Kinetics of Radical Chain Polymerization: 2. Linear Waves of Macroradical Growth

2019 ◽  
Vol 53 (5) ◽  
pp. 341-350 ◽  
Author(s):  
I. P. Kim ◽  
V. A. Benderskii
Keyword(s):  
Radical Chain ◽  
Linear Waves ◽  
Chain Polymerization ◽  
Kinetics Of

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.

Kinetics of the thermal reactions of ethylene. Part I

1968 ◽  
Vol 46 (14) ◽  
pp. 2415-2426 ◽  
Author(s):  
M. L. Boyd ◽  
T-M. Wu ◽  
M. H. Back
Keyword(s):  
Activation Energy ◽  
Molecular Weight ◽  
Free Radical ◽  
Induction Period ◽  
Pressure Range ◽  
Kcal Mole ◽  
Radical Chain ◽  
Thermal Reactions ◽  
Chain Polymerization ◽  
Kinetics Of

The pyrolysis of ethylene has been studied in the temperature range 500–600 °C and the pressure range 15–60 cm. The main products were ethane, propylene, butene, butadiene, and a polymer of molecular weight corresponding to C8 or higher. Small amounts of methane, butane, unsaturated C5, unsaturated C6, and benzene were also measured. Of the main products, propylene, butene, and butadiene showed an induction period, as long as several minutes at the lowest temperature. The order with respect to ethylene of ethane, propylene, and butene was close to two and the activation energy of the rates was approximately 40 kcal/mole. The results have been interpreted in terms of a free radical chain polymerization. It is suggested that the polymer formed is unstable and decomposes to yield the products for which an induction period was observed.

THE KINETICS OF THE DECOMPOSITION REACTIONS OF THE LOWER PARAFFINS: IV. THE ROLE OF FREE RADICALS IN THE DECOMPOSITION OF n-BUTANE

1939 ◽  
Vol 17b (3) ◽  
pp. 105-120 ◽  
Author(s):  
E. W. R. Steacie ◽  
H. O. Folkins
Keyword(s):  
Nitric Oxide ◽  
Ethylene Oxide ◽  
Complete Suppression ◽  
Radical Chain ◽  
Decomposition Reactions ◽  
Maximum Inhibition ◽  
A Chain ◽  
Kinetics Of ◽  
Oxide Inhibition

An investigation has been made of the inhibition of free radical chain processes in the decomposition of n-butane by the addition of nitric oxide. The method was to initiate chains in butane at low temperatures by means of ethylene oxide, and then to investigate the efficiency of nitric oxide in suppressing these chains.It was found that nitric oxide is not completely efficient as a chain breaker, inasmuch as sensitization by ethylene oxide persisted in the presence of large amounts of nitric oxide. It is therefore concluded that maximum inhibition of organic decomposition reactions by nitric oxide does not in all cases correspond to complete suppression of chains, and hence the real chain length in such reactions may be greater than that inferred from the results of the nitric oxide inhibition method.

Sign in / Sign up

Export Citation Format

Share Document