Isotope effect and

Stabilization of a carbocation intermediate by benzylic conjugation, as in the 1-phenylethyl system shown in entry 8, leads to substitution with diminished stereosped-ficity. A thorough analysis of stereochemical, kinetic, and isotope effect data on solvolysis reactions of 1-phenylethyl chloride has been carried out. The system has been analyzed in terms of the fate of the intimate ion-pair and solvent-separated ion-pair intermediates. From this analysis, it has been estimated that for every 100 molecules of 1-phenylethyl chloride that undergo ionization to an intimate ion pair (in trifluoroethanol), 80 return to starting material of retained configuration, 7 return to inverted starting material, and 13 go on to the solvent-separated ion pair. 

Here Tq are coordinates in a reference volume Vq and r = potential energy of Ar crystals has been computed [288] as well as lattice constants, thermal expansion coefficients, and isotope effects in other Lennard-Jones solids. In Fig. 4 we show the kinetic and potential energy of an Ar crystal in the canonical ensemble versus temperature for different values of P we note that in the classical hmit (P = 1) the low temperature specific heat does not decrease to zero however, with increasing P values the quantum limit is approached. In Fig. 5 the isotope effect on the lattice constant (at / = 0) in a Lennard-Jones system with parameters suitable for Ne atoms is presented, and a comparison with experimental data is made. Please note that in a classical system no isotope effect can be observed, x "" and the deviations between simulations and experiments are mainly caused by non-optimized potential parameters. 

A positive iodinating species was postulated to account for the kinetics and isotope effect observed in the iodination of some amines by iodine in aqueous potassium iodide (in some cases in the presence of acetate, lactate, or phosphate ion). The isotope effects (kH/kD values in parenthesis) for these compounds studied were 2,4,6-trideutero-m-dimethylaminobenzenesulphonate ion, 25 °C (1.0) 2,4,6-trideutero-m-dimethyIbenzoate ion, 30 °C (1.4) 2,4,6-trideutero-dimethylaniline, 30 °C, lactate (3.0) 2,4,6-trideuteromethylaniline, 25 °C, acetate (3.2) 2,4,6-trideuteroaniline, 25 °C (3.5), phosphate (4.0) 2,4,6-trideutero-metanilate ion, 35 °C (2.0) 2,4,6-trideutero-m-aminobenzoate ion, 30 °C (4.8), phosphate (3.0) 2,6-dideutero-l-dimethylaminobenzene-4-sulphonate ion, 25 °C, phosphate (1.0) 4-deutero-l-dimethylaminobenzene-3-sulphonate ion, 25 °C, phosphate (1.0). The kinetics of these reactions was given by... 

Rare-Gas-Hydrogen Reactions. Ion-molecule reactions in the rare gas-hydrogen system are of great interest both theoretically and experimentally. The properties of the reactants and products are well known or may be calculated, and the properties of the intermediate three-body complex pose a tractable theoretical problem. Systematic studies of cross-section energy dependence and isotope effects in these systems have been undertaken by Friedman and co-workers (29, 47, 49, 67), by Koski and co-workers (2, 3), and by Giese and Maier (15, 16). 

The hydrogen molecule does not chemisorb onto clean sintered gold surfaces at or above 78 K [147] but on unsintered films, a small amount of H2 is chemisorbed if gold surface atoms of low coordination number are present [148]. Stobinski [149] found that H2 can also chemisorb on thin sintered Au films if the surface is covered at low temperatures with a small amount of gold equivalent to 1-3 Au monolayers prior to H2 exposure. This suggests a fundamental role of surface Au atoms of low coordination number in the chemisorption process. Deuterium molecules also chemisorb in a similar fashion on gold films at 78 K and isotope effects were... 

Giitlich et al. [4, 6] have studied SCO in solid [Fe(2-pic)3]Cl2-EtOH (2-pic = 2-picolylamine), particularly the influence of dilution with Zn and Co, the nature of noncoordinated anions and crystal solvent, the HID and isotope effect,... 

The reaction proceeds via a cyclic TS involving coordination of both the alcohol and ketone oxygens to the aluminum. Computational (DFT) and isotope effect studies are consistent with the cyclic mechanism.190 Hydride donation usually takes place from... 

Kinetics and isotope effects are consistent with this mechanism.92 The reagent is electrophilic in character and reaction is facilitated by ERG substituents in the alkene. A B3LYP/6-31G computation found the transition structures and Ea values shown in... 

Goldstein, E., Beno, B., Houk, K. N., 1996, Density Functional Theory Prediction of the Relative Energies and Isotope Effects for the Concerted and Stepwise Mechanism of the Diels-Alder Reaction of Butadiene and Ethylene , J. Am. Chem. Soc., 118, 6036. 

Sokolov, N. D., Savel ev, V. A., 1977, Dynamics of the Hydrogen Bond Two-Dimensional Model and Isotopic Effects , Chem. Phys., 22, 383. 

Al-Soufi W, Grellmann KH, Nickel B (1991) Keto-enol tautomerization of 2-(2 -hydroxy-phenyl)benzoxazole and 2-(2 -hydroxy-4 -methylphenyl) benzoxazole in the triplet state hydrogen tunneling and isotope effects. 1. Transient absorption kinetics. J Phys Chem 95 10503-10509... 

Fig. 12 Sodium complexed perepoxides III and IY and isotope effect negating zwitterion V as an intrazeolite intermediate.

Rate and equilibrium constant data, including substituent and isotope effects, for the reaction of [Pt(bpy)2]2+ with hydroxide, are all consistent with, and interpreted in terms of, reversible addition of the hydroxide to the coordinated 2,2 -bipyridyl (397). Equilibrium constants for addition of hydroxide to a series of platinum(II)-diimine cations [Pt(diimine)2]2+, the diimines being 2,2 -bipyridyl, 2,2 -bipyrazine, 3,3 -bipyridazine, and 2,2 -bipyrimidine, suggest that hydroxide adds at the 6 position of the coordinated ligand (398). Support for this covalent hydration mechanism for hydroxide attack at coordinated diimines comes from crystal structure determinations of binuclear mixed valence copper(I)/copper(II) complexes of 2-hydroxylated 1,10-phenanthroline and 2,2 -bipyridyl (399). 

Spence MJ, Bottrell SH, Thornton SI, Richnow HH, Spence KH (2005) Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer. J Con... 

DePaolo, D. J. (1981). Trace-element and isotopic effects of combined wallrock assimilation and fractional crystallization. Earth Planet. Sci. Letters, 53, 189-202. 

Statistical Mechanics of Ideal Gases and Isotope Effects 4.5.1 General Remarks... 

Evaluation of Partition Functions, q, and Isotope Effects on Partition Functions, qheavy/qiight for Ideal Gases... 

Abstract Isotope effects on the PVT properties of non-ideal gases and isotope effects on condensed phase physical properties such as vapor pressure, molar volume, heats of vaporization or solution, solubility, etc., are treated in some thermodynamic detail. Both pure component and mixture properties are considered. Numerous examples of condensed phase isotope effects are employed to illustrate theoretical and practical points of interest. 

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