Solvent effects of water and fluorosulfuric acid on proton transfer equilibriums and the energies of solvation of gaseous onium ions

Taft, Robert W.; Wolf, J. Frederick; Beauchamp, J. L.; Scorrano, Gianfranco; Arnett, Edward M.

doi:10.1021/ja00472a035

Cited by 79 publications

(89 citation statements)

References 3 publications

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“…The thermochemical data resulting from the plots, AH0,-,,,, AGO,-,,,, and AS0 ,-,, , are shown in Table 1. A second set of experiments involved the measurement of equilibria [8] which involve proton and hydrate transfer.…”

Section: Resultsmentioning

confidence: 99%

“…The van't Hoff plots for the equilibrium constants of reaction [8] for Ro = CH, and R = C2H5 and n = 0 to 3 are shown in Fig. 2.…”

Section: Resultsmentioning

confidence: 99%

“…The corresponding AGO, AH0, and AS0 values are given in Table 1. Unfortunately equilibria [8] for Ro = C2H5 and R = CF,CH, could not be measured directly because of the large difference between the proton affinities of ethyl and trifluoroethyl amine.…”

Section: Resultsmentioning

confidence: 99%

“…The van't Hoff plots for reaction [8], Fig. 2, illustrate in a very graphic manner the attenuating effect of the aqueous medium on the proton transfer between methyl and ethyl amine.…”

Section: Resultsmentioning

confidence: 99%

“…Typical gas mixtures were 0.1 mTom RNH,, 0.02-2 Tom H20, third gas CH, at -4 Tom. The proton and hydrate transfer equilibria (see reaction [8] and section on Results and Discussion) were measured with known mixtures of the two amines CH3NH2 and C,H,NH,. The ratio methyl to ethyl amine was large in order to keep the methyl and ethylammonium intensities of similar magnitude.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen bonding solvent effect on the basicity of primary amines CH₃NH₂, C₂H₅NH₂, and CF₃CH₂NH₂

Lau¹,

Kebarle²

1981

Can. J. Chem.

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Can. J. Chem. 59,151 (1981).The equilibria RNH,+(H,O),-, + H 2 0 = RNH,+(H2O), were measured for R = CH,, C2H,, and CF3CH2 from n = 1 ton = 3 with a pulsed electron beam high Ion source pressure mass spectrometer. The proton and hydrate transfer equilibria CH,NH,+(H,OX, + C2H,NH, = CH,NH2 + C,H,NH,+(H,OX, were measured for n = 0 ton = 3. These dataallow the evaluationof AH0 and AGO for the reactions: RoNH3+(H20X, + RNH3+ = RoNH3+ + RNH,+(H,OX,. AH0 = GAHoO,,(RNH,+), AG = 8AGoo,,(RNH3+). Thesedataare compared withGAE,, (STO-3G) evaluated by Hehre and Taft. Ingeneral good agreement is observed at n = 3. The GAHo0,,(RNH3+) c GAE0,,(RNH3+) are also found close to the ion hydration free energy difference in aqueous solutions.

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Section: Resultsmentioning

confidence: 99%

“…The van't Hoff plots for the equilibrium constants of reaction [8] for Ro = CH, and R = C2H5 and n = 0 to 3 are shown in Fig. 2.…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…The van't Hoff plots for reaction [8], Fig. 2, illustrate in a very graphic manner the attenuating effect of the aqueous medium on the proton transfer between methyl and ethyl amine.…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Hydrogen bonding solvent effect on the basicity of primary amines CH₃NH₂, C₂H₅NH₂, and CF₃CH₂NH₂

Lau¹,

Kebarle²

1981

Can. J. Chem.

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Basicity and solvent effects on hydrogen bonding in NR3��HCOOH (R=H, CH3) model systems

Pérez

Zapata‐Torres

Parra-Mouchet

et al. 1999

Int. J. Quant. Chem.

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The effect of the basicity of methyl-amines on hydrogen bonding (HB) with HCOOH is examined in both gas and solution phases. In the gas phase, the strength of HB may be related to the proton affinity (PA) difference between the carboxylate anion and the methyl-amine, ?PA = PA(HCOO-) -PA(NR3). The changes in the driving potential ?PA are explained on the basis of electronic substituent effects. The electronic substituent effects are rationalized in terms of local reactivity indices such as the Fukui function and the local hardness and softness at the basic center. A simple model is then proposed to explain the enhancement HB in the solution phase. The HB pattern in the solution phase is changed by electrostatic and nonelectrostatic solvation of the zwitterionic and neutral species in equilibrium.

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Steric Effects on the Proton-Transfer Equilibria of Ketones, Sulfoxides, and Phenols

et al. 1999

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The proton‐transfer equilibrium of several bases and acids, including some sterically hindered ketones, sulfoxides, and phenols, has been investigated by means of the determination of the thermodynamics of the equilibrium, NMR 13C relaxation measurements, and quantum chemical calculations. The analysis of such data yields information about the steric effects on basicity or acidity and about the underlying reasons for the anomalous behavior of species having a sterically hindered basic or acidic site. Thus, it is demonstrated that the anomalously low basicity of two sterically hindered ketones (tBu2CO and PhCOtBu) is enthalpic in origin and stems from steric hindrance to the solvation of their protonated forms. No such effect is found for analogous sulfoxides, whereas phenols display a more complex behavior.

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Solvent effects of water and fluorosulfuric acid on proton transfer equilibriums and the energies of solvation of gaseous onium ions

Cited by 79 publications

References 3 publications

Hydrogen bonding solvent effect on the basicity of primary amines CH₃NH₂, C₂H₅NH₂, and CF₃CH₂NH₂

Hydrogen bonding solvent effect on the basicity of primary amines CH₃NH₂, C₂H₅NH₂, and CF₃CH₂NH₂

Basicity and solvent effects on hydrogen bonding in NR3��HCOOH (R=H, CH3) model systems

Steric Effects on the Proton-Transfer Equilibria of Ketones, Sulfoxides, and Phenols

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Solvent effects of water and fluorosulfuric acid on proton transfer equilibriums and the energies of solvation of gaseous onium ions

Cited by 79 publications

References 3 publications

Hydrogen bonding solvent effect on the basicity of primary amines CH3NH2, C2H5NH2, and CF3CH2NH2

Hydrogen bonding solvent effect on the basicity of primary amines CH3NH2, C2H5NH2, and CF3CH2NH2

Basicity and solvent effects on hydrogen bonding in NR3���HCOOH (R=H, CH3) model systems

Steric Effects on the Proton-Transfer Equilibria of Ketones, Sulfoxides, and Phenols

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Hydrogen bonding solvent effect on the basicity of primary amines CH₃NH₂, C₂H₅NH₂, and CF₃CH₂NH₂

Hydrogen bonding solvent effect on the basicity of primary amines CH₃NH₂, C₂H₅NH₂, and CF₃CH₂NH₂

Basicity and solvent effects on hydrogen bonding in NR3��HCOOH (R=H, CH3) model systems