Influence of hydrodynamic interaction on the diffusion-controlled reaction kinetics of molecules with highly anisotropic reactivity

2003 ◽  
Vol 118 (3) ◽  
pp. 1301-1311 ◽  
Author(s):  
A. I. Shushin
Keyword(s):  
Reaction Kinetics ◽  
Hydrodynamic Interaction ◽  
Diffusion Controlled ◽  
Kinetics Of ◽  
Diffusion Controlled Reaction

Modulation spectroscopy. Kinetics for the self-reactions of some α-aminoalkyl radicals in solution

1982 ◽  
Vol 60 (3) ◽  
pp. 274-278 ◽  
Author(s):  
Paul R. Marriott ◽  
Arlindo L. Castelhano ◽  
David Griller
Keyword(s):  
Absorption Spectrum ◽  
Reaction Kinetics ◽  
Unpaired Electron ◽  
Rate Constants ◽  
Lone Pair ◽  
The Self ◽  
Modulation Spectroscopy ◽  
Alkyl Radicals ◽  
Diffusion Controlled ◽  
Kinetics Of

The optical spectra and reaction kinetics of some a-aminoalkyl radicals, RĊHN(CH2R)2; R≡H, Me, Ph, were measured in solution using the technique of modulation spectroscopy. These radicals undergo diffusion controlled self-reaction with rate constants [Formula: see text]. When R≡Ph, the absorption spectrum has a well defined maximum at 346 nm; ε = 3390 M−1 cm−1, while the spectra when R≡H or Me were less intense [Formula: see text] and tailed into the visible. These spectra are substantially red-shifted when compared with those of simple alkyl radicals, an effect which is thought to be due to the interaction between the unpaired electron and the lone pair of electrons on nitrogen.

Kinetics of Hill-Hermans diffusion of an unstable reagent

1955 ◽  
Vol 228 (1174) ◽  
pp. 397-410
Keyword(s):  
Continuous Method ◽  
Polymer Chemistry ◽  
Reactive Site ◽  
Transient Effect ◽  
Rubber Latex ◽  
Rate Law ◽  
First Order ◽  
Diffusion Controlled ◽  
Kinetics Of ◽  
Diffusion Controlled Reaction

This work deals with a generalization of the widely applicable theory of Hill's, later developed by Hermans. It concerns the diffusion-controlled reaction of a reagent with a polymer across an interface, in the course of which the reagent is captured by an infinitely reactive site ('sink') inside the polymer. For certain applications, it becomes necessary to introduce an alternative fate which the reagent may suffer during diffusion to the sink, namely, deactivation or decomposition. The present kinetic theory of this effect is based on the method of considering the elementary jumps responsible for diffusion, while Hill and Hermans used the complementary, continuous method based on Fick's law. The present derivation of a general rate law for the conversion of the polymer is based on a pseudo lattice model. The rate law takes the form of an infinite spectrum of first-order decay terms, and is little dependent on details of the model used or on curvature of the interface. It does depend critically on a stability constant s of the reagent, which is unity for a perfectly stable and zero for a completely unstable one. In the former case the rate law reduces substantially to that of Hill and Hermans, but covers the initial transient effect as well as the steady state. As s →0, the rate law converges uniformly to that of a first-order chemisorption of a monolayer over the appropriate range. Intermediate cases (0 < s < 1) are of interest in the chemistry of rubber latex, and probably in other fields of polymer chemistry.

Recovering boundaries for partly diffusion-controlled reaction kinetics

1996 ◽  
Vol 212 (1) ◽  
pp. 99-114 ◽  
Author(s):  
Nicholas J.B. Green ◽  
Rowland D. Spencer-Smith ◽  
Alix G. Rickerby
Keyword(s):  
Reaction Kinetics ◽  
Diffusion Controlled ◽  
Diffusion Controlled Reaction
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