Evaluation of the basic ionization constants of water and alcohols from their ionization potentials

Inductive Effects on Molecular Ionization Potentials. V. Hydrogen Sulfide and Aliphatic Thioethers

“…The same effect manifests itself in a greater basicity, the greater is the electron density at the S-atom of the sulfide nolecule. This effect is similar to that recently denonstrated for alcohols [4]. It isinteresting that we are able to include hydrogen sulf'ide as the siJrplest thioether in the series.…”

“…The entire chemistry of thioethers, in fact, is dependent on the behavior of the 3p sulfur lone pair electrons. Electron-releasing alkyl groups bonded to the S-atom of an alkyl sulfide nolecule facilitates electron renoval, and thereby lowers the Er; the presence of electron-withdrawing groups should likewise cause an increase in the ionization energy [4]. The same effect manifests itself in a greater basicity, the greater is the electron density at the S-atom of the sulfide nolecule.…”

Electropolymerization of Pyrrole and Electrochemical Study of Polypyrrole. 2. Influence of Acidity on the Formation of Polypyrrole and the Multipathway Mechanism

“…Results and conclusions obtained under different conditions are hardly comparable. Nevertheless, with regard to the effect of protons in both aqueous and acetonitrile solution, we should bear in mind that water as a solvent provides a very good protonphilic environment from the viewpoints of both its quantity and its basicity (p K a = −3.43) . Although the acid-catalyzed trimerization and polymerization proceed via pyrrole protonation in strongly acidic aqueous solutions, − dilute solutions of pyrrole in aqueous sulfuric acid are rather stable 36c.…”

Linear free energy correlations in mass spectrometry

“…A number of early studies reported that the ionization energies of alkanethiols, 27 alkyl alcohols, 28 alkyl halides 29 and alkylamines 30 were linear functions of the inductive substituent constant I for the alkyl group as evaluated by Taft and Lewis. 31 More recent evaluations 4,7,9 of inductive substituent constants concluded that I for alkyl groups are essentially zero.…”