ISSN:
0022-3832
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
By using the methods which have been developed to describe the activation energy of chemical reactions in terms of bond energies and the repulsing energies between reacting centers, the factors influencing the activation energies of reactions between radicals and monomers are discussed. Calculations are reported on a number of simple prototype reactions involving radicals and atoms and ethylenic bonds. It is found that the heat of reactions is a most important factor in determining the activation energies of such reactions and this result is extended to a wide variety of substituted radicals and monomers. The variation in the heat of reaction is expressed in terms of the resonance energies of the reacting radicals and molecules. Another important factor is the energy of repulsion between the reacting centers, and this energy is affected by (a) the charge distribution on the reacting centers and (b) the steric effect of substituent groups. The effect of substituents on the charge distribution is discussed in terms of the molecular orbital method, an attempt being made to distinguish between the influence on the π electrons of the inductive and mesomeric effect of substituents.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1948.120030607
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