THE KINETICS OF THE DECOMPOSITION REACTIONS OF THE LOWER PARAFFINS: VI. ETHANE

1940 ◽  
Vol 18b (7) ◽  
pp. 203-216 ◽  
Author(s):  
E. W. R. Steacie ◽  
Gerald Shane
Keyword(s):  
Thermal Decomposition ◽  
Free Radical ◽  
Static Method ◽  
Point Of View ◽  
Temperature Range ◽  
Decomposition Reactions ◽  
Kinetics Of

The kinetics of the thermal decomposition of ethane have been investigated by the static method in the temperature range 565° to 640 °C. The reaction was found to be uninfluenced by surface. The rate of the reaction can be expressed by[Formula: see text]The products of the reaction are ethylene, hydrogen, and a small amount of methane and probably higher hydrocarbons.The reaction is discussed from the point of view of free radical mechanisms, and it is suggested that the results cast serious doubt on the validity of the Rice-Herzfeld mechanism and its modification by Küchler and Theile.

THE KINETICS OF THE THERMAL DECOMPOSITIONS OF THE LOWER PARAFFINS: V. THE NITRIC OXIDE INHIBITED DECOMPOSITION OF n-BUTANE

1940 ◽  
Vol 18b (1) ◽  
pp. 1-11 ◽  
Author(s):  
E. W. R. Steacie ◽  
H. O. Folkins
Keyword(s):  
Nitric Oxide ◽  
Thermal Decomposition ◽  
Free Radical ◽  
High Pressures ◽  
Free Radical Processes ◽  
Temperature Range ◽  
Radical Recombination ◽  
Radical Processes ◽  
Kinetics Of ◽  
Good Agreement

A detailed investigation of the inhibition by nitric oxide of the thermal decomposition of n-butane has been carried out over the temperature range 500° to 550 °C.In all cases it was found that inhibition decreased with increasing butane concentration. This suggests that radical recombination occurs in the normal decomposition by ternary collisions with butane molecules acting as third bodies.The activation energies of the normal and inhibited reactions have been determined. For high pressures the two values are in good agreement, viz., 58,200 and 57,200 cal. per mole respectively. The products of the inhibited reaction were also found to be the same as those of the normal reaction.It is concluded that free radical processes predominate, involving comparatively short chains.

THE KINETICS OF THE DECOMPOSITION REACTIONS OF THE LOWER PARAFFINS: VII. THE NITRIC OXIDE INHIBITED DECOMPOSITION OF ETHANE

1940 ◽  
Vol 18b (11) ◽  
pp. 351-357 ◽  
Author(s):  
E. W. R. Steacie ◽  
Gerald Shane
Keyword(s):  
Nitric Oxide ◽  
Activation Energy ◽  
Thermal Decomposition ◽  
Free Radical ◽  
Radical Chain ◽  
Decomposition Reactions ◽  
Rearrangement Mechanism ◽  
Chain Lengths ◽  
Kinetics Of

An investigation has been made of the nitric oxide inhibited thermal decomposition of ethane. Apparent chain lengths of 2.4 to 5 are found at temperatures from 640° to 565 °C. The activation energy of the inhibited reaction is found to be 77.3 Kcal. The results are discussed and it is concluded that the thermal decomposition of ethane proceeds mainly by a rearrangement mechanism and that free-radical chain mechanisms for the ethane decomposition are untenable.

Mechanism of the Pyrolysis of Acetylene

1971 ◽  
Vol 49 (13) ◽  
pp. 2199-2204 ◽  
Author(s):  
M. H. Back
Keyword(s):  
Free Radical ◽  
Chain Mechanism ◽  
Kinetic Characteristics ◽  
Radical Chain ◽  
Temperature Range ◽  
Decomposition Reactions ◽  
Radical Chain Mechanism ◽  
Initiation Reaction ◽  
Kinetics Of ◽  
Subsequent Addition

A free radical chain mechanism is presented to describe the kinetics of the pyrolysis of acetylene over the temperature range 700–2400 °K. The mechanism is based on the following initiation reaction[Formula: see text]and subsequent addition, abstraction, and decomposition reactions of the radicals involved are shown to account for the products observed and for the kinetic characteristics of the reaction.

Consecutive reactions in the thermal decomposition of phenylalkyldiazirines

1977 ◽  
Vol 55 (20) ◽  
pp. 3596-3601 ◽  
Author(s):  
Michael T. H. Liu ◽  
Barry M. Jennings
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Parameters ◽  
Diazo Compounds ◽  
First Order ◽  
Temperature Range ◽  
Decomposition Reactions ◽  
Consecutive Reactions ◽  
Rate Processes ◽  
Subsequent Decomposition

The thermal decomposition of phenyl-n-butyldiazirine and of phenylmethyldiazirine in DMSO and in HOAc have been investigated over the temperature range 80–130 °C. The intermediate diazo compounds, 1-phenyl-1-diazopentane and 1-phenyldiazoethane respectively have been detected and isolated. The decomposition of phenyl-n-butyldiazirine and the subsequent decomposition of its product, 1-phenyl-1-diazopentane, are an illustration of consecutive reactions. The kinetic parameters for the isomerization and decomposition reactions have been determined. The isomerization of phenylmethyldiazirine to 1-phenyldiazoethane is first order and probably unimolecular but the kinetics for the subsequent reactions of 1-phenyldiazoethane are complicated by several competing rate processes.

