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Investigations on the influence of charge density on the mutual deactivation of polyion-macroradicals—II

✍ Scribed by W. Görlich; W. Schnabel

Publisher
Elsevier Science
Year
1973
Tongue
English
Weight
420 KB
Volume
9
Category
Article
ISSN
0014-3057

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✦ Synopsis

Abstraet--Bimolecular rate constants (2 kR) of the reaction R. + R. in aqueous solution were measured using the pulse radiolysis technique. R. designates radicals produced by H atom abstraction from polyvinyl alcohol partially acetalyzed with glyoxylic acid. Due to the expansion of the coils, 2 kR increases with x,, the content of ionized base units in mole 70. Above a critical value x~(crit), 2 kR decreases due to intermolecular repulsion, x~(crit) decreases with increasing chain length a~ [x~(crit) ~ 0"5 mole % at a, = 3000 and x~(crit) ~ 1.5 mole % at a, = 270]. In the presence of NaC104, the following salt effects were observed: for x, > x~(crit), 2 kR is increased because the intermolecular repulsion is partially depressed by screening. Below x~(crit), 2 kR is decreased since the coil expansion is diminished. At very low values of x, where the coil expansion due to intramolecular repulsion is negligible, no salt effect was detectable.

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