Deuterium Kinetic Isotope Effect in the Hydrogen—Iodine Reaction

Sullivan, John H.

doi:10.1063/1.1734134

Cited by 34 publications

(11 citation statements)

References 23 publications

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“…The isotopes have the same number of electrons, and there is no difference between the wave function and the potential curved surface in the Born–Oppenheimer approximation. On the other hand, there is a difference in vibration energy of C–H and C–D bonds due to the difference of the mass number. − Here, the Gibbs free energy can be expressed in the following equations: where h is the Planck constant, n is the principal number, k s is the spring constant of chemical bond, and μ is the reduced mass of atoms involved in chemical bond. A chemical bond with a deuterium is more stable than that with a protium resulting from a lower vibration energy and deuterium having a larger mass number than protium.…”

Section: Introductionmentioning

confidence: 99%

Isotope Effects on Hydrogen Bonding and CH/CD−π Interaction

et al. 2018

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We study the isotope effect by liquid chromatography (LC) with a variety of separation media under reversed and normal phase conditions using the protiated and/or deuterated compounds as the solutes. Results of reversed phase LC (RPLC) suggested that the protiated compounds were more hydrophobic than that of deuterated compounds due to the isotope effect based on the hydrogen bonding between hydrogen atoms of isotopologues and hydroxy groups in the mobile phase. The importance of the hydrogen bonding was also supported by the separation of isotopologues with a silica stationary phase on normal phase LC (NPLC), where the deuterated compounds showed stronger hydrogen bonding to hydroxy groups on silanol. Additionally, we investigated the difference of the strength between CH−π and CD−π interactions. Comparison of free energies of isotopologues by RPLC suggested that the CH−π interaction was slightly stronger than CD−π interaction. Finally, we demonstrated the separation of a few isotopologues on NPLC using a column coated with C70-fullerene, which is capable of strong π-based interactions, by effective CH/CD−π interactions.

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Section: Introductionmentioning

confidence: 99%

Isotope Effects on Hydrogen Bonding and CH/CD−π Interaction

et al. 2018

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“…These investigations include the triatomic systems H + H2/,2 CI+H 2 ,·,4 Br+H 2 / and I+H 2 6 as well as the more complex reactions CF.+CH 4 /,8 CI+CH 4 ,9,10 and CF.+ H2.1l In each case, a comparison has been made between the experimental kinetic isotope effect and that obtained from theory in the hopes of gaining more knowledge concerning the potential energy surfaces of these reactions. Most of the calculations have been carried out using the absolute rate theory approach.…”

Section: Introductionmentioning

confidence: 99%

ESR Study of the Kinetic Isotope Effect in the Reaction of H and D Atoms with CH4

Kurylo

Hollinden

Timmons

1970

The Journal of Chemical Physics

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Articles you may be interested inCommunication: Full dimensional quantum rate coefficients and kinetic isotope effects from ring polymer molecular dynamics for a seven-atom reaction OH + CH4 → CH3 + H2O Rate coefficients and kinetic isotope effects of the X + CH4 → CH3 + HX (X = H, D, Mu) reactions from ring polymer molecular dynamics J. Chem. Phys. 138, 094307 (2013); 10.1063/1.4793394 Erratum: Kinetic isotope effects in the reaction of fluorine atoms with molecular hydrogen. I. H2/D2 kinetic isotope effect ESR atom detection has been employed to determine the kinetic isotope effect involved in the reactions: H +C~---H2+CH3, D+C~---HD+CH3.(1)(2) New data were obtained for Reaction (1) leading to a slightly revised value for k, of (6.2S±2.00) X 10 '3 exp[ -(11 600±lS0) / RTJ in units of cm 3 mole-l·sec-l . Assuming that the ratio of pre-exponential factors for Reactions (1) and (2) is 1.38 we compute a value for k2 of (4.S±2.0) X 10 13 exp[ -(11100±lS0) / RTJ cm 3 mole-'·sec ' . The observed kinetic isotope effect is compared with those calculated from absolute rate theory using the semiempirical Sato potential energy surface, or that obtained from the empirical bondenergy-bond-order (BEBO) method. These two methods give equally good predictions of the value of k,jk 2 • Application of a one-dimensional tunnel correction results in poorer agreement between theory and experiments.

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“…However, the isotopic- competition method cannot be used and only the comparison of Ho with D2 has been made (33). Surprisingly enough, the theoretical isotope effects (from either LEPS or BEBO surfaces) are in much better agreement with experiment than they were for H2 + Br, partly because the experiments are done at higher temperatures; as the temperature dependence in Eq.…”

Section: Kinetic Isotope Effects: Experiments and Theory Comparedmentioning

confidence: 99%

Transition-State Models and Hydrogen-Isotope Effects

Weston

1967

Science

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The transition-state theory of chemical kinetics, coupled with relatively crude methods of constructing potential-energy surfaces for reacting systems, has great utility in the forecasting of kinetic properties. In particular, it permits prediction of the effect of isotopic substitution on rate constants, and comparison of these predictions with experimental data provides a particularly sensitive test for the combination of potential-energy surface and transition-state theory. More rigorous tests of each of these factors depend on future developments in quantum chemistry, in studies of chemical reactions in molecular beams, and in detailed trajectory calculations of scattering processes.

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Deuterium Kinetic Isotope Effect in the Hydrogen—Iodine Reaction

Cited by 34 publications

References 23 publications

Isotope Effects on Hydrogen Bonding and CH/CD−π Interaction

Isotope Effects on Hydrogen Bonding and CH/CD−π Interaction

ESR Study of the Kinetic Isotope Effect in the Reaction of H and D Atoms with CH4

Transition-State Models and Hydrogen-Isotope Effects

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