ISSN:
0025-116X
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
Organic radicals were produced in the tensides C16H33(OCH2CH2)21OH and C14H29(OCH2CH2)3-SO3Na in aqueous solutions using a short pulse of high energy electrons. The radicals were formed by OH attack on the (OCH2CH2)x-parts of the tensides. The decay of the 250nm absorption of the radicals was recorded at different initial radical concentrations and tenside concentrations. Several radicals could be produced in one micelle. Radicals formed in the same micelle decay within microseconds or faster. The half life time τ1 in a micelle carrying two radicals is 2,0·10-6 s for C16H33(OCH2CH2)21 OH and less than 6·10-7 s for C14H29(OCH2CH2)3SO3Na. A model for intramicellar radical-radical reactions is proposed according to which the rate is faster in tensides of high critical micelle concentration. Single radicals in micelles of C16H33(OCH2CH2)21OH can deactivate each other without leaving the micelles. This intermicellar reaction is discussed in terms of the rate of diffusion-controlled micelle-micelle encounters, an encounter time of 7·10-8s, and the above time τ1 for intramicellar reaction. The observed rate constant 2k of intermicellar reaction is 3,5·106 mol-1·l·s-1. At low tenside concentrations, the bimolecular rate constant increases since more single tenside radicals are present in solution. They react rapidly (ca. 108 mol-1·l·s-1) with radicals in micelles. Single radicals in C14H33(OCH2CH2)3-SO3Na micelles cannot directly react with each other because of the Coulombic repulsion between two anionic micelles. Reaction occurs after the exit of a tenside radical from its micelle, the rate of which depends on the micellar equilibrium Mn⇄Mn-1+M (M: tenside molecule; n: agglomeration number of micelle). A single radical in solution reacts with a single radical in a micelle with 2k = 1,0·108 mol-1·l·s-1 and with another single radical in solution with 4,0·107 mol-1·l·s-1.γ-Irradiation of both tensides in aqueous solution leads to slight increases in viscosity, followed by turbidity beyond the “gel dose” and phase separation. These effects are explained in terms of crosslinking of tenside molecules. Formation of a large network requires bridges between all participating tenside molecules (not only bridges between micelles).
Additional Material:
11 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/macp.1978.021790915
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