Kinetic study of the fast halogen-trihalide ion equilibria in protic media by the Raman-laser temperature-jump technique. A non-diffusion-controlled ion-molecule reaction

1986 ◽  
Vol 90 (18) ◽  
pp. 4382-4388 ◽  
Author(s):  
Marie Francoise Ruasse ◽  
Jean Aubard ◽  
Bernard Galland ◽  
Alain Adenier
Keyword(s):  
Kinetic Study ◽  
Temperature Jump ◽  
Raman Laser ◽  
Molecule Reaction ◽  
Diffusion Controlled ◽  
Laser Temperature Jump ◽  
Protic Media

Kinetics of the stacking of ethidium bromide by the raman laser temperature-jump method

1974 ◽  
Vol 2 (4) ◽  
pp. 385-389 ◽  
Author(s):  
Douglas H. Turner ◽  
Raymond Yuan ◽  
George W. Flynn ◽  
Norman Sutin
Keyword(s):  
Ethidium Bromide ◽  
Temperature Jump ◽  
Raman Laser ◽  
Laser Temperature Jump ◽  
Kinetics Of

Primary products and processes in the γ-radiolysis of 2-methyltetrahydrofuran

1965 ◽  
Vol 285 (1402) ◽  
pp. 319-338 ◽  
Keyword(s):  
Glassy Phase ◽  
Kcal Mole ◽  
Radical Species ◽  
Molecule Reaction ◽  
Positive Ions ◽  
Primary Products ◽  
Diffusion Controlled ◽  
Thermal Bleaching ◽  
The Matrix ◽  
Kinetics Of

From a study of the u. v., visible, near i. r. and e. s. r. spectra induced by γ -irradiation at 77°K in glassy MTHF and in glassy MTHF containing various additives and from a study of controlled temperature increases on these spectra, the following conclusions are drawn. (1) The primary products of the radiolysis are electrons ( e - ) and positive ions ( MTHF + ) which undergo a rapid ion-molecule reaction to give O CH 3 radicals ( R ⋅). (2) e - can either be trapped in the glassy MTHF matrix or can be captured by either napththalene, ferric chloride, carbon tetrachloride, nitrous oxide or trans -stilbene if these substances are present. (3) The e - T are bleachable by light or heat and disappear independently of the radicals R⋅ without either augmentation of R⋅ or the production of any new radical species. (4) e - T and R⋅ disappear thermally and independently by second-order reactions, the rate constants being K e - + e - (M -1 S -1 ) = 10 12⋅4±1⋅1 exp ─ [0⋅85 ± 0⋅10 kcal/mole/ R ( T ─ 75)] and K R˙ + R˙ (M -1 S -1 ) = 10 13⋅3±1⋅4 exp ─ [1⋅20 ± 0⋅15 kcal/mole/ R ( T ─ 75)]. These rate expressions suggest that both reactions are diffusion controlled at low temperatures in the glassy phase. (5) The kinetics of the thermal bleaching of e - T indicate that the electrons migrate distances of about 150 Å from their parent positive ions before being trapped in the matrix. (6) The effect of FeCl 3 in reducing the formation of e - T at 77°K and its lack of effect on the thermal bleaching of e - T suggests that the reaction e - + FeCl 3 → FeCl 2 + Cl - only occurs before the electron is thermalized.

Sign in / Sign up

Export Citation Format

Share Document