The acid dissociation constants of 2,3-quinoxalinedithiol

Sodium salts of 2,3-quinoxalinedithiol have been prepared and used for determination of the acid ionization constants by potentiometric titration. The fully protonated form of the reagent was used in an alternative determination of the first ionization constant by a solubility method. The constants are pK(2), == 6.84 +/- 0.04 and pK(2) = 9.95 +/- 0.03.     

The dissociation of ethylenedithiodiacetic acid in aqueous solution

The dissociation of ethylenedithiodiacetic acid (H₂Edtda) was studied by potentiometric titration at 298.15 K and ionic strength values of 0.5, 1.0, and 1.5 against the background of sodium and lithium nitrates. The concentration and thermodynamic dissociation constants were determined.     

Studies on fluorescein-IV Notes on obtaining acid dissociation constants from the titration curves of dibasic acids

Equations have been derived by which the dissociation constants of a dibasic acid can be calculated from three points on a titration curve. The equations hold irrespective of the ratio of the dissociation constants, that is, irrespective of whether an end-point break appears at one equivalent of base added per mole of dibasic acid. Conditions have also been established, under which each dissociation constant can be evaluated from a single point on the titration curve.     

Effects of carbonyl-group geometrical parameters on carboxylic-acid dissociation constants in aqueous solution

CNDO/2 has provided a correlation giving the carboxylic-acid ionization constants in aqueous solution on the basis of known OCO bond angles in the carboxyl groups. It is shown that the equation can be used to determine which carboxyl groups in a polycarboxylic acid ionize first.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 3, pp. 318–324, May–June, 1988.     

Rate constants for ion pair formation and dissociation in water

The reactive flux time correlation function for an associating ion pair in water is obtained by computer simulation. The transmission coefficient is found directly from the reactive flux and also through the method of absorbing barriers. Rate constants for the transitions between the contact and solvent-separated states of the ion pair are calculated.     

Thermodynamic dissociation constants of N-phenylbenzohydroxamic acids and benzohydroxamic acid

Thermodynamic association constants of benzohydroxamic acid and several ortho-substituted N-phenylbenzohydroxamic acids have been determined by pH titration in aqueous dioxan media at 25 degrees and 35 degrees . Empirical pH corrections for mixed aqueous media have been applied. The pK(a) values do not vary linearly with the reciprocal of dielectric constant of the medium, but a plot of pK(a) vs. the mole fraction of dioxan is linear at a given temperature. Values of DeltaG degrees , DeltaH degrees and DeltaS degrees are tabulated.     

The solubility of tri-n-octylamine in water and phosphoric acid solutions

The solubility of tri-n-octylamine (TOA) in water and phosphoric acid is reported. Equilibration is achieved by circulating the solutioin through PVC pieces saturated with the absorbed amine in a glass tube. The dissolved TOA is determined by capillary gas chromatography which can detect amine concentrations down to 10 μg l^?1. The solubility of TOA in water is 0.039 mg l^?1 and in 5.5 M phosphoric acid 0.82 mg l^?1; these values are much lower than those reported in the literature.     

Determination of acid dissociation constants by capillary electrophoresis

Capillary electrophoresis affords a simple, automated approach for the measurement of pKa values in the range 2-11 at a throughput of less than 1 h per sample per instrument. Agreement with literature values is usually within 0.20 log units with a precision better than 0.07 log units. The attractive features of capillary electrophoresis for pKa measurements are: (1) conventional instrumentation with a high level of automation are suitable for all measurements; (2) because it is a separation method samples need not be of high purity; (3) samples of low water solubility with suitable chromophores are easily handled (detection limits in the microM range); (4) sample consumption per measurement is in the microgram range; and (5) since only mobilities are measured, exact knowledge of concentrations is not needed. The general approach can be extended to pKa measurements in aqueous-organic solvent mixtures and non-aqueous solvents with suitable calibration. The widespread use of absorbance detection in capillary electrophoresis means that the sample must have a suitable chromophore for detection. The main source of controllable error is the accuracy of buffer standardization and their stability in use, and uncontrollable error, the retentive interactions of the sample with the column wall. The latter seems to be a rare problem in practice for typical operating conditions.     

Surface dissociation constants for solid oxide/aqueous solution systems

Summary An equation for the surface potential ₀ was used to define the surface dissociation constant of surface hydroxyls at a solid oxide/aqueous solution interface.Using the measurements of the surface charge, the Gouy-Chapman theory and crystallo-chemical data for oxides, the calculations of the surface dissociation constants have been carried out. The values of the acidic surface dissociation constants (in minus logarithmic scale) fall in range 8.7±0.8 at ionic strength 1 M and in the range 7.2±0.7 at 10^–3 M KNO₃ These constants exceed by 2 to 5 orders of magnitude the dissociation constants of M(OH) _naq species in solution.With 1 table     

Potentiometric dissociation constants and analytical properties of α-mercaptobenzeneacetic acid

The α-mercaptobenzeneacetic acid has been synthesized and screened for its properties as an analytical reagent. The acid dissociation constants have been determined potentiometrically in 0.1 M KNO₃ and 0.5 M KNO₃ ethanol-water 20% (v/v) solutions at 25 ± 0.1 °C.     

