A KINETIC STUDY OF THE METATHETICAL AND ADDITION REACTIONS CHARACTERISTIC OF ALLYL POLYMERIZATION

1962 ◽  
Vol 40 (4) ◽  
pp. 796-803 ◽  
Author(s):  
A. C. R. Brown ◽  
D. G. L. James
Keyword(s):  
Experimental Data ◽  
Free Radicals ◽  
Gas Phase ◽  
Rate Constants ◽  
Allyl Alcohol ◽  
Reasonable Agreement ◽  
Chain Transfer ◽  
Addition Reactions ◽  
Radical Reactivity ◽  
Transfer Processes

The rate constants of the reactions[Formula: see text]have been measured in the gas phase between 50° and 142 °C:[Formula: see text]where ki is the (known) rate constant for the reaction[Formula: see text]The significance of these values is discussed in relation to the propagation and chain transfer processes in the polymerization of allyl alcohol. A consideration of the rates of addition of free radicals to a series of monomers of diverse reactivity reveals that a correlation exists between the rate constants for the addition of the ethyl radical in the gas phase and of certain polymer radicals in the liquid phase.An application of the general equation proposed by Bamford, Jenkins, and Johnston for radical reactivity leads to the conclusion that kp ≈ 2k7 and that kP/kf ≈ k7/k6 = 1.8 for allyl alcohol at 60 °C. Predictions based upon these relationships are compared with experimental data for the propagation and degree of homopolymerization of allyl alcohol and for inhibition and propagation in copolymerization; reasonable agreement is found in all cases.

Muonium Addition Reactions and Kinetic Isotope Effects in the Gas Phase: k∞ Rate Constants for Mu + C2H2

2015 ◽  
Vol 119 (28) ◽  
pp. 7247-7256 ◽  
Author(s):  
Donald J. Arseneau ◽  
David M. Garner ◽  
Ivan D. Reid ◽  
Donald G. Fleming
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Addition Reactions ◽  
Kinetic Isotope

Theoretical analysis of counter-current absorption of a poorly soluble gas based on the PDE-AD model

1986 ◽  
Vol 51 (6) ◽  
pp. 1222-1239 ◽  
Author(s):  
Pavel Moravec ◽  
Vladimír Staněk
Keyword(s):  
Experimental Data ◽  
Liquid Phase ◽  
Gas Phase ◽  
Transfer Functions ◽  
Packed Bed ◽  
Packed Bed Column ◽  
Interfacial Transport ◽  
Gaseous Component ◽  
Poorly Soluble ◽  
Counter Current

Expression have been derived in the paper for all four possible transfer functions between the inlet and the outlet gas and liquid steams under the counter-current absorption of a poorly soluble gas in a packed bed column. The transfer functions have been derived for the axially dispersed model with stagnant zone in the liquid phase and the axially dispersed model for the gas phase with interfacial transport of a gaseous component (PDE - AD). calculations with practical values of parameters suggest that only two of these transfer functions are applicable for experimental data evaluation.

Diffusion model for deposition of epitaxial GaAs layers prepared by the MOCVD method

1991 ◽  
Vol 56 (10) ◽  
pp. 2020-2029
Author(s):  
Jindřich Leitner ◽  
Petr Voňka ◽  
Josef Stejskal ◽  
Přemysl Klíma ◽  
Rudolf Hladina
Keyword(s):  
Experimental Data ◽  
Growth Rate ◽  
Kinetic Model ◽  
Gas Phase ◽  
Substrate Surface ◽  
Deposition Process ◽  
Hydrogen Atmosphere ◽  
Epitaxial Gaas ◽  
Kinetics Of ◽  
Good Agreement

The authors proposed and treated quantitatively a kinetic model for deposition of epitaxial GaAs layers prepared by reaction of trimethylgallium with arsine in hydrogen atmosphere. The transport of gallium to the surface of the substrate is considered as the controlling process. The influence of the rate of chemical reactions in the gas phase and on the substrate surface on the kinetics of the deposition process is neglected. The calculated dependence of the growth rate of the layers on the conditions of the deposition is in a good agreement with experimental data in the temperature range from 600 to 800°C.

