Tautomeric equilibria and pKa values for 'sulfurous acid' in aqueous solution: a thermodynamic analysis

1979 ◽  
Vol 57 (4) ◽  
pp. 454-457 ◽  
Author(s):  
J. Peter Guthrie
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Aqueous Solutions ◽  
Equilibrium Constants ◽  
Acid Solutions ◽  
Sulfurous Acid ◽  
Free Energy Of Formation ◽  
Dilute Aqueous Solutions ◽  
Sulfite Ion ◽  
Energy Of Formation

The free energy of formation of dimethyl sulfite in aqueous solution can be calculated as −91.45 ± 0.79 kcal/mol; this calculation required measurement of the solubility of dimethyl sulfite. From this value and the pKa of SO(OH)2, using previously reported methods, the free energy of formation of SO(OH)2 can be calculated to be −129.26 ± 0.89 kcal/mol. Comparison of this value with the value obtained from the free energy of formation of 'sulfurous acid' solutions, calculated from the free energy of formation of sulfite ion and the apparent pKa, values, permits evaluation of the free energy of covalent hydration of SO2 as 1.6 + 1.0 kcal/mol, in agreement with earlier qualitative spectroscopic observations. From the apparent pKa and the anticipated pKa values for the tautomers (SO(OH)2, pK1 = 2.3; HSO2(OH), pK1 = −2.6) it is possible to calculate the free energy change for tautomerization of SO(OH)2 to H—SO2(OH) as +4.5 ± 1.2 kcal/mol. All equilibrium constants required for Scheme 1, describing the species present in dilute aqueous solutions of SO2, have been calculated. In agreement with previous Raman studies the major tautomer of 'bisulfite ion' is calculated to be H—SO3−.

Energetics of acetic acid enol in aqueous solution. A new method for thermodynamic estimation

1993 ◽  
Vol 71 (12) ◽  
pp. 2123-2128 ◽  
Author(s):  
J. Peter Guthrie
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Acetic Acid ◽  
Satisfactory Agreement ◽  
Marcus Theory ◽  
New Method ◽  
Free Energy Of Formation ◽  
Independent Estimate ◽  
Energy Of Formation

A new disproportionation calculation allows the estimation of the free energy of formation of the enol of acetic acid as 65 ± 2 kcal/mol. The value of pKE derived from this free energy, pKE = 21 ± 2, is in satisfactory agreement with information from the literature about rates of exchange. Analysis of the data on rates of exchange of the C-H protons of acetic acid using Marcus theory allows an independent estimate of the enol content. Exchange in acid and in base lead to internally consistent estimates, pKE = 19.3 ± 2.2, which are within the combined uncertainties of the values from the thermodynamic estimate.

The Solubility of Metallic Selenium under Anoxic Conditions

2000 ◽  
Vol 663 ◽  
Author(s):  
Yoshihisa Iida ◽  
Tetsuji Yamaguchi ◽  
Shinichi Nakayama ◽  
Tomoko Nakajima ◽  
Yoshiaki Sakamoto
Keyword(s):  
Free Energy ◽  
Solid Phase ◽  
Equilibrium Constants ◽  
Absorption Spectrometry ◽  
X Ray Diffraction ◽  
Molar Free Energy ◽  
Anoxic Conditions ◽  
X Ray ◽  
Free Energy Of Formation ◽  
Energy Of Formation

ABSTRACTThe solubility of metallic selenium was measured in a mixture of 0.1M-NaCl and 0.05M-N2H4under anoxic conditions (O2 < 1 ppm) by both oversaturation and undersaturation methods. Equilibrium was attained in 40 days. The aqueous selenium species identified were HSe at pH between 5 and 8, and Se42at pH between 10 and 13, by UV-Vis absorption spectrometry. The solid phase was identified as Se (cr) by X-ray diffraction. The equilibrium constants ofSe(cr) + H+ + 2e- = HSe- logK0 = -6.5±0.5 and4Se(cr) + 2e- = Se42- logK0 = -16.8±0.5were determined. The standard molar free energy of formation of HSe- and Se42-was determined to be (37.1±2.9) and (95.9±2.9) kJ/mol, respectively.

