THE REACTION OF NITROGEN ATOMS WITH ETHYLENE

1949 ◽  
Vol 27b (8) ◽  
pp. 721-731
Author(s):  
C. A. Winkler ◽  
J. H. Greenblatt
Keyword(s):  
Activation Energy ◽  
Double Bond ◽  
Hydrogen Cyanide ◽  
Steric Factor ◽  
Methyl Radical

Reaction of nitrogen atoms with ethylene has been found to produce hydrogen cyanide, ethane, and a polymerizable material. The yield of hydrogen cyanide was approximately 70% of the ethylene consumed by nitrogen atoms, while the amount of polymerizable material averaged about 16% by weight of the hydrogen cyanide produced. The yield of ethane increased as the excess of ethylene over nitrogen atoms was increased. The reaction was found to proceed by "clean-up of nitrogen atoms. An activation energy of 6.9 kcal. was calculated from collision yields, a steric factor of 0.1 being assumed. A mechanism for the reaction has been proposed, involving rupture of the ethylene double bond with formation of hydrogen cyanide and a methyl radical, the methyl radical then reacting further with nitrogen atoms.

scholarly journals THE REACTION OF NITROGEN ATOMS WITH METHANE AND ETHANE

1951 ◽  
Vol 29 (11) ◽  
pp. 1010-1021 ◽  
Author(s):  
H. Blades ◽  
C. A. Winkler
Keyword(s):  
Activation Energy ◽  
Nitrogen Atom ◽  
High Temperatures ◽  
Hydrogen Cyanide ◽  
Active Species ◽  
Second Order ◽  
Steric Factor ◽  
Atomic Nitrogen ◽  
Atom Concentration ◽  
Nitrogen Stream

Methane reacted with nitrogen atoms at temperatures above 300°C. to produce hydrogen cyanide. An activation energy of 11 kcal. and a steric factor of 5 × 10−3 were obtained. The reaction of ethane with nitrogen atoms was studied up to 295°C., with hydrogen cyanide the only product found in measurable amounts. At high temperatures, nitrogen atom consumption was complete in excess ethane, and the hydrogen cyanide production under these conditions, compared with the atom concentration determined by a Wrede gauge, indicated the active species in the nitrogen stream to be only atomic nitrogen. The ethane – nitrogen atom reaction was second order, with an activation energy of 7 ± 1 kcal. and a steric factor between 10−1 and 10−3.

THE REACTION OF ACTIVE NITROGEN WITH PROPANE

1954 ◽  
Vol 32 (4) ◽  
pp. 351-355 ◽  
Author(s):  
M. Onyszchuk ◽  
L. Breitman ◽  
C. A. Winkler
Keyword(s):  
Activation Energy ◽  
Flow Rate ◽  
Rate Constants ◽  
Hydrogen Cyanide ◽  
Main Product ◽  
Second Order ◽  
Steric Factor ◽  
Active Nitrogen ◽  
Flow Rates ◽  
Order Rate

The reaction of nitrogen atoms with propane has been found to produce hydrogen cyanide as the main product, together with smaller amounts of acetylene, ethylene, and ethane, which were recovered at all propane flow rates. Complete consumption of nitrogen atoms was not attained at any propane flow rate used at 63 °C, but was attained at 250 °C for ratios of propane to nitrogen atoms greater than 1.3. An activation energy of 5.6 ± 0.6 kcal. and a steric factor between 10−2 and 10−3 was estimated from second order rate constants.

THE REACTION OF ACTIVE NITROGEN WITH PROPYLENE

1952 ◽  
Vol 30 (12) ◽  
pp. 915-921 ◽  
Author(s):  
G. S. Trick ◽  
C. A. Winkler
Keyword(s):  
Double Bond ◽  
Nitrogen Atom ◽  
Hydrogen Cyanide ◽  
Atomic Hydrogen ◽  
Atomic Nitrogen ◽  
Active Nitrogen

The reaction of nitrogen atoms with propylene has been found to produce hydrogen cyanide and ethylene as the main products, together with smaller amounts of ethane and propane and traces of acetylene and of a C4 fraction. With excess propylene, the nitrogen atoms were completely consumed and for the reaction at 242 °C., 0.77 mole of ethylene was produced for each mole of excess propylene added. For reactions at lower temperatures, less ethylene was produced. The proposed mechanism involves formation of a complex between the nitrogen atom and the double bond of propylene, followed by decomposition to ethylene, hydrogen cyanide, and atomic hydrogen. The ethylene would then react with atomic nitrogen in a similar manner.

