Deuterium solvent isotope effect on the basicity of methanol. Deuterium fractionation factor for CH3OL2+ in aqueous solution

1986 ◽  
Vol 90 (4) ◽  
pp. 543-545 ◽  
Author(s):  
Joseph L. Kurz ◽  
Stanley L. Hazen ◽  
Linda C. Kurz
Keyword(s):  
Aqueous Solution ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Fractionation Factor ◽  
Solvent Isotope

The solvent deuterium isotope effect on the hydroxide-ion-catalyzed conversion of acetaldehyde to its enolate ion

1988 ◽  
Vol 66 (9) ◽  
pp. 2440-2442
Author(s):  
J. R. Keeffe ◽  
A. J. Kresge
Keyword(s):  
Water Molecule ◽  
Proton Transfer ◽  
Isotope Effect ◽  
Deuterium Isotope Effect ◽  
Solvent Isotope Effect ◽  
Fractionation Factor ◽  
Hydroxide Ion ◽  
Solvent Isotope

Rates of proton transfer from acetaldehyde to the hydroxide ion were measured by iodine scavenging in H2O and in D2O solution at 25 °C; the results give the solvent isotope effect [Formula: see text]. This value is somewhat more consistent with an estimate, made using fractionation factor theory, for hydron transfer directly from the substrate to the hydroxide ion than with another estimate, made similarly, for hydron transfer through an intervening water molecule.

Solvent isotope effect on orientational correlation times of the nitrate ion in dilute aqueous solution

1990 ◽  
Vol 94 (16) ◽  
pp. 6179-6183 ◽  
Author(s):  
M. Nakahara ◽  
A. Adachi ◽  
H. Kiyoyama ◽  
A. Shimizu ◽  
Y. Taniguchi ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Correlation Times ◽  
Nitrate Ion ◽  
Dilute Aqueous Solution ◽  
Solvent Isotope ◽  
Orientational Correlation

Solvent and substrate isotope effects on the enolization and carbon-acid ionization of isobutyrophenone

1996 ◽  
Vol 74 (12) ◽  
pp. 2481-2486 ◽  
Author(s):  
J.R. Keeffe ◽  
A.J. Kresge
Keyword(s):  
Isotope Effect ◽  
Isotope Effects ◽  
Isotopic Fractionation ◽  
Medium Effect ◽  
Solvent Isotope Effect ◽  
Fractionation Factor ◽  
Solvent Isotope ◽  
Carbon Acid ◽  
Fractionation Factors ◽  
Acid Ionization

Bromine scavenging was used to measure rates of acid-catalyzed enolization of isobutyrophenone in H2O and in D2O solution and of isobutyrophenone-α-d in D2O solution. The results provide the solvent isotope effect kH +/kD + = 0.56 and the substrate isotope effect kH/kD = 6.2 on the enolization reaction, both of which are consistent with the generally accepted mechanism for this process. The present results in combination with literature information also provide the solvent isotope effect on the enolization equilibrium, KE(H2O)/KE(D2O) = 0.92, and the solvent isotope effect on the ionization of isobutyrophenone as a carbon acid, kaK(H2O)/kaK(D2O) = 5.4, as well as the product of isotopic fractionation factor and medium effect, [Formula: see text], for isobutyrophenone enol and the medium effect, Φ = 0.47, for its enolate ion. The isotope effect on KE is the first ever determined for the keto–enol equilibrium of a simple aldehyde or ketone; its near-unit value is consistent with expectation on the basis of fractionation factors for the species involved. Key words: isobutyrophenone, keto–enol equilibrium, carbon-acid ionization, solvent isotope effects, isotopic fractionation factors.

Solvent isotope effect on the hydroxide-ion-catalyzed hydration of ketenes in aqueous solution

1999 ◽  
Vol 77 (4) ◽  
pp. 459-462
Author(s):  
J. Andraos ◽  
Y. Chiang ◽  
S.J. Eustace ◽  
A.J. Kresge ◽  
S.W. Paine ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Hydroxide Ion ◽  
Solvent Isotope

Medium isotope effect for isobutyrophenone in aqueous solution. Solvent isotope effects on carbonyl group hydration

1989 ◽  
Vol 67 (5) ◽  
pp. 792-793 ◽  
Author(s):  
J. R. Keeffe ◽  
A. J. Kresge
Keyword(s):  
Isotope Effect ◽  
Deuterium Oxide ◽  
Isotope Effects ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Solvent Isotope Effect ◽  
Fractionation Factor ◽  
Solvent Isotope ◽  
Solvent Isotope Effects ◽  
Fractionation Factors

A medium solvent isotope effect of Φ = 0.827 ± 0.013 was determined for transfer of isobutyrophenone from H2O to D2O. This result, in conjunction with the average solvent isotope effect on hydration of a number of carbonyl compounds, leads to [Formula: see text] as the fractionation factor for the hydroxyl group hydrogens of the hydration reactions' gem-diol products, which is consistent with the expectation that fractionation factors for uncharged hydroxyl groups should be unity. Keywords: isobutyrophenone, fractionation factors, solvent isotope effects, deuterium oxide.

Kinetic solvent isotope effect studies on the methanolysis of 1-phenylethyl chlorides

1993 ◽  
Vol 6 (6) ◽  
pp. 361-366 ◽  
Author(s):  
Ikchoon Lee ◽  
Won Heui Lee ◽  
Hai Whang Lee
Keyword(s):  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Solvent Isotope

Neutral Solvolysis of Acyl Carbon and the Temperature Dependence of the Kinetic Solvent Isotope Effect

1975 ◽  
Vol 53 (6) ◽  
pp. 869-877 ◽  
Author(s):  
B. Rossall ◽  
R. E. Robertson
Keyword(s):  
Temperature Dependence ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Acyl Carbon ◽  
Rate Of Hydrolysis ◽  
Solvent Isotope ◽  
Neutral Conditions ◽  
Hydrolysis Of

The temperature dependence of the rate of hydrolysis of benzoic, phthalic, and succinic anhydrides have been determined in H2O and D2O under "neutral" conditions. Corresponding data have been obtained for methyl trifluoroacetate. While both series supposedly react by the same BAc2 mechanism, remarkable differences are made obvious by this investigation. Possible sources of such differences are proposed.

Proton-coupled electron transfer between [Ru(bpy)2(py)OH2]2+ and [Ru(bpy)2(py)O]2+. A solvent isotope effect (kH2O/kD2O) of 16.1

1981 ◽  
Vol 103 (10) ◽  
pp. 2897-2899 ◽  
Author(s):  
Robert A. Binstead ◽  
Bruce A. Moyer ◽  
George J. Samuels ◽  
Thomas J. Meyer
Keyword(s):  
Electron Transfer ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Proton Coupled Electron Transfer ◽  
Solvent Isotope

An Unusual Solvent Isotope Effect in the Reaction of W(CO)5(solv) (solv = Cyclohexane or Cyclohexane-d12) with THF

2000 ◽  
Vol 19 (9) ◽  
pp. 1682-1691 ◽  
Author(s):  
Riki Paur-Afshari ◽  
J. Lin ◽  
Richard H. Schultz
Keyword(s):  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Solvent Isotope
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