Temperature-dependent kinetics studies of the reactions bromine atom(2P3/2) + hydrogen sulfide .tautm. mercapto + hydrogen bromide and bromine atom(2P3/2) + methanethiol .tautm. methylthiol + hydrogen bromide. Heats of formation of mercapto and methylthio radicals

1992 ◽  
Vol 96 (6) ◽  
pp. 2518-2528 ◽  
Author(s):  
J. M. Nicovich ◽  
K. D. Kreutter ◽  
C. A. Van Dijk ◽  
P. H. Wine
Keyword(s):  
Hydrogen Sulfide ◽  
Hydrogen Bromide ◽  
Bromine Atom ◽  
Heats Of Formation ◽  
Temperature Dependent ◽  
Kinetics Studies

Energies of interaction and other properties of clathrate compounds

1954 ◽  
Vol 223 (1153) ◽  
pp. 238-250 ◽  
Keyword(s):  
Formic Acid ◽  
Hydrogen Chloride ◽  
Sulphur Dioxide ◽  
Hydrogen Bromide ◽  
Energy Difference ◽  
Heats Of Formation ◽  
Free Energies ◽  
Clathrate Compounds ◽  
Intermolecular Contacts

Heats of formation of clathrate compounds of β-quinol with argon, oxygen, nitrogen, hydrogen chloride, hydrogen bromide, formic acid and methanol have been determined calorimetrically. For the argon and oxygen compounds, the heats of formation were determined for samples of widely differing composition, and they vary linearly with the fraction of available spaces filled. Using the energy difference between α- and β-quinol obtained directly or by extrapolation of the measurements on the argon and oxygen compounds, the energies of interaction of the enclosed molecules with the β-quinol cage have been determined. Their values are interpreted in terms of the polarizabilities of the enclosed molecules and the number of intermolecular contacts occurring. The free energies of formation, and the colours of the sulphur dioxide and oxygen clathrate compounds are also discussed briefly.

The relative rates of bromination of cyclohexane and cyclopentane with molecular bromine. Comparison of the reactions in solution and in vapor phase

1981 ◽  
Vol 59 (9) ◽  
pp. 1368-1374 ◽  
Author(s):  
Dennis D. Tanner ◽  
Tomoki C-S. Ruo ◽  
Hideki Takiguchi ◽  
Andre Guillaume
Keyword(s):  
Vapor Phase ◽  
Hydrogen Bromide ◽  
Bromine Atom ◽  
Relative Rate ◽  
Solution Phase ◽  
Molecular Bromine ◽  
Transfer Rates ◽  
Relative Rate Constants ◽  
Halogenated Alkanes ◽  
Relative Transfer

The relative rates of transfer of the cyclopentyl radical with molecular bromine and hydrogen bromide (k2′/k−1′) and with hydrogen tribromide and hydrogen bromide (k3′/k−1′) have been determined. The relative transfer rates are compared with the analogous values previously reported for the reactions of cyclohexyl radicals (k2/k−1 and k3/k−1). Utilizing the values of k2′/k−1 and k2/k−1 the competitive vapor phase rates of bromine atom abstraction of hydrogen from the two substrates could be obtained. An expression using a combination of the five sets of relative rate constants was used to determine the effect of competitive cage reversal which occurs in the solution phase bromination of the two substrate radicals with caged hydrogen bromide. For two structurally similar radicals, cage reversal (internal return) was found to affect the relative rates of bromination by 30%, while the relative transfer rates, although differing each by a factor of two, fortuitously nearly cancel each other's effect.The effect of both internal and external reversal reactions on the relative rates of bromination of structurally dissimilar substrates, halogenated alkanes and their parent hydrocarbons, is discussed.

The thermal decomposition of n-propyl bromide

1968 ◽  
Vol 21 (4) ◽  
pp. 973 ◽  
Author(s):  
JTD Cross ◽  
VR Stimson
Keyword(s):  
Thermal Decomposition ◽  
Rate Constant ◽  
Hydrogen Bromide ◽  
Bromine Atom ◽  
Order Reaction ◽  
Chain Mechanism ◽  
Initial Concentration ◽  
First Order ◽  
Reaction Proceeds ◽  
Atom Chain

Mechanisms already proposed or formally possible for the decomposition of n-propyl bromide as a 312-order reaction are shown to be unsatisfactory, and the reaction has been reinvestigated. Two reactions occur simultaneously: (a) a first-order reaction identifiable with the maximally inhibited reaction and presumably molecular; (b) a reaction second order in the initial concentration and somewhat autocatalysed as the reaction proceeds. The rate constant is given by k2 == 1018.1exp(-49300/RT)sec-1ml mole-1 Reaction (b) is catalysed by hydrogen bromide and inhibited by propene, and a bromine atom chain mechanism with hydrogen bromide catalysed initiation is proposed. Bromine-catalysed decomposition has also been studied. The mechanism of the inhibition is discussed.

scholarly journals Predicting sulfur solubility in hydrogen sulfide, carbon dioxide, and methane with an improved thermodynamic model

RSC Advances ◽  
2018 ◽  
Vol 8 (29) ◽  
pp. 16069-16081 ◽  
Author(s):  
Changjun Li ◽  
Gang Liu ◽  
Yang Peng
Keyword(s):  
Carbon Dioxide ◽  
Hydrogen Sulfide ◽  
Thermodynamic Model ◽  
Binary Interaction ◽  
Temperature Dependent ◽  
Interaction Coefficients ◽  
Sulfur Solubility

The binary interaction coefficients between sulfur and H2S, CO2or CH4are not constant, but temperature dependent. Three-parameter temperature-dependent equations for the binary interaction coefficients between sulfur and solvents are proposed.

The gas-phase decomposition of ethyl bromide

1971 ◽  
Vol 24 (10) ◽  
pp. 2031
Author(s):  
DA Kairaitis ◽  
VR Stimson
Keyword(s):  
Gas Phase ◽  
Initial Rate ◽  
Hydrogen Bromide ◽  
Bromine Atom ◽  
Ethyl Bromide ◽  
Phase Decomposition ◽  
Unimolecular Decomposition ◽  
Chain Reaction ◽  
Insight Into

The gas-phase decomposition of ethyl bromide at 423� in the presence of both ethylene and hydrogen bromide has been investigated. These additives, which are also the products, each influence the rate strongly but in opposite ways. The variation of initial rate with reactant pressure is given by (P in cm) ������������� k1 (min-1) = 15.2x10-3+19.5x10-3(PEtBrPHBr/PEne)1/2 This has been interpreted in terms of a unimolecular decomposition together with a bromine atom carried chain reaction with simple steps that involve the products. Some insight into the unaccompanied decomposition has been gained. Some remarks about the role of olefinic inhibitors in reactions producing hydrogen bromide have been made.

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