Dissociation of Hydroxamic Acids: Solvent Effects

1993 ◽  
Vol 58 (5) ◽  
pp. 1109-1121 ◽  
Author(s):  
Otto Exner ◽  
Martin Hradil ◽  
Jiří Mollin
Keyword(s):  
Ionic Strength ◽  
Solvent Effects ◽  
Dissociation Constants ◽  
Mixed Solvents ◽  
Hydroxamic Acids ◽  
Polar Solvents ◽  
Benzohydroxamic Acid ◽  
Methyl Cellosolve ◽  
Methyl Derivatives

The dissociation constants of benzohydroxamic, 4-chlorobenzohydroxamic, and 4-nitrobenzohydroxamic acids, and their N-methyl and O-methyl derivatives, were measured spectrophotometrically or potentiometrically in mixtures of 2-propanol and water. The results were extrapolated to zero ionic strength. The ratio of dissociation constants of the N-methyl and O-methyl derivatives can be taken to represent - with some approximation - the ratio of NH and OH acidities of the parent acid. This ratio increases with substitution by electron-attracting substituents, and decreases with solvent permittivity: some irregularities might be attributable to the effects of mixed solvents, It follows that 4-nitrobenzohydroxamic acid behaves essentially as N-acid in all solvents, 4-chlorobenzohydroxamic acid only in 90% 2-propanol or 80% methyl cellosolve. In benzohydroxamic acid the NH and OH acidities are comparable, the latter prevails slightly in water, the former in less polar solvents. Some apparent discrepancies in the literature can be explained in the same terms, only a few results have not yet been explained.

Extraction of hafnium by means of some substituted 1-phenyl-3-methyl-4-benzoyl-pyrazol-5-ones

1981 ◽  
Vol 46 (8) ◽  
pp. 1901-1905 ◽  
Author(s):  
Oldřich Navrátil ◽  
Jiří Smola
Keyword(s):  
Ionic Strength ◽  
Aqueous Phase ◽  
Dissociation Constants ◽  
Parent Substance ◽  
Benzoyl Group ◽  
Extraction Constants ◽  
Extraction Parameters ◽  
Substituted 1

Distribution between aqueous phase and benzene or chloroform was studied for 1-phenyl-3-methyl-4-benzoylpyrazol-5-ones with 2-chloro, 4-methoxy, 3-nitro, and 4-nitro substitution in the benzoyl group (ionic strength of the aqueous phase 0.1) and for hafnium in their presence (ionic strength 2.0). The distribution and dissociation constants of the reagents and the extraction constants of their hafnium complexes were determined. Hafnium was found to be extracted as the HfA4 species. The extraction parameters of the derivatives in question do not differ substantially from those of the parent substance.

scholarly journals Potentiometric and spectrophotometric studies of the complexation of Schiff-base hydrazones containing the pyrimidine moiety

2003 ◽  
Vol 68 (10) ◽  
pp. 729-749 ◽  
Author(s):  
H.S. Seleem ◽  
B.A. El-Shetary ◽  
S.M.E. Khalil ◽  
M. Shebl
Keyword(s):  
Schiff Base ◽  
Ionic Strength ◽  
Thermodynamic Parameters ◽  
Stability Constants ◽  
Elemental Analysis ◽  
Mass Spectra ◽  
Dissociation Constants ◽  
The Stability ◽  
Pyrimidine Moiety ◽  
Metal Ligand

Three Schiff-base hydrazones (ONN ? donors) were prepared by condensation of 2-amino-4-hydrazino-6-methylpyrimidine with 2-hydroxyacetophenone 2-methoxybenzaldehyde and diacetyl to yield 2-OHAHP, 2-OMeBHPand DHP respectively. The structures of these ligands were elucidated by elemental analysis, UV, IR, 1H-NMR and mass spectra. The metal?ligand stability constants of Mn2+, Fe3+,Co2+,Ni2+,Cu2+, Zn2+,Cd2+,UO22+ and Th4+ chelates were determined potentiometrically in two different media (75%(v/v) dioxane?water and ethanol?water) at 283, 293, 303 and 313 K at an ionic strength of 0.05 M (KNO3). The thermodynamic parameters of the 1:1 and 1:2 complexes were evaluated and are discussed. The dissociation constants of 2-OHAHP, 2-OMeBHP and DHPligands and the stability constants of Co2+, Ni2 and Cu2+ with 2-OHAHP were determined spectrophotometrically in 75 % (v/v) dioxane?water.

