Separation of the polarization of a two-electron transfer reaction into those of consecutive one-electron transfer reactions by potential-step chronoamperometry in the oxidation of O2− ion by Pt/YSZ oxygen electrodes

1997 ◽  
Vol 42 (23-24) ◽  
pp. 3461-3470 ◽  
Author(s):  
T. Kenjo ◽  
N. Shiroichi
2011 ◽  
Vol 8 (3) ◽  
pp. 1152-1157
Author(s):  
Prabla Kumari ◽  
Alaka Das ◽  
Dillip Kumar Baral ◽  
A. K. Pattanaik ◽  
P. Mohanty

The kinetics of the electron transfer reaction of NADH with 12-tungstocobaltate(III) has been studied over the range 5.07 ≤ 104[NADH] ≤ 15.22 mol dm-3, 7.0 ≤ pH ≤ 8.0 and 20 ≤ t ≤ 35oC in aqueous medium. The electron transfer reaction showed first-order dependence each in [NADH]Tand [12-tungstocobaltate(III)]T. The products of the reaction were found to be NAD+and 12-tungstocobaltate(II). The activation parameters ΔH#(kJ mol-1) and ΔS#(JK-1mol-1) of the electron transfer reactions were found to be 64.4±1.8 and -48.86±6.0. Negative value of ΔS#is an indicative of an ordered transition state for the electron transfer reaction.


2018 ◽  
Vol 6 (2) ◽  
pp. 163
Author(s):  
Bharati Behera ◽  
Jashoda Behera

The kinetics of the electron transfer reaction of NADH with Cis-[Co(en)2(H2O)2]3+ has been studied over the range 1.0 ≤ 102 [NADH] ≤ 3.0 mol dm-3, 7.0 ≤ pH ≤ 8.0 and 200C ≤ t ≤ 350C in aqueous medium. The rate of electron transfer reaction was found to be first-order dependence each in [NADH]T and Cis-[Co(en)2(H2O)2]3+T. The products of the reaction were found to be NAD+ and Co(II). The corresponding activation parameters of the electron transfer reactions were found to be as ΔH#=27.55 kJ mol-1 and  ΔS#= -189.35 JK-1mol-1. 


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
P. Krishnaveni ◽  
V. Ganesh

AbstractModern day hospital treatments aim at developing electrochemical biosensors for early diagnosis of diseases using unconventional human bio-fluids like sweat and saliva by monitoring the electron transfer reactions of target analytes. Such kinds of health care diagnostics primarily avoid the usage of human blood and urine samples. In this context, here we have investigated the electron transfer reaction of a well-known and commonly used redox probe namely, potassium ferro/ferri cyanide by employing artificially simulated bio-mimics of human sweat and saliva as unconventional electrolytes. Typically, electron transfer characteristics of the redox couple, [Fe(CN)6]3−/4− are investigated using electrochemical techniques like cyclic voltammetry and electrochemical impedance spectroscopy. Many different kinetic parameters are determined and compared with the conventional system. In addition, such electron transfer reactions have also been studied using a lyotropic liquid crystalline phase comprising of Triton X-100 and water in which the aqueous phase is replaced with either human sweat or saliva bio-mimics. From these studies, we find out the electron transfer reaction of [Fe(CN)6]3−/4− redox couple is completely diffusion controlled on both Au and Pt disc shaped electrodes in presence of sweat and saliva bio-mimic solutions. Moreover, the reaction is partially blocked by the presence of lyotropic liquid crystalline phase consisting of sweat and saliva bio-mimics indicating the predominant charge transfer controlled process for the redox probe. However, the rate constant values associated with the electron transfer reaction are drastically reduced in presence of liquid crystalline phase. These studies are essentially carried out to assess the effect of sweat and saliva on the electrochemistry of Fe2+/3+ redox couple.


2019 ◽  
Vol 116 (9) ◽  
pp. 3407-3412 ◽  
Author(s):  
Yueqi Li ◽  
Hui Wang ◽  
Zixiao Wang ◽  
Yanjun Qiao ◽  
Jens Ulstrup ◽  
...  