Aromatic oxidation by cobaltic acetate in acetic acid

1969 ◽  
Vol 47 (3) ◽  
pp. 387-392 ◽  
Author(s):  
Koichiro Sakota ◽  
Yoshio Kamiya ◽  
Nobuto Ohta
Keyword(s):  
Activation Energy ◽  
Electron Transfer ◽  
Acetic Acid ◽  
Bond Energy ◽  
Hydrogen Abstraction ◽  
Steric Factor ◽  
Benzyl Acetate ◽  
Kcal Mole ◽  
First Order ◽  
Reversible Electron Transfer

A detailed kinetic study of oxidation of toluene and its derivatives by cobaltic acetate in 95 vol% acetic acid is reported. The reaction was found to be profoundly affected by a steric factor and rather insensitive to the C—H bond energy. The order of reactivities of various alkylbenzenes is quite reversal to that of hydrogen abstraction reactions. The reaction was of first-order with respect to toluene, of second-order with respect to cobaltic ion and of inverse first-order with respect to cobaltous ion. The oxidation by cobaltic ion seems to proceed via an initial reversible electron transfer from toluene to cobaltic ion, yielding [Formula: see text] which is oxidized into benzyl acetate by another cobaltic ion. The apparent activation energy for toluene was found to be 25.3 kcal mole−1, and the same activation energy was found for ethylbenzene, cumene, diphenylmethane, and triphenylmethane.

STUDIES ON HOMOGENEOUS FIRST ORDER GAS REACTIONS: XI. THE DECOMPOSITION OF BENZYLIDENE DIACETATE, o-CHLOROBENZYLIDENE DIACETATE AND BENZYLIDENE DIBUTYRATE

1940 ◽  
Vol 18b (8) ◽  
pp. 223-230 ◽  
Author(s):  
N. A. D. Parlee ◽  
J. C. Arnell ◽  
C. C. Coffin
Keyword(s):  
Double Bond ◽  
Steric Factor ◽  
Reverse Reaction ◽  
Breaking Point ◽  
Reaction Velocity ◽  
First Order ◽  
Gas Reactions

Benzylidene diacetate, o-chlorobenzylidene diacetate, and benzylidene dibutyrate decompose unimolecularly at rates given by the equation previously found for crotonylidene diacetate and furfurylidene diacetate, viz., [Formula: see text]. The fact that these esters all have a double bond at the same distance from the breaking point of the molecule is considered significant in connection with their identical reaction velocity, which is about six times that of ethylidene diacetate. Benzylidene diacetate decomposes at the same rate in both the liquid and vapour states to reach an equilibrium given by the equation [Formula: see text]. The reverse reaction with a rate given by [Formula: see text] is characterized by a steric factor of 10−4.

ADDITION OF ETHYL RADICALS TO ETHYLENE

1957 ◽  
Vol 35 (7) ◽  
pp. 588-594 ◽  
Author(s):  
J. A. Pinder ◽  
D. J. Le Roy
Keyword(s):  
Activation Energy ◽  
Reaction Zone ◽  
Addition Reaction ◽  
Steric Factor ◽  
Square Root ◽  
Temperature Range ◽  
Ethyl Radical ◽  
Ethyl Radicals

The addition of ethyl radicals to ethylene has been studied in the temperature range 58° to 123 °C. The radicals were produced by the mercury photosensitized decomposition of hydrogen in the presence of ethylene, and the rate of the addition reaction was measured in terms of the rate of formation of n-hexane by the combination of ethyl and butyl radicals. Corrections were made for the non-uniformity of radical concentrations in the reaction zone. Assuming a negligible activation energy for the combination of two ethyl radicals, the activation energy for the addition reaction is 5.5 kcal. per mole; the steric factor, relative to the square root of the steric factor for ethyl radical combination, is 5.0 × 10−5.