An homogeneous growth model of gallium arsenide epitaxial layers from the gas phase

1989 ◽  
Vol 54 (11) ◽  
pp. 2933-2950
Author(s):  
Emerich Erdös ◽  
Petr Voňka ◽  
Josef Stejskal ◽  
Přemysl Klíma
Keyword(s):  
Experimental Data ◽  
Gallium Arsenide ◽  
Kinetic Study ◽  
Gas Phase ◽  
Growth Model ◽  
Epitaxial Layers ◽  
Inhomogeneous Model ◽  
Homogeneous Models ◽  
Active Centres

This paper represents a continuation and ending of the kinetic study of the gallium arsenide formation, where a so-called inhomogeneous model is proposed and quantitatively formulated in five variants, in which two kinds of active centres appear. This model is compared both with the experimental data and with the previous sequence of homogeneous models.

Methylene. III. Gas phase reactions with 1-chloropropane

1969 ◽  
Vol 312 (1509) ◽  
pp. 141-161 ◽  
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Hydrogen Abstraction ◽  
The Other ◽  
Gas Phase Reactions ◽  
Other Hand ◽  
Chlorine Substituent ◽  
High Degree ◽  
Singlet Methylene

The work described in this and the following paper is a continuation of that in parts I and II, devoted to elucidation of the mechanism of the reactions of methylene with chloroalkanes, with particular reference to the reactivities of singlet and triplet methylene in abstraction and insertion processes. The products of the reaction between methylene, prepared by the photolysis of ketene, and 1-chloropropane have been identified and estimated and their dependence on reactant pressures, photolysing wavelength and presence of foreign gases (oxygen and carbon mon­oxide) has been investigated. Both insertion and abstraction mechanisms contribute significantly to the over-all reaction, insertion being relatively much more important than with chloroethane. This type of process appears to be confined to singlet methylene. If, as seems likely, there is no insertion into C—Cl bonds under our conditions (see part IV), insertion into C2—H and C3—H bonds occurs in statistical ratio, approximately. On the other hand, the chlorine substituent reduces the probability of insertion into C—H bonds in its vicinity. As in the chloroethane system, both species of methylene show a high degree of selectivity in their abstraction reactions. We find that k S Cl / k S H >7.7, k T Cl / k T H < 0.14, where the k ’s are rate constants for abstraction, and the super- and subscripts indicate the species of methylene and the type of atom abstracted, respectively. Triplet methylene is discriminating in hydrogen abstraction from 1-C 3 H 7 Cl, the overall rates for atoms attached to C1, C2, C3 being in the ratios 2.63:1:0.

ChemInform Abstract: Absolute Rate Measurements for Some Gas-Phase Addition Reactions of Dimethylsilylene

ChemInform ◽  
1988 ◽  
Vol 19 (39) ◽  
Author(s):  
J. E. BAGGOTT ◽  
M. A. BLITZ ◽  
H. M. FREY ◽  
P. D. LIGHTFOOT ◽  
R. WALSH
Keyword(s):  
Gas Phase ◽  
Addition Reactions ◽  
Absolute Rate

An experimental study of the reactivity of the hydroxide anion in the gas phase at room temperature, and its perturbation by hydration

1981 ◽  
Vol 59 (11) ◽  
pp. 1615-1621 ◽  
Author(s):  
Scott D. Tanner ◽  
Gervase I. Mackay ◽  
Diethard K. Bohme
Keyword(s):  
Experimental Study ◽  
Proton Transfer ◽  
Gas Phase ◽  
Rate Constants ◽  
Room Temperature ◽  
Gas Phase Reactions ◽  
Flowing Afterglow ◽  
Hydroxide Anion

Flowing afterglow measurements are reported which provide rate constants and product identifications at 298 ± 2 K for the gas-phase reactions of OH− with CH3OH, C2H5OH, CH3OCH3, CH2O, CH3CHO, CH3COCH3, CH2CO, HCOOH, HCOOCH3, CH2=C=CH2, CH3—C≡CH, and C6H5CH3. The main channels observed were proton transfer and solvation of the OH−. Hydration with one molecule of H2O was observed either to reduce the rate slightly and lead to products which are the hydrated analogues of the "nude" reaction, or to stop the reaction completely, k ≤ 10−12 cm3 molecule−1 s−1. The reaction of OH−•H2O with CH3—C≡CH showed an uncertain intermediate behaviour.

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