Electron transfer reactions can now be followed at the single-molecule level, but the connection between the microscopic and macroscopic data remains to be understood. By monitoring the conductance of a single molecule, we show that the individual electron transfer reaction events are stochastic and manifested as large conductance fluctuations. The fluctuation probability follows first-order kinetics with potential dependent rate constants described by the Butler–Volmer relation. Ensemble averaging of many individual reaction events leads to a deterministic dependence of the conductance on the external electrochemical potential that follows the Nernst equation. This study discloses a systematic transition from stochastic kinetics of individual reaction events to deterministic thermodynamics of ensemble averages and provides insights into electron transfer processes of small systems, consisting of a single molecule or a small number of molecules.


1979 ◽  
Vol 34 (9) ◽  
pp. 1093-1098 ◽  
Author(s):  
Ulrich Steiner

Abstract The radical yield in the electron transfer reactions between thionine triplet and various halogenanilines, as measured by kinetic flash spectroscopy in the microsecond time region, decreases by application of magnetic fields up to 4 kGauss. The relative magnetic field effect parallels the influence of the heavy atom substituents on the intersystem crossing rate constant in the triplet exciplex supposed to be the primary product of the electron transfer reaction. The magnetic field effect is suggested to be due to differences of the g-factors in the geminate radical pair, originating by dissociation of the triplet exciplex.


1978 ◽  
Vol 56 (16) ◽  
pp. 2216-2220 ◽  
Author(s):  
Sadayuki Matsuda ◽  
Akihiko Yamagishi

The effects of potassium ion on the electron-transfer reactions between Fe(CN)64− and 7,7,8,8-tetracyanoquinodimethane (TCNQ) or chloranil (QCl4) were studied with temperature-jump equipment; [Formula: see text]. The solvent was a 1:1 (v/v) mixture of acetonitrile–water. In both Systems, the forward rate constants (kr) were unaffected by the addition of KCl; kf(Fe(CN)64−/TCNQ) = (2.9 ± 0.2) × 106 M−1 s−1, and kr(Fe(CN)64−/QCl4) = (5.2 ± 0.4) × 104 M−1 s−1 On the other hand, the backward rate constants (kb) increased with the increase of the KCl concentration. The results are interpreted in terms of ion-pairing equilibria of Fe(CN)64− and Fe(CN)63−.


Electron transfer reactions of Co complexes with Fe 2+ (inner sphere) and with V 2+ (outer sphere) are studied in the presence of polyelectrolytes. Anionic polyelectrolytes accelerate the reactions remarkably, as expected. Two points are noteworthy: (1) the acceleration for the Fe 2+ systems is larger than that for the V 2+ reactions, in spite of the fact that both are divalent, and (2) electron transfer reaction between cationic species (Co(NH 3 ) 4 (N 3 ) 2 + and Fe 2+ ) is accelerated, though slightly, by addition of a cationic polyelectrolyte. This is in qualitative agreement with predictions based on Brönsted-Bjerrum-Manning theory. Temperature dependence study shows that the acceleration observed for the Fe 2+ cases is due to entropic gain whereas that in the case of V 2+ is ascribed to decrease in the enthalpy of activation.


2020 ◽  
Vol 24 (09) ◽  
pp. 1099-1104
Author(s):  
Kei Sakakibara ◽  
Kenta Tomida ◽  
Tatsuo Nakagawa ◽  
Takeyoshi Yagyu ◽  
Hideo D. Takagi ◽  
...  

We report the dynamics of a intramolecular photoinduced electron transfer reaction of Zn(II)-porphyrin dyads that have a 2,2[Formula: see text]-bipyridine moiety at the periphery in the presence of Cu[Formula: see text] in methanol studied using laser flash photolysis with a sub-nanosecond time resolution. The photoinduced electron transfer reactions were observed from the excited [Formula: see text] and [Formula: see text] states of the Zn(II)-porphyrin to the Cu(II)-2,2[Formula: see text]-bipyridine moiety, and the structural dependence of the reactivity were discussed in terms of the distance between the electron donating and accepting centers.


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