REACTION OF OXYGEN ATOMS WITH BUTADIENE

1960 ◽  
Vol 38 (11) ◽  
pp. 2187-2195 ◽  
Author(s):  
R. J. Cvetanović ◽  
L. C. Doyle
Keyword(s):  
Pressure Dependence ◽  
Rate Constants ◽  
Room Temperature ◽  
Relative Rate ◽  
Excess Energy ◽  
General Mechanism ◽  
Arrhenius Parameters ◽  
Heats Of Reaction ◽  
Relative Rate Constants ◽  
Oxygen Atoms

Reaction of oxygen atoms with 1,3-butadiene has been investigated at room temperature. It is found that it conforms to the general mechanism established previously for the analogous reactions of monoolefins. Only 1,2-addition occurs, and the addition products, butadiene monoxide and 3-butenal, possess excess energy when formed as a result of high heats of reaction. The pressure dependence of the formation of the addition products yields the values of the "lifetimes" of the initially produced "hot" molecules. The relative rate constants have been determined at 25 and 127 °C and from these the relative values of the Arrhenius parameters have been calculated.

ELECTROPHILIC CHARACTER OF OXYGEN ATOMS

1960 ◽  
Vol 38 (10) ◽  
pp. 1678-1687 ◽  
Author(s):  
R. J. Cvetanović
Keyword(s):  
Vapor Phase ◽  
Rate Constants ◽  
Relative Rate ◽  
Potential Significance ◽  
Relative Rate Constants ◽  
Electrophilic Character ◽  
Oxygen Atoms

The relative rates of reactions of oxygen atoms with a number of olefins in the vapor phase determined in previous work are summarized and supplemented by some additional results. The uncertainty in the values of the relative rate constants is now believed to be reduced to only a few per cent. A number of simple correlations observed previously have been re-examined on the basis of the more complete and more accurate list of values available at present. These correlations show a distinct electrophilic character of oxygen atoms in their reactions with olefins and their potential significance for the understanding of the finer details of these addition processes is discussed.

The relative rate constants of oxygen, O(3P), atoms with different gaseous unsaturated compounds at room temperature

1986 ◽  
Vol 64 (9) ◽  
pp. 1925-1929 ◽  
Author(s):  
H. Deslauriers ◽  
G. J. Collin
Keyword(s):  
Double Bond ◽  
Rate Constants ◽  
Room Temperature ◽  
Relative Rate ◽  
Unsaturated Hydrocarbon ◽  
Ionization Potentials ◽  
Total Rate ◽  
Simple Method ◽  
Unsaturated Compounds ◽  
Relative Rate Constants

A simple method is proposed in order to measure the relative rate constants of the interactions between oxygen O(3P) atoms and unsaturated hydrocarbon. A 147 nm photolysis of air is used to produce the O(3P) atoms. In the presence of 1,2-butadiene, these oxygen atoms have a very clean reaction that gives rise to propylene formation. By including a suitable additive, and by looking at the formation of propene versus the [additive]/[1,2-butadiene] ratio, the absolute values of the various O(3P) + unsaturated hydrocarbon interactions can be evaluated. These rate constants increase with the number of substituents attached to the double bond. Moreover, a correlation between the total rate constants and ionization potentials is also observed.

Kinetics of the successive chlorination of 1,2-dichloroethane in the liquid phase

1969 ◽  
Vol 22 (6) ◽  
pp. 1177 ◽  
Author(s):  
DS Caines ◽  
RB Paton ◽  
DA Williams ◽  
PR Wilkinson
Keyword(s):  
Liquid Phase ◽  
Rate Constants ◽  
Relative Rate ◽  
Stirred Tank ◽  
Continuous Stirred Tank Reactor ◽  
Alternative Pathways ◽  
Tank Reactor ◽  
Relative Rate Constants ◽  
Continuous Stirred Tank ◽  
Kinetics Of

Liquid 1,2-dichloroethane has been chlorinated by dissolved chlorine to a succession of chloroethanes up to the ultimate hexachloroethane. The results of both batch and continuous stirred tank reactor systems have been analysed by computer techniques to give a set of relative rate constants from which one can predict the product composition for a given chlorine uptake, the aim in this work being to optimize the production of tetrachloroethanes. An unusual feature of the kinetics is that 1,1,1,2- and 1,1,2,2-tetrachloroethanes provide alternative pathways between 1,1,2-trichloroethane and pentachloroethane.

RECOMBINATION OF OPPOSITELY CHARGED AQUEOUS CLUSTER IONS USING ELECTROSTATICALLY MERGED ION BEAMS

1996 ◽  
Vol 03 (01) ◽  
pp. 655-660 ◽  
Author(s):  
B. PLASTRIDGE ◽  
K.A. COWEN ◽  
D.A. WOOD ◽  
M.H. COHEN ◽  
J.V. COE
Keyword(s):  
Rate Constants ◽  
Cluster Size ◽  
Collision Energy ◽  
Relative Rate ◽  
Center Of Mass ◽  
Cluster Ions ◽  
Charged Cluster ◽  
Relative Rate Constants ◽  
Oppositely Charged ◽  
Electrostatic Quadrupole

A new method for studying cluster-cluster interactions is introduced which involves merging mass-selected beams of oppositely charged cluster ions with an electrostatic quadrupole deflector. Recombination is monitored by measuring the rate of fast neutral production. Relative rate constants have been measured for the reaction of H 3O+( H 2 O )n+ OH −( H 2 O )m as a function of cluster size (m=n=0–3), which display a pronounced enhancement with clustering. Relative rate constants have also been measured as a function of center-of-mass collision energy for a heavily clustered reaction (n=3, m=3) and a lightly clustered reaction (n=1, m=0) revealing that clustering produces a dramatic change in the reaction mechanism.

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