scholarly journals Escape of anions from geminate recombination in THF due to charge delocalization

2017 ◽  
Vol 19 (48) ◽  
pp. 32272-32285
Author(s):  
Hung-Cheng Chen ◽  
Andrew R. Cook ◽  
Sadayuki Asaoka ◽  
Jeffery S. Boschen ◽  
Theresa L. Windus ◽  
...  
Keyword(s):  
Pulse Radiolysis ◽  
Radical Anions ◽  
Geminate Recombination ◽  
Charge Delocalization

Geminate recombination of 24 radical anions (M˙−) with solvated protons (RH2+) was studied in tetrahydrofuran (THF) with pulse radiolysis.

Effects of quaternary ammonium salts on reactions of aromatic radical anions formed in tetrahydrofuran by pulse radiolysis

1984 ◽  
Vol 88 (11) ◽  
pp. 2368-2372 ◽  
Author(s):  
Yukio Yamamoto ◽  
Shoichi Nishida ◽  
Katsuyoshi Yabe ◽  
Koichiro Hayashi ◽  
Seishi Takeda ◽  
...  
Keyword(s):  
Quaternary Ammonium ◽  
Pulse Radiolysis ◽  
Quaternary Ammonium Salts ◽  
Ammonium Salts ◽  
Radical Anions ◽  
Aromatic Radical

Selenium-Selenium Bond Cleavage of Diaryl Diselenide Radical Anions During Pulse Radiolysis

ChemPlusChem ◽  
2014 ◽  
Vol 80 (1) ◽  
pp. 68-73 ◽  
Author(s):  
Sachiko Tojo ◽  
Mamoru Fujitsuka ◽  
Akihiko Ouchi ◽  
Tetsuro Majima
Keyword(s):  
Pulse Radiolysis ◽  
Bond Cleavage ◽  
Radical Anions

ChemInform Abstract: MECHANISM OF TRYPTOPHAN OXIDATION BY SOME INORGANIC RADICAL-ANIONS- A PULSE RADIOLYSIS STUDY

1976 ◽  
Vol 7 (47) ◽  
pp. no-no
Author(s):  
M. L. POSENER ◽  
G. E. ADAMS ◽  
P. WARDMAN ◽  
R. B. CUNDALL
Keyword(s):  
Pulse Radiolysis ◽  
Radical Anions ◽  
Tryptophan Oxidation

Geminate-ion kinetics with competing ion fragmentation in nonpolar liquids with halocarbons

1990 ◽  
Vol 68 (9) ◽  
pp. 918-924 ◽  
Author(s):  
Rolf E. Bühler
Keyword(s):  
Low Temperatures ◽  
Pulse Radiolysis ◽  
Room Temperature ◽  
Ion Concentration ◽  
Geminate Recombination ◽  
Rate Law ◽  
Ion Fragmentation ◽  
Nonpolar Liquids ◽  
Ion Recombination ◽  
Semi Empirical

The semi-empirical rate law for geminate-ion recombination by van den Ende, Warman, and Hummel, which predicts a linear dependence of the ion concentration with t−0.6, is modified to include simultaneous ion fragmentation. The theory is applied to the kinetics, as observed by pulse radiolysis of liquid methylcyclohexane (MCH) solutions of N2O, CHCl3, or tert-butylchloride (t-BuCl) at low temperatures. In MCH saturated with N2O (−130 °C), the solvent cation (MCH+, λmax = 550 nm) moves about 400 times faster than prediced by diffusion. With the known conductivity data at room temperature, an activation energy of about 2.7 kJ/mol can be derived. The solvent cation MCH+ does not appear to fragment. With t-BuCl added to MCH (−134 °C), MCH+ (λmax = 550 nm) and t-BuCl− (λmax = 450 nm) are observed simultaneously. The initial kinetics corresponds to the parent ion (MCH+) recombination with t-BuCl−. Then the MCH+ fragmentation with k1(−134 °C) = 3 × 105 s−1 is observed, followed by the geminate recombination of some fragment cation with t-BuCl−. The fragment cation recombines 300 times slower than the parent cation. With CHCl3 added to MCH (−130 °C), the MCH+ absorption is hidden within the [Formula: see text] band (λmax = 470 nm); however, the fragmentation is detected from kinetic analysis to occur in about 2 × 106 s−1. The modified t−0.6 rate law appears to be a very useful tool to study simultaneous ion recombination and ion fragmentation.

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