also given for reactions initiated by Hg1986(3P1) atoms. The solid mercury compounds formed were examined for enrichment in the isotope initiating the reaction. Such enrichment would be evidence for the primary formation of the mercury compound.Three HgO-forming substrates were studied: water vapor, nitrous oxide, and oxygen. The Hg2Cl2-forming substrates studied included hydrogen chloride, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, isopropyl chloride, and boron trichloride. One Hg2Br2-forming substrate was examined—isopropyl bromide.Among the HgO-forming substrates only water vapor gave enrichment in Hg202 in the HgO product. The Hg202 content of the oxide was found to vary from 32 to 35%, depending on reaction conditions, compared to a natural abundance of 29.6%. With water vapor – butadiene mixtures, oxides containing as high as 90% Hg202 were obtained. Similar enrichment factors were obtained for Hg1986(3P1) reactions.Hydrogen chloride and the alkyl chlorides yielded calomels containing a maximum of 45% Hg202. Methyl chloride gave similar enrichment factors in Hg198 for the Hg1986(3P1) reaction. The calomel formed in the boron trichloride reaction showed no enrichment.Addends such as butadiene and benzene, when added to hydrogen chloride, increased the Hg202 enrichment from 45% to 60%.For those reactions which yield mercury compounds enriched in the initiating mercury isotope, evidence is presented for a single primary process. Failure to obtain pure isotopes is attributed to exchange reactions with adsorbed natural mercury during recovery of the enriched mercury from the product. It is postulated that the addends react with the mercury product and reduce chemisorption of natural mercury on the product.The significance of these findings in the mechanisms of the reactions studied is discussed.

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