Activation Energy of Methyl Radical Decay in Methane Hydrate

2005 ◽  
Vol 109 (44) ◽  
pp. 21086-21088 ◽  
Author(s):  
Kei Takeya ◽  
Kouhei Nango ◽  
Takeshi Sugahara ◽  
Kazunari Ohgaki ◽  
Atsushi Tani
Keyword(s):  
Activation Energy ◽  
Methane Hydrate ◽  
Methyl Radical ◽  
Radical Decay

Steric Factor and Activation Energy of the Reaction Na+C2H5Cl = NaCl+C2H5

1952 ◽  
Vol 20 (6) ◽  
pp. 1016-1020 ◽  
Author(s):  
R. J. Cvetanović ◽  
D. J. Le Roy
Keyword(s):  
Activation Energy ◽  
Steric Factor

THE STERIC FACTOR IN THE HYDROLYSIS OF β-1,4′-OLIGOGLUCOSIDES BY MYROTHECIUM CELLULASE

1956 ◽  
Vol 34 (1) ◽  
pp. 102-115 ◽  
Author(s):  
D. R. Whitaker
Keyword(s):  
Activation Energy ◽  
Rate Constant ◽  
Rate Constants ◽  
Activation Energies ◽  
Enzymic Activity ◽  
Degree Of Polymerization ◽  
Steric Factor ◽  
Collision Theory ◽  
Hydrolysis Of

A comparison of the rate constants and activation energies for the hydrolysis of cellobiose, cellotriose, cellotetraose, and cellopentaose by Myrothecium cellulase showed that while the rate constant was increased by a factor of about 450 as the degree of polymerization (D.P.) of the substrate was increased from two to five, the activation energy remained at about 12,000 cal. The results are interpreted, in terms of classical collision theory, as indicating that the increase in rate constant with D.P. is determined by an increase in the steric factor with D.P. Addition of a β-linked sorbityl group to an oligoglucoside increased the rate constant; the increase was less than that from addition of an anhydroglucose unit and, relative to the latter, diminished as the D.P. of the chain undergoing addition was increased. Exposing the enzyme to conditions favoring thermal or surface denaturation caused varying losses in enzymic activity towards the four oligoglucosides; wherever the loss in activity towards one oligoglucoside differed substantially from the loss in activity towards any other oligoglucoside, the greater loss was shown towards the substrate of lower D.P. The results are discussed.

THE PHOTO-OXIDATION OF AZOMETHANE

1955 ◽  
Vol 33 (3) ◽  
pp. 496-506 ◽  
Author(s):  
G. R. Hoey ◽  
K. O. Kutschke
Keyword(s):  
Carbon Dioxide ◽  
Activation Energy ◽  
Room Temperature ◽  
Major Product ◽  
Steric Factor ◽  
Primary Process ◽  
Methyl Radicals ◽  
Low Oxygen ◽  
Secondary Product ◽  
Photo Oxidation

The photo-oxidation of azomethane has been studied at low oxygen pressures (0.02 to 1 mm.) in the temperature range ca. 25 °C. to 161 °C. The primary process in the normal photolysis of azomethane is essentially unaffected by the presence of oxygen. Carbon monoxide is probably a secondary product of the oxidation of methyl radicals. Carbon dioxide formation is quite small, and therefore neither methyl radicals nor CH3N=N—CH2 radicals are oxidized appreciably to carbon dioxide. Nitrous oxide, which is a major product of the oxidation, is most likely formed from the oxidation of CH3N=NCH2 radicals. The suggested mechanism of N2O formation is:[Formula: see text] The reaction of methyl radicals with oxygen was found to proceed with a negligible activation energy and a steric factor of the order of 10−2. Evidence for the occurrence of the reactions[Formula: see text]at room temperature was obtained.

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