Some symmetry-induced isotope effects in the kinetics of recombination reactions

2004 ◽  
Vol 121 (2) ◽  
pp. 800-812 ◽  
Author(s):  
Russell T Pack ◽  
Robert B. Walker
Keyword(s):  
Isotope Effects ◽  
Recombination Reactions ◽  
Kinetics Of

Kinetics of the reduction of nicotinonitrile cations by 1,4-dihydronicotinamides

1985 ◽  
Vol 63 (6) ◽  
pp. 1245-1249 ◽  
Author(s):  
John W. Bunting ◽  
John C. Brewer
Keyword(s):  
Ionic Strength ◽  
Transition State ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Spectral Studies ◽  
Close Correspondence ◽  
Charge Generation ◽  
Kinetic Isotope ◽  
Hammett Σ Constants ◽  
Kinetics Of

The rates of reduction of a series of 1-(Z-benzyl)nicotinonitrile cations by a series of 1-(X-benzyl)-1,4-dihydronicotinamides have been studied at 25 °C in 20% CH3CN – 80% H2O (pH 7.0 (5 mM phosphate), ionic strength 1.0 (KCl)). Spectral studies indicate the formation of 1,4-dihydronicotinonitrile products, without the formation of the isomeric 1,2-dihydro- or 1,6-dihydro-nicotinamide intermediates. Second-order rate constants (k2) for these reductions are closely correlated with the Hammett σ constants for X and Z. Thus, for X = H, log k2 = 0.63σz − 1.05, while for Z = 4-CN, log k2 = −0.64σx − 0.65. The close correspondence between these ρx and ρz values indicates that charge neutralization on the nicotinonitrile cation exactly balances charge generation on the nicotinamide cation product in the rate-determining transition state. Thus the migrating hydrogen species is electrically neutral in the rate-determining transition state, which contrasts with the hydridic transition states previously reported in the reduction of isoquinolinium cations by 1,4-dihydronicotinamides. When 1-benzyl-4,4-dideuterio-1,4-dihydronicotinamide is used as the reductant, primary kinetic isotope effects of 3.0 and 2.7 are observed for the reduction of the 1-methylnicotinonitrile and 1-(4-cyanobenzyl)-nicotinonitrile cations, respectively. These data are evaluated in terms of the various mechanistic possibilities for hydride transfer.

scholarly journals Isotope Effects on the Crystallization Kinetics of Selectively Deuterated Poly(ε‐Caprolactone)

2019 ◽  
Vol 57 (12) ◽  
pp. 771-779 ◽  
Author(s):  
Lengwan Li ◽  
Dongsook Chang ◽  
Matthias M. L. Arras ◽  
Wei Li ◽  
Tianyu Li ◽  
...  
Keyword(s):  
Crystallization Kinetics ◽  
Isotope Effects ◽  
Kinetics Of

scholarly journals Properties of Feshbach and “shape”-resonances in ozone and their role in recombination reactions and anomalous isotope effects

2018 ◽  
Vol 212 ◽  
pp. 259-280 ◽  
Author(s):  
Alexander Teplukhin ◽  
Dmitri Babikov
Keyword(s):  
Isotope Effects ◽  
Reaction Pathways ◽  
Recombination Reactions ◽  
Shape Resonances

Three reaction pathways for formation of symmetric and asymmetric isotopologues of ozone.

The kinetics of elementary reactions involving the oxides of sulphur II. Chemical reactions in the sulphur dioxide afterglow

1966 ◽  
Vol 295 (1443) ◽  
pp. 363-379 ◽  
Keyword(s):  
Excited States ◽  
Sulphur Dioxide ◽  
Kinetic Studies ◽  
Absolute Intensity ◽  
Third Order ◽  
Elementary Reactions ◽  
The Third ◽  
Dominant Process ◽  
Recombination Reactions ◽  
Kinetics Of

The main recombination reactions in the sulphur dioxide afterglow are shown to be O + SO 2 + M = SO 3 + M (1) and O + SO + M = SO 2 + M , (2) with rate constants of (4·7 ± 0·8) x 10 15 and (3·2 ± 0·4) x 10 17 cm 6 mole -2 s -1 respectively at 300°K for M = Ar. Reaction (2) is the dominant process removing sulphur monoxide (SO) which is otherwise remarkably unreactive. The absolute intensity of the sulphur dioxide afterglow is found to be I = 1·5 x 10 8 [O] [SO] cm 3 mole -1 s -1 for argon carriers at pressures between 0·25 an d 3·0 mmHg. The afterglow emission comes from three excited states of SO 2 . Spectroscopic and kinetic studies show that these are populated subsequent to or by the third order combination reaction (2). Excited SO 2 is removed mainly by electronic quenching.