THE KINETICS OF THE THERMAL DECOMPOSITION OF VINYL ISOPROPYL ETHER

1953 ◽  
Vol 31 (4) ◽  
pp. 418-421 ◽  
Author(s):  
Arthur T. Blades
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Free Radical ◽  
Ethyl Ether ◽  
Close Agreement ◽  
Flow System ◽  
Isopropyl Ether ◽  
Radical Decomposition ◽  
A Minor ◽  
Kinetics Of

The thermal decomposition of vinyl isopropyl ether in the presence of toluene has been studied in a flow system in the temperature range 447–521 °C. In this range, the data indicate a purely intramolecular decomposition into propylene and acetaldehyde, the activation energy for the reaction being in close agreement with that found for the decomposition of vinyl ethyl ether. At 570 °C. a minor free radical decomposition of the ether becomes apparent. Some qualitative studies of the decomposition of vinyl isobutyl ether are also reported.

THE KINETICS OF CONSECUTIVE SECOND ORDER REACTIONS

1947 ◽  
Vol 25b (4) ◽  
pp. 415-419 ◽  
Author(s):  
C. Potter ◽  
W. C. Macdonald
Keyword(s):  
Second Order ◽  
Static Method ◽  
Point Of View ◽  
Kinetics Of

A study of consecutive competitive second order reactions is reported. It is shown that identical equations can be obtained by two different approaches. A static method is described where equations are developed by considering the changes brought about in the system by the addition of small quantities of one of the reactants. Equations are also developed from the point of view of kinetics. These equations express the concentrations of the products as functions of the concentration of one of the reactants and the ratio of the velocity constants.

scholarly journals The thermal decomposition of acetone

1944 ◽  
Vol 183 (992) ◽  
pp. 33-37 ◽  
Keyword(s):  
Thermal Decomposition ◽  
Free Radical ◽  
Decomposition Reactions ◽  
Chain Processes

Inhibition by propylene shows that free radical chains occur in the thermal decomposition of acetone. Quantitative investigations permit of conclusions about the mechanism of the chain processes, which are compared and contrasted with those occurring in other decomposition reactions.

scholarly journals The rupture of carbon-nitrogen bonds. Kinetics of the thermal decomposition of ω-azotoluene vapour

1936 ◽  
Vol 156 (888) ◽  
pp. 455-462 ◽  
Keyword(s):  
Thermal Decomposition ◽  
Energy Of Activation ◽  
Azo Compounds ◽  
Temperature Range ◽  
The Difference ◽  
Lower Temperature ◽  
Nitrogen Bonds ◽  
Kinetics Of

The energy of activation found for the benzalazine decomposition is somewhat higher than those hitherto recorded for the decompositions of azo-compounds. The difference between the azine- and azo-decompositions can only be appreciated, however, on comparing the decomposition of benzalazine with that of its aromatic azo-analogue, i . e ., ω-azotoluene. According to Thiele,* when the latter substance is heated in vacuo , gas liberation begins at 15°-180° C. C 6 H 5 . CH 2 ─ N = N ─ CH 2 . C 6 H 5 = N 2 + C 6 H 5 . CH 2 . CH 2 . C 6 H 5 . This reaction is analogous to the benzalazine decomposition (measured at 318°- 180° C), C 6 H 5 . CH = N ─ N = CH. C 6 H 5 = N 2 + C 6 H 5 . CH = CH. C 6 H 5 , and resembles the aliphatic azo-decompositions investigated by Rams-perger over the temperature range 250° - 350° C, though occurring at a lower temperature than these.

The kinetics of the oxidation of ammonia by nitrous oxide

1964 ◽  
Vol 17 (2) ◽  
pp. 202 ◽  
Author(s):  
TN Bell ◽  
JW Hedger
Keyword(s):  
Thermal Decomposition ◽  
Nitrous Oxide ◽  
Free Radical ◽  
Rate Equation ◽  
Radical Mechanism ◽  
15N Isotope ◽  
Free Radical Mechanism ◽  
Products Of Reaction ◽  
Kinetics Of ◽  
Decomposition Of Nitrous Oxide

Ammonia is oxidized by nitrous oxide smoothly and homogeneously at temperatures between 658 and 730� and total pressures up to 250 mm. The products of reaction, nitrogen, water, and hydrazine are accounted for by a free-radical mechanism initiated by oxygen atoms which result from the thermal decomposition of nitrous oxide. Ammonia labelled with the 15N-isotope was used to distinguish between the nitrogen formed from the nitrous oxide and that from the ammonia. The kinetics follow an empirical rate equation, ������������� Rate = k'[N2O]1.56 + k"[N2O]0.61[NH3]. This is of a form which shows the importance of the ammonia molecule participating in the activation of nitrous oxide through bimolecular collision. Assigning a collisional efficiency of unity for like N2O-N2O collisions, the efficiency of ammonia in the process ������������ NH3 + N2O → NH3 + N2O* is determined as 0.85.

Kinetics of the thermal reactions of ethylene. Part II. Ethylene–ethane mixtures

1968 ◽  
Vol 46 (14) ◽  
pp. 2427-2433 ◽  
Author(s):  
M. L. Boyd ◽  
M. H. Back
Keyword(s):  
Free Radical ◽  
Product Formation ◽  
Radical Chain ◽  
Thermal Reactions ◽  
Temperature Range ◽  
Initiation Step ◽  
Chain Polymerization ◽  
Main Effects ◽  
Kinetics Of ◽  
Simplified Mechanism

Mixtures of ethane and ethylene have been pyrolyzed in the temperature range 563–600 °C and at pressures from 30–60 cm. The products were similar to those obtained from the pyrolysis of ethylene by itself, described m Part I, with a marked increase in the yields of the saturated products. The initial rates of product formation and the dependence of these rates on the concentration of ethane suggest that the initiation step is the same as that proposed in the pyrolysis of ethylene alone, viz.[Formula: see text]and that the reaction[Formula: see text]is not an important source of radicals. A simplified mechanism is outlined to account for the main effects of ethane on the free radical chain polymerization.

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