Studies on fluorescein-III The acid strengths of fluorescein as shown by potentiometric titration

Potentiometric back-titration of yellow solid fluorescein (H(2)Fl) and of red solid fluorescein in alkali with acid yielded titration curves that were practically identical in shape and position. The end-points at pH 8.5, 5.40 and 3.3 corresponded, respectively, to titration of the excess of standard alkali, and the successive protonations Fl(2-) + H(+) = HFl(-) and HFl(-) + H(+) = H(2)Fl. The pH at the mid-point of the first protonation yielded a value of 6.36 for pK(HFl) (ionic strength 0.10). Because of precipitation of yellow fluorescein during the second protonation step, a value for pK(H(2)Fl) could not be obtained. The total concentration of fluorescein at the first appearance of the precipitate fell on the curve for the solubility of yellow fluorescein as a function of pH. The titrations and the pK values found for the three acid groups of protonated fluorescein (H(3)Fl(+)) have been interpreted on the basis that in water fluorescein exists in only one structural form the yellow zwitterion. Similar back-titrations of alkalinized solutions of yellow or red fluorescein in 50% aqueous ethanol showed that in this medium fluorescein is present in only one form, presumably the quinonoid structure, with much weaker apparent acid functions, pK'(1) = 6.38 and PK'(2) = 7.16 (ionic strength 0.10).     

The effect of temperature on the solubility of benzoic acid derivatives in water

Using a laser monitoring observation technique, solubilities of o-nitro-benzoic acid, p-hydro-benzoic acid, p-methyl-benzoic acid and m-methyl-benzoic acid in water have been measured in the temperature range 290.15–323.15 K. The experimental data are regressed with the Wilson equation and the λH equation. The experimental results show that solubilities of these compounds in the range of 10⁻⁴–10⁻⁵ mole fraction in water, increase significantly with temperature. Except for o-nitro-benzoic acid, the solubility data are described adequately with the Wilson equation. The λH equation gives good agreement with all experimental data. The results indicate that the molecular structure and interactions affect the solubilities significantly.     

Medium effects on the acid dissociation constants of some diimine heterocyclic bases

The acid dissociation constants of the protonated form of diimine heterocyclic compounds (imidazole, 2-methylimidazole, 2,2-bipyridyl, and 1,10-phenanthroline) were determinedpH-meterically in aqueous media containing different amounts of organic solvents, viz. amphiprotic (methanol, ethanol), dipolar aportic (DMSO), and low basic aprotic (acetonitrile) at 25±0.1 °C. It was observed that by increasing the amount of alcohol orDMSO in the aqueous medium thepK _a, values of the investigated compounds decreased. On the other hand, thepK _a values increased as the amount of acetonitrile in the medium was increased. These results are discussed in terms of various solvent characteristics. It is concluded that solvent effects, viz. differences in stabilization of the free base by dispersion forces and of the proton by its interaction with solvent molecules in amphiprotic or dipolar aprotic solvent-aqueous media relative to that in pure aqueous one, as well as the basicity effect of acetonitrile play a vital role in the ionisation equilibria of the investigated compounds.

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Mediumeffekte auf die Säuredissoziationskonstanten einiger heterocyclischer Diimin-Basen

Zusammenfassung Die Säuredissoziationskonstanten der protonierten Formen der heterocyclischen Dimin-Basen Imidazol, 2-Methylimidazol, 2,2-Bipyridyl und 1,10-Phenanthrolin wurdenpH-metrisch in wäßrigem Medium mit einem Anteil an organischen Lösungsmitteln bei 25±0.1 °C bestimmt. Dabei wurden als amphiprotische Zusätze Methanol und Ethanol, als dipolar aprotisches organisches LösungsmittelDMSO und als aprotisches niederer Basizität Acetonitril ausgewählt. Es wurde beobachtet, daß bei ansteigenden Konzentrationen an Alkohol oderDMSO diepK _a-Werte der untersuchten Verbindungen kleiner werden. Andererseits bewirkt Acetonitril ein Ansteigen derpK _a-Werte. Die Ergebnisse werden mittels verschiedener Lösungsmittelparameter diskutiert. Lösungsmitteleffekte wie Stabilisierung der freien Base mittels Dispersionskräften, Protonwechselwirkungen in den verschiedenen Lösungsmittelgemischen und Basizitätseffekte des Acetonitril spielen dabei eine entscheidende Rolle.

     

The acidity and solubility constants of tetracyclines in aqueous solutions

Solubility measurements over the pH range 2.6–7.6 for tetracycline, chlortetracycline, dimethylchlortetracycline and oxytetracycline are used to determine thermodynamic values for the solubility constant and the first and second acidity constants of these compounds.     

Potentiometric determination of aqueous dissociation constants of flavonols sparingly soluble in water

Two different approaches were evaluated and used to estimate the aqueous pK(a) values of some flavonols sparingly soluble in water (morin, fisetin and quercetin) from their pK(a) values in methanol/water mixtures obtained by potentiometry. Both approaches lead to similar results, although one of them requires only one pK(a) value at one unique methanol/water mixture, whereas the other (the classical Yasuda-Shedlovsky plot) requires several pK(a) data at different methanol/water mixtures. Thus, the first approach is recommended because it is faster and simpler. The automated potentiometric method is strongly recommended for pK(a) determination of these types of compounds because of its simplicity and speed of operation.     

The dissociation constants of alizarin fluorine blue

Dissociation constants for the analytical reagent alizarin fluorine blue (3-aminomethylalizarin-N N-diacetic acid) have been determined by potentiometric titration at ionic strength 0.1, and are k(1) = 1.28 +/- 0.30 x 10(-5); k(2) = 2.82 +/- 0.24 x 10(-8); k(3) = 3.72 +/- 0.19 x 10(-11); k(4) = 6.39 +/- 0.12 x 10(-12).