Microenvironment effects on the kinetics of electron-transfer reactions involving dithionite ions and viologens. 1. A comparison between two types of polyelectrolytes
- Universite de Nancy I, Vandoeuvre-les-Nancy (France)
The retardation of the rate of electron-transfer reactions constitutes a major goal in the development of energy-producing photochemical processes. The stopped-flow technique was used in this work to investigate the retarding effects of two polyelectrolytes on the rate of reduction of a series of dialkylviologens (N,N{prime}-dialkyl-4,4{prime}-bipyridinium, with alkyl chains varying from methyl to hexadecyl) by sodium dithionite. The apparent rate constants for reduction have been measured in the absence and in the presence of polyelectrolytes having widely different shapes: poly(styrenesulfonic acid) (PSSH), which is essentially linear, and maleic acid-cetyl vinyl ether (MA-CVE), which is a polysoap. The latter one was shown to be much more efficient than the former. The larger retardation effect (about 50-fold) was obtained with MA-CVE in combination with di-C{sub 16}-viologen. The effect of polyelectrolyte concentration on the observed pseudo-first-order rate constant could be theoretically predicted for both polyelectrolytes.
- OSTI ID:
- 6404241
- Journal Information:
- Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:19; ISSN 0022-3654; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
140505* -- Solar Energy Conversion-- Photochemical
Photobiological
& Thermochemical Conversion-- (1980-)
AMINES
AMMONIUM COMPOUNDS
AZINES
CHEMICAL REACTIONS
ELECTROLYTES
ELECTRON TRANSFER
HETEROCYCLIC COMPOUNDS
KINETICS
MEASURING METHODS
MICELLAR SYSTEMS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PYRIDINES
PYRIDINIUM COMPOUNDS
QUATERNARY COMPOUNDS
REACTION KINETICS