The Isotope Effect on Acid-Catalyzed Slow Proton Transfer in Dilute Aqueous Solution

1962 ◽  
Vol 84 (20) ◽  
pp. 3976-3977 ◽  
Author(s):  
A. J. Kresge ◽  
Y. Chiang
Keyword(s):  
Aqueous Solution ◽  
Proton Transfer ◽  
Isotope Effect ◽  
Dilute Aqueous Solution ◽  
Acid Catalyzed

Kinetics of acid-catalyzed hydration in aqueous solution of 1-methoxy- and 1-methylthio-2-phenylethyne and some related acetylenes

1987 ◽  
Vol 65 (2) ◽  
pp. 441-444 ◽  
Author(s):  
N. Banait ◽  
M. Hojatti ◽  
P. Findlay ◽  
A. J. Kresge
Keyword(s):  
Aqueous Solution ◽  
Proton Transfer ◽  
Isotope Effect ◽  
Rate Constants ◽  
Acid Catalysis ◽  
The Other ◽  
Buffer Solutions ◽  
Hydronium Ion ◽  
Acid Catalyzed ◽  
Kinetics Of

The rates of conversion of C6H5C≡COCH3 to C6H5CH2CO2CH3 were measured in dilute HClO4/H2O, DCIO4/D2O, and H3PO4–H2PO2−/H2O buffer solutions, and the rates of conversion of C6H5C≡CSCH3 to C6H5CH2COSCH3, C6H5C≡CH to C6H5COCH3, 2,4,6-(CH3)3C6H2C≡CH to 2,4,6-(CH3)3C6H2COCH3, and p-CH3OC6H4C≡CCH3 to p-CH3OC6H4COCH2CH3 were measured in concentrated HClO4/H2O solutions, all at 25 °C. The reaction of C6H5C≡COCH3 showed general acid catalysis and gave the isotope effect [Formula: see text], which indicates that it proceeds through rate-determining proton transfer from catalyst to substrate. The hydronium ion catalytic coefficient for this reaction is [Formula: see text], and those for the other four, in the order given above, are [Formula: see text], and 8.5 × 10−6 M−1 s−1. Relative reactivities based on these rate constants are discussed.

Ketonization equilibria of phenol in aqueous solution

1999 ◽  
Vol 77 (5-6) ◽  
pp. 605-613 ◽  
Author(s):  
Marco Capponi ◽  
Ivo G Gut ◽  
Bruno Hellrung ◽  
Gaby Persy ◽  
Jakob Wirz
Keyword(s):  
Aqueous Solution ◽  
Proton Transfer ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Flash Photolysis ◽  
Equilibrium Constants ◽  
Thermodynamic Cycle ◽  
Acidity Constant ◽  
Kinetic Isotope ◽  
Carbon Acids

The two keto tautomers of phenol (1), cyclohexa-2,4-dienone (2) and cyclohexa-2,5-dienone (3), were generated by flash photolysis of appropriate precursors in aqueous solution, and the pH-rate profiles of their enolization reactions, 2 –> 1 and 3 –> 1, were measured. The rates of the reverse reactions, 1 –> 2 and 1 –> 3, were determined from the rates of acid-catalyzed hydron exchange at the ortho- and para-positions of 1; the magnitude of the kinetic isotope effect was assessed by comparing the rates of hydrogenation of phenol-2t and -2d. The ratios of the enolization and ketonization rate constants provide the equilibrium constants of enolization, pKE(2, aq, 25°C) = -12.73 ± 0.12 and pKE(3, aq, 25°C) = -10.98 ± 0.15. Combination with the acidity constant of phenol also defines the acidity constants of 2 and 3 through a thermodynamic cycle. These ketones are remarkably strong carbon acids: pKa(2) = -2.89 ± 0.12 and pKa(3) = -1.14 ± 0.15. They disappear by proton transfer to the solvent with lifetimes, τ(2) = 260 μs and τ(3) = 13 ms, that are insensitive to pH in the range from 3-10.Key words: proton transfer, tautomers, flash photolysis, kinetic isotope effect, pH-rate profiles.

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

Acid-catalyzed enolization of acetophenone: catalysis by bisulfate ion in sulfuric acid solutions

1986 ◽  
Vol 64 (6) ◽  
pp. 1224-1227 ◽  
Author(s):  
J. R. Keeffe ◽  
A. J. Kresge ◽  
J. Toullec
Keyword(s):  
Aqueous Solution ◽  
Sulfuric Acid ◽  
Acidity Constant ◽  
Acidity Function ◽  
Acid Solutions ◽  
Dilute Aqueous Solution ◽  
Acid Catalyzed ◽  
The Difference ◽  
Carbon Acid ◽  
Sulfuric Acid Solutions

Rates of acid-catalyzed enolization of acetophenone in dilute aqueous solution, measured under conditions where the solvated proton is the only acidic species present, give a hydrogen ion catalytic coefficient, [Formula: see text], that is 35% smaller than the value obtained by X acidity function extrapolation of measurements made in moderately concentrated sulfuric acid solutions. The difference may be attributed to catalysis by bisulfate ion in the sulfuric acid solutions; this is supported by direct measurement of the bisulfate ion catalytic coefficient in dilute sulfuric acid. This revised value of [Formula: see text] leads to new, but only slightly different, values of the keto–enol equilibrium constant for acetophenone in aqueous solution, pKE = 7.96 ± 0.04, the acidity constant for acetophenone ionizing as a carbon acid, [Formula: see text] and the encounter-controlled rate constant for the reaction of acetophenone enol with molecular bromine, k = (3.2 ± 0.4) × 109 M−1 s−1.

The Secondary Isotope Effect on Proton Transfer from the Hydronium Ion in Aqueous Solution

1964 ◽  
Vol 86 (22) ◽  
pp. 5014-5016 ◽  
Author(s):  
A. J. Kresge ◽  
D. P. Onwood
Keyword(s):  
Aqueous Solution ◽  
Proton Transfer ◽  
Isotope Effect ◽  
Hydronium Ion

Ethanol recovery from dilute aqueous solution by perstraction using supported ionic liquid membrane (SILM)

2021 ◽  
Vol 298 ◽  
pp. 126811
Author(s):  
Ting-Yi Huang ◽  
Jia Shin Ho ◽  
Shuwen Goh ◽  
Tzyy Haur Chong
Keyword(s):  
Aqueous Solution ◽  
Ionic Liquid ◽  
Liquid Membrane ◽  
Supported Ionic Liquid ◽  
Dilute Aqueous Solution ◽  
Ethanol Recovery

scholarly journals Freeze concentration of dilute aqueous solution

1968 ◽  
Vol 17 (3) ◽  
pp. 354-355 ◽  
Author(s):  
Atsushi MIZUIKE ◽  
Shigeki KANO
Keyword(s):  
Aqueous Solution ◽  
Freeze Concentration ◽  
Dilute Aqueous Solution
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