Why are organic acids stronger acids than organic alcohols?

Siggel, M. R. F.; Thomas, T. D.

doi:10.1021/ja00275a022

Cited by 87 publications

(55 citation statements)

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“…In particular, we have shown that the added acid strength of benzoic acid over phenol is attributable to initial-state effects rather than final-state charge delocalization. This conclusion serves to extend recent findings (9). W e have also exploited existing proton affinity -binding energy correlations to extract PA values for the acids under study.…”

Section: Discussionsupporting

confidence: 73%

“…Note that if we had started with the conclusions of Siggel and Thomas (9), which they supported with quantum mechanical calculations, a very good value for the acidity of benzoic acid could have been obtained from our binding energy. This shows the usefulness of core binding energies in deriving gas phase acidities.…”

Section: Core Binding Energies and Gas Phase Aciditiessupporting

confidence: 59%

“…Cumming and Kebarle (17) reported a AH: of 349.8 kcal/mol. Recently Siggel and Thomas (9) established that, in contradiction to the commonly held notion that the stronger acidity of organic acids compared to alcohols is due to resonance stabilization of the anion of the acid, the difference in acidities is caused largely by the initial-state charge distribution, which leads to a less attractive potential at the proton in acids than in alcohols. Using eqs.…”

Section: Core Binding Energies and Gas Phase Aciditiesmentioning

confidence: 95%

“…The contributions to these two quantities can be broken down into a ground-state effect (which includes inductive contributions) and a final-state relaxation effect dependent on the polarizability of the surrounding molecule. Previous studies (8,9) have established the following relationships:…”

Section: Introductionmentioning

confidence: 99%

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The core binding energies of some gaseous aromatic carboxylic acids and their relationship to profon affinities and gas phase acidities

McQuaide¹,

Banna²

1988

Can. J. Chem.

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The C 1s and O 1s core binding energies of gaseous benzoic, phthalic, isophthalic, and terephthalic acids have been measured by X-ray photoelectron spectroscopy. The π-donor relaxation energies associated with the carbonyl oxygen ionization in these systems have been found to be around 2 eV, close to the value for acetic acid. Comparison of the O 1s binding energies in phenol and benzoic acid with the gas phase acidities shows that the increased acidity of benzoic acid is attributable mostly to initial-state inductive effects. A number of O 1s – proton affinity correlations have been used to predict proton affinities for these acids. It is found that benzoic acid is the strongest base and the weakest acid.

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Section: Discussionsupporting

confidence: 73%

Section: Core Binding Energies and Gas Phase Aciditiessupporting

confidence: 59%

Section: Core Binding Energies and Gas Phase Aciditiesmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

The core binding energies of some gaseous aromatic carboxylic acids and their relationship to profon affinities and gas phase acidities

McQuaide¹,

Banna²

1988

Can. J. Chem.

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“…More specifically, it was claimed that the acidity is determined by the ground state potential exerted on the proton in AH, to be donated in the deprotonation process. [25] It is likely that the potential in AH mentioned above is to some extent related to IP Koop 1 in A À , but the latter is a property of the final state as far as the acidity is concerned and not to the initial state of the acid. Analogously, the corresponding values for the series HCOO À , CH 3 COO À , FCOO À , and CF 3 COO À are À 46.6 (À 52.4), À 43.1 (À 54.2), À 63.8 (À 83.8), and À 66.1 (À 91.0), respectively, in kcal mol À1 units, which concurs with the conclusion that the final state has a decisive influence.…”

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confidence: 99%

Anionic versus Neutral Protonation—An Ab Initio Analysis with a Triadic Formula

Maksić

Vianello

2002

ChemPhysChem

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Origins of relative acidity: First and second period hydrides

Laidig

Streitwieser

1996

J. Comput. Chem.

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The origins of the trends of relatively acidity across and between the first and second period hydrides (BH3, CH4, NH3, H2O, HF, AIH3, SiH4, PH3, H2S, and HCl) were investigated using molecular and subsystem quantum mechanics at the Hartree‐Fock (HF)/6–31 + + G **//HF/6–31 + + G ** level of theory. The total deprotonation energies, Δ Eacid, are interpreted in terms of three component processes: Δ E1; deprotonation without electronic and nuclear relaxation; Δ E2, electronic relaxation within the acid geometry; and Δ E3, nuclear relaxation. Δ E1 is given from the electrostatic potential at the acidic proton, Δ E3 + Δ E2 (= Δ E *) is given from the calculated energy of the conjugate anion at the acid geometry. The increased acidity across a given period is shown to be already mostly an inherent property of the acid. © 1996 by John Wiley & Sons, Inc.

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Why are organic acids stronger acids than organic alcohols?

Cited by 87 publications

References 0 publications

The core binding energies of some gaseous aromatic carboxylic acids and their relationship to profon affinities and gas phase acidities

The core binding energies of some gaseous aromatic carboxylic acids and their relationship to profon affinities and gas phase acidities

Anionic versus Neutral Protonation—An Ab Initio Analysis with a Triadic Formula

Origins of relative acidity: First and second period hydrides

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