The tetrahedral intermediate from the hydration of N-methylformanilide

1993 ◽  
Vol 71 (12) ◽  
pp. 2109-2122 ◽  
Author(s):  
J. Peter Guthrie ◽  
Jonathan Barker ◽  
Patricia A. Cullimore ◽  
Jinqiao Lu ◽  
David C. Pike
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Dimethyl Acetal ◽  
Heat Of Formation ◽  
Basic Solution ◽  
Tetrahedral Intermediate ◽  
Rate Determining Step ◽  
Free Energy Of Formation ◽  
Hydrolysis Of ◽  
Energy Of Formation

Heats of hydrolysis of N-methylformanilide dimethyl acetal have been measured in basic solution. The heat of formation of N-methylformanilide was obtained by determining the equilibrium constant in aqueous solution for its formation from formic acid and N-methylaniline as a function of temperature:[Formula: see text]. These data permit the calculation of the heat of formation of N-methylformanilide dimethyl acetal, [Formula: see text]. The free energy of formation of the tetrahedral intermediate in the hydrolysis of N-methylformanilide was calculated by methods we have previously reported. Consideration of the energetics of the intermediates and the known rates of reaction leads to the conclusion that the rate-determining step for alkaline hydrolysis is cleavage of the C—N bond.

The enol content of simple carbonyl compounds: a thermochemical approach

1979 ◽  
Vol 57 (2) ◽  
pp. 240-248 ◽  
Author(s):  
J. Peter Guthrie ◽  
Patricia A. Cullimore
Keyword(s):  
Aqueous Solution ◽  
Free Energy ◽  
Carbonyl Compounds ◽  
Free Energy Change ◽  
Energy Change ◽  
Free Energies ◽  
Enol Ethers ◽  
Free Energy Of Formation ◽  
Hydrolysis Of ◽  
Energy Of Formation

From the heats of hydrolysis of enol ethers, the heats of formation of the enol ethers, and thence the free energies of formation of the enol ethers in aqueous solution can be calculated. For this calculation it was necessary to determine the free energies of transfer from the gas phase to aqueous solution. By methods previously published it was possible to estimate the free energy change for the hypothetical hydrolysis reaction leading from the enol ether to the enol, which in turn made possible calculation of the free energy of formation of the enol. Finally the free energy change for enolization in aqueous solution could be calculated using the known free energy of formation of the corresponding keto tautomer. In this way the following were determined: carbonyl compound, pKenol = −log ([enol]/[keto]): acetaldehyde, 5.3; propionaldehyde, 3.9; isobutyraldehyde, 2.8; acetone, 7.2; 2-butanone, 8.3; 3-pentanone, 7.8; cyclopentanone, 7.2; cyclohexanone, 5.7; acetophenone, 6.7.

Equilibrium in the formation of barium carbonate from barium sulphate

1976 ◽  
Vol 54 (24) ◽  
pp. 3872-3875
Author(s):  
Harry Horlings ◽  
Donald S. Scott ◽  
John R. Wynnyckyj
Keyword(s):  
Free Energy ◽  
Barium Carbonate ◽  
Equilibrium Constants ◽  
Barium Sulphate ◽  
Heat Of Reaction ◽  
Temperature Range ◽  
Free Energy Of Formation ◽  
Energy Of Formation

Heat of reaction and free energy of formation at 25 °C were determined from experimental equilibrium yields for the reaction[Formula: see text]in an aqueous solution.The values are 5045 and 1927 cal/mol respectively. Equilibrium constants for the reaction were determined over a temperature range from 20 to 193 °C.

The reactions of oligoalcohols with arsenic, arsenous, boric and germanic acids

1980 ◽  
Vol 45 (10) ◽  
pp. 2645-2655 ◽  
Author(s):  
Antonín Mikan ◽  
Miloš Bartušek
Keyword(s):  
Aqueous Solutions ◽  
Equilibrium Constants ◽  
Dilute Aqueous Solutions

The reactions of sorbitol, mannitol, adonitol, dulcitol, glucose and glycerol with H3AsO4, H3AsO3, H3BO3 and GeO2 acids in dilute aqueous solutions were studied by potentiometric neutralization titrations. The formation of the following chelates was demonstrated: As(V)L3-, As(III)L(OH)2-, HAs(III)L(OH)2, BL2-, GeL2(OH)- and GeL32- and the equilibrium constants for their formation were found. Conditions for formation of these chelates of organic oligohydroxy compounds are discussed.

Sign in / Sign up

Export Citation Format

Share Document