Polymer solvent dynamic effects on an electron-transfer cross-reaction rate at a redox polymer/polymer solution interface

The dehydrogenation of 1,4-dihydronaphthalene by tetrachloro-p-benzoquinone in phenetole solution has been investigated. The present work does not fully confirm earlier studies which report that the reaction follows second-order kinetics and that the hydride ion transfer is rate determining. In the investigations described in this paper second-order kinetics are only observed in the later stages of the reaction and a 1:1 stoichiometry of the reactants in the process is not obtained. Substitution of tritium in the 1,4-positions of the hydrocarbon appears to not significantly affect the reaction rate. The present results indicate that charge-transfer complexes are formed in the reaction and it is suggested that electron transfer within these complexes could be the rate-determining step in the dehydrogenation.

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Nonadiabatic instanton calculation of multistate electron transfer reaction rate: Interference effects in three and four states systems

The Journal of Chemical Physics ◽

10.1063/1.1371262 ◽

2001 ◽

Vol 114 (22) ◽

pp. 9959-9968 ◽

Cited By ~ 19

Author(s):

Seogjoo Jang ◽

Jianshu Cao

Keyword(s):

Electron Transfer ◽

Reaction Rate ◽

Transfer Reaction ◽

Electron Transfer Reaction ◽

Interference Effects

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Concerted double proton-transfer electron-transfer between catechol and superoxide radical anion

Physical Chemistry Chemical Physics ◽

10.1039/c7cp03930a ◽

2017 ◽

Vol 19 (38) ◽

pp. 26179-26190 ◽

Cited By ~ 13

Author(s):

Jorge Quintero-Saumeth ◽

David A. Rincón ◽

Markus Doerr ◽

Martha C. Daza

Keyword(s):

Electron Transfer ◽

Proton Transfer ◽

Superoxide Anion ◽

Radical Anion ◽

Reaction Rate ◽

Superoxide Radical ◽

Superoxide Radical Anion ◽

Double Proton Transfer

Catechol reacts with a superoxide anion via concerted double proton-transfer electron-transfer with a reaction rate that is dominated by tunneling.

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Differential Diffusivity Effects in Reactive Convective Dissolution

Fluids ◽

10.3390/fluids3040083 ◽

2018 ◽

Vol 3 (4) ◽

pp. 83 ◽

Cited By ~ 8

Author(s):

V. Loodts ◽

H. Saghou ◽

B. Knaepen ◽

L. Rongy ◽

A. De Wit

Keyword(s):

Diffusion Coefficients ◽

Reaction Rate ◽

Chemical Species ◽

Mixing Zone ◽

Simultaneous Presence ◽

Dynamic Effects ◽

Density Profiles ◽

Differential Diffusion ◽

Different Types ◽

Double Diffusive

When a solute A dissolves into a host fluid containing a reactant B, an A + B → C reaction can influence the convection developing because of unstable density gradients in the gravity field. When A increases density and all three chemical species A, B and C diffuse at the same rate, the reactive case can lead to two different types of density profiles, i.e., a monotonically decreasing one from the interface to the bulk and a non-monotonic profile with a minimum. We study numerically here the nonlinear reactive convective dissolution dynamics in the more general case where the three solutes can diffuse at different rates. We show that differential diffusion can add new dynamic effects like the simultaneous presence of two different convection zones in the host phase when a non-monotonic profile with both a minimum and a maximum develops. Double diffusive instabilities can moreover affect the morphology of the convective fingers. Analysis of the mixing zone, the reaction rate, the total amount of stored A and the dissolution flux further shows that varying the diffusion coefficients of the various species has a quantitative effect on convection.

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