The comparative chemistry of ammine and methylamine complexes of rhodium(III) and cobalt(III)

1977 ◽  
Vol 55 (17) ◽  
pp. 3166-3171 ◽  
Author(s):  
Thomas Wilson Swaddle
Keyword(s):  
Ionic Strength ◽  
Spectral Data ◽  
Electron Donor ◽  
Dissociation Constants ◽  
Base Hydrolysis ◽  
Acid Dissociation ◽  
Rate Coefficients ◽  
Acid Dissociation Constants ◽  
First Order ◽  
Kinetics Of

For the aquation of (CH3NH2)5RhCl2+, the first order rate coefficients are represented by ΔHaq* = 101.9 kJ mol−1 and ΔSaq* = −50.2 JK−1 mol−1 in 0.1 M HClO4, while for base hydrolysis the rate is first order in [(CH3NH2)5RhCl2+] and [OH−] at ionic strength 0.10 M and the rate coefficients (in M−1 s−1) are represented by ΔHOH*> = 108.6 kJ mol−1 and ΔSOH* = 74.1 J K−1 mol−1. Acid dissociation constants are reported for (RNH2)5MOH23+ (R = H or CH3; M = Rh or Co), and these, combined with spectral data, show CH3NH2 to be a poorer electron donor than NH3 in complexes of this type, contrary to expectations. The comparative kinetics of reactions of (RNH2)5MCl2+ support the assignment of an Ia mechanism to aquation when M = Rh or Cr, Id to aquation when M = Co, and Dcb for base hydrolysis in all these cases.

Determination of Co(II) and Ni(II)-humate stability constants at high ionic strength NaCl solutions

2000 ◽  
Vol 88 (9-11) ◽  
Author(s):  
D.N. Kurk ◽  
Gregory R. Choppin
Keyword(s):  
Humic Acid ◽  
Ionic Strength ◽  
Solvent Extraction ◽  
Potentiometric Titration ◽  
Stability Constants ◽  
Dissociation Constants ◽  
High Ionic Strength ◽  
Extraction Technique ◽  
Solvent Extraction Technique

Complexation of Ni(II) and Co(II) by unfractionated humic acid (HA) was measured in 0.3 to 5.0 m NaCl solutions at pH 6 and 20 °C, using a solvent extraction technique. The dissociation constants and capacities of the humic acid were investigated in 0.1 to 5.0 m NaCl solutions at 25 °C using potentiometric titration methods.

Determination of dissociation constants of p-hydroxybenzophenone in aqueous organic mixtures – Solvent effects

2008 ◽  
Vol 86 (5) ◽  
pp. 462-469 ◽  
Author(s):  
M I Sancho ◽  
A H Jubert ◽  
S E Blanco ◽  
F H Ferretti ◽  
E A Castro
Keyword(s):  
Solvent Effects ◽  
Dissociation Constants ◽  
Reaction Medium ◽  
Reversed Phase ◽  
Glass Electrode ◽  
Molecular Structures ◽  
Acid Dissociation ◽  
Acidity Constant ◽  
Pka Values ◽  
Solvent Water

The apparent acidity constant of p-hydroxybenzophenone, which is a practically insoluble drug in water but of great pharmaceutical interest, was determined by reversed-phase high-performance liquid chromatography in organic solvent – water mixtures (acetonitrile–water, ethanol–water, and methanol–water), varying the reaction medium permittivity in the interval 56 to 70, at constant ionic strength (0.050) and temperature (30 °C). A combined glass electrode calibrated with aqueous standard buffers was used to obtain pH readings based on the concentration scale (swpH). The pKa values from chromatographic data were obtained using the Hardcastle–Jano equation. Moreover, excellent linear relationships between the pKa values and solvation properties of the reaction medium (relative permittivity and Acity) were used to derive acid dissociation constants in aqueous solution. It has been concluded that the pKa values extrapolated from such solvent–water mixtures are consistent with each other and with previously reported measurements. In addition, the molecular structures of all the chemical species involved in the acid–base dissociation equilibrium studied were calculated with a B3LYP/6–311++G(d,p) method that makes use of the polarizable continuum model (PCM). Taking into account the theoretical pKa values, the conclusions obtained match our experimental determinations.Key words: solvent effects, p-hydroxybenzophenone, acidity constant, solvation parameters, structure, DFT calculation.

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