Ultraviolet absorption spectra of the CH2Cl and CHCl2 radicals and the kinetics of their self-recombination reactions from 273 to 686 K

1991 ◽  
Vol 87 (15) ◽  
pp. 2367 ◽  
Author(s):  
Pascal B. Roussel ◽  
Phillip D. Lightfoot ◽  
Francoise Caralp ◽  
Val�ry Catoire ◽  
Robert Lesclaux ◽  
...  
Keyword(s):  
Absorption Spectra ◽  
Ultraviolet Absorption ◽  
Recombination Reactions ◽  
Kinetics Of

Studies on Hydrogen–Oxygen Systems in the Electrical Discharge. VII. Deuterium Isotope Effects in the Chemistry of the Hydrogen Polyoxides

1975 ◽  
Vol 53 (16) ◽  
pp. 2490-2497 ◽  
Author(s):  
José L. Arnau ◽  
Paul A. Giguère
Keyword(s):  
Hydrogen Peroxide ◽  
Electrical Discharge ◽  
Microwave Discharge ◽  
Isotope Effects ◽  
Cold Trap ◽  
Manometric Method ◽  
Deuterium Isotope Effects ◽  
Kinetics Of ◽  
Hydrogen Polyoxides ◽  
Hydrogen Peroxide Vapor

The kinetics of oxygen evolution on warming the trapped products (at −196 °C) from water or hydrogen peroxide vapor dissociated in a glow discharge were studied by the manometric method. Under closely controlled conditions it was possible to distinguish clearly the decomposition of the two intermediates, H2O3 and H2O4. The latter begins to decompose measurably following crystallization of the glassy solid at about −115°; the trioxide decomposes readily between −50 and −35°. Typically, the yields of H2O3 from dissociated water vapor were of the order of 3 to 5 mol%; those of H2O4, only about one-tenth as much. Varying the distance between the microwave discharge and the cold trap was found to affect differently the yields of the various products. Those of water and peroxide showed a simple, direct correlation; the minor constituents H2O3 and H2O4 followed entirely different patterns. Only a small fraction of the peroxide is formed via the H2O4 intermediate in these systems. Less water, and more of the higher oxides, were obtained from dissociated hydrogen peroxide than from water vapor.The deuterated systems showed some unusual isotope effects. The yields of D2O3 were always higher (up to twice and even more) than those of H2O3 under similar conditions. The other products showed little or no such effect, except for occluded oxygen and ozone which decreased by about half. Finally, the deuterium polyoxides decompose at slightly higher temperatures (10 to 15°) than their hydrogen analogs. Mechanisms are proposed for the formation and decomposition of the polyoxides.

The hydrogen isotope effect in the bromination of 2-carbethoxy cyclo pentanone

1956 ◽  
Vol 235 (1203) ◽  
pp. 453-468 ◽  
Keyword(s):  
Isotope Effect ◽  
Hydrogen Isotope ◽  
Deuterium Oxide ◽  
Isotope Effects ◽  
Activation Energies ◽  
Tunnel Effect ◽  
Fluoride Ion ◽  
Energy Barriers ◽  
Hydrogen Isotope Effect ◽  
Kinetics Of

Measurements are reported on the kinetics of the base-catalyzed bromination of 2-car-bethoxycyclopentanone, with either hydrogen or deuterium in the active position. The solvent throughout was deuterium oxide, the catalysts employed were the solvent, monochloroacetate ion and fluoride ion, and measurements were made at 5° intervals over the range 10 to 70°C. The observed activation energies are all greater for the deutero- than for the proto-ester, but the differences are greater than would be expected on current theories of isotope effects. The observed collision factors are in every case greater for deuterium than for hydrogen, especially for catalysis by fluoride ion, where the ratio of these factors is A D / A H = 24 ± 4. These observations can only be accounted for by invoking the tunnel effect, i. e. by supposing that the motion of the proton is markedly non-classical in nature. It is shown that this hypothesis leads to reasonable dimensions for the energy barriers involved, and some if its general consequences are discussed.

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