Chelating equilibria of 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol and 4-(2-pyridylazo)resorcinol with La(III) ions

1988 ◽  
Vol 53 (3) ◽  
pp. 526-542
Author(s):  
Dimitrii Borisovich Gladilovich ◽  
Vlastimil Kubáň ◽  
Josef Havel
Keyword(s):  
Absorption Band ◽  
Organic Solvent ◽  
Aqueous Solutions ◽  
Equilibrium Constant ◽  
Absorption Maximum ◽  
Aqueous Ethanol ◽  
Equilibrium Constants ◽  
Organic Component ◽  
Alkaline Solutions ◽  
Hydrolysis Products

2-(5-Bromo-2-pyridylazo)-5-diethylaminophenol (BrPADAP) with lanthanum(III) ions in 50% (v/v) aqueous ethanol or 30-50% (v/v) aqueous dimethylformamide (DMF) forms unprotonated chelates ML and ML2 characterized by a double absorption band with maxima at 550 and 570 nm. The ML2 species is rather unstable, hydrolyzing readily to the M(OH)L chelate, which exhibits an absorption maximum at 570 nm. The molar absorptivities of the ML, ML2, and M(OH)L species, lying in the regions of 5.3-6.5, 7.0-7.2, and 6.5-7.2 m2 mmol-1, respectively, depend on the kind and fraction of the organic component in the solvent. The conditional equilibrium constants (-log βpqr = 3.3-4.0, 12.2-12.5, and 7.8-8.2, respectively) decrease with increasing fraction of the organic solvent; in systems with high proportions of ethanol orDMF, the formation of higher species is greatly suppressed. 4-(2-Pyridylazo)resorcinol (PAR) with La(III) in acid aqueous solutions forms the MLH and ML species with absorption maxima at 490 and 506 nm, respectively ( ε = 1.2 and 2.5 m2 mmol-1, respectively) and with conditional equilibrium constants –log βpqr = -3.4 and 3.5, respectively. In alkaline solutions with excess PAR, the ML2 species with the absorption maximum at 509 mn (ε = 4.6 m2 mmol-1) and conditional equilibrium constant –log βpqr = 8.1 is formed. This chelate hydrolyses readily forming the M(OH)L species and other hydrolysis products. The ML2 species of the two reagents, forming in ammoniacal buffer at pH 9.0 – 9.5 (PAR) and 8.2 – 8.4 (BrPADAP), can be used for a sensitive (ε = 3.8 and 6.1 m2 mmol-1, respectively) post-column derivatization of lanthanoids after their separation by IEC or HPLC or for their FIA determination.

The retroaldol reaction of cinnamaldehyde

1984 ◽  
Vol 62 (8) ◽  
pp. 1441-1445 ◽  
Author(s):  
J. Peter Guthrie ◽  
Kevin J. Cooper ◽  
John Cossar ◽  
Brian A. Dawson ◽  
Kathleen F. Taylor
Keyword(s):  
Equilibrium Constant ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Alkaline Solutions ◽  
Formation Reaction

Rate and equilibrium constants have been measured for the hydration and retroaldol reactions of cinnamaldehyde. The equilibrium constant for the 1,4-addition of water to cinnamaldehyde is 4.42 × 10−3. The rate constants for hydroxide catalyzed reaction, extrapolated to zero hydroxide concentration (to correct for the addition of hydroxide to the aldol carbonyl), are: [Formula: see text];[Formula: see text]; and [Formula: see text]. The rate of the formation reaction was measured by adding small amounts of acetaldehyde to alkaline solutions of benzaldehyde: [Formula: see text] and Koverall = 1480 M−1. The course of the synthetically useful reaction of acetaldehyde with benzaldehyde is discussed in the light of these results.

Transient species produced in irradiated water and aqueous solutions containing oxygen

1966 ◽  
Vol 289 (1418) ◽  
pp. 321-341 ◽  
Keyword(s):  
Aqueous Solution ◽  
Absorption Band ◽  
Aqueous Solutions ◽  
Rate Constants ◽  
Alkaline Solutions ◽  
Absolute Rate ◽  
Radical Ions ◽  
Transient Species ◽  
Fast Electrons ◽  
Transient Spectra

Transient spectra of a number of radicals and radical ions have been observed in aqueous solution saturated with oxygen and irradiated by a short intense pulse of fast electrons. Depending upon the conditions of pH and upon solute concentrations, absorption maxima are produced in both the visible and ultraviolet regions of the spectrum. In oxygenated alkaline solutions the u.v. absorption contains four components which decay at different rates. One of these is the second absorption band of 0 - 3 and it is concluded that the others are due to the species O - 2 , HO - 3 and HO - 2 . It is suggested that the short lived u.v. absorption observed in alkaline N20 saturated solution is due to the species O - . Absolute rate constants have been obtained for several of the reactions involved and a comprehensive mechanism for the radiolysis is proposed.

The reactions of oligoalcohols with arsenic, arsenous, boric and germanic acids

1980 ◽  
Vol 45 (10) ◽  
pp. 2645-2655 ◽  
Author(s):  
Antonín Mikan ◽  
Miloš Bartušek
Keyword(s):  
Aqueous Solutions ◽  
Equilibrium Constants ◽  
Dilute Aqueous Solutions

The reactions of sorbitol, mannitol, adonitol, dulcitol, glucose and glycerol with H3AsO4, H3AsO3, H3BO3 and GeO2 acids in dilute aqueous solutions were studied by potentiometric neutralization titrations. The formation of the following chelates was demonstrated: As(V)L3-, As(III)L(OH)2-, HAs(III)L(OH)2, BL2-, GeL2(OH)- and GeL32- and the equilibrium constants for their formation were found. Conditions for formation of these chelates of organic oligohydroxy compounds are discussed.

Selective electrooxidation of acetaldehyde in aqueous ethanol alkaline solutions on silver-containing electrodes

2021 ◽  
pp. 138076
Author(s):  
S.A. Kleinikova ◽  
K.V. Gor'kov ◽  
E.V. Gerasimova ◽  
N.N. Dremova ◽  
E.V. Zolotukhina
Keyword(s):  
Aqueous Ethanol ◽  
Alkaline Solutions

scholarly journals Capacitive deionization in organic solutions: case study using propylene carbonate

RSC Advances ◽  
2016 ◽  
Vol 6 (7) ◽  
pp. 5865-5870 ◽  
Author(s):  
S. Porada ◽  
G. Feng ◽  
M. E. Suss ◽  
V. Presser
Keyword(s):  
Organic Solvent ◽  
Aqueous Solutions ◽  
Propylene Carbonate ◽  
Capacitive Deionization ◽  
Organic Solutions

We present a study of the performance of capacitive deionization (CDI) when applied to electrosorption in an organic solvent, finding enhanced cell charging voltages and improved salt sorption over electrosoprtion in aqueous solutions.

SOME EQUILIBRIUM CONSTANTS OF TRANSITION METAL HALIDES

1960 ◽  
Vol 38 (10) ◽  
pp. 1827-1836 ◽  
Author(s):  
M. W. Lister ◽  
P. Rosenblum
Keyword(s):  
Ionic Strength ◽  
Transition Metal ◽  
Equilibrium Constant ◽  
Spectrophotometric Method ◽  
Equilibrium Constants ◽  
Cell Voltage ◽  
Metal Halides ◽  
Complex Ions ◽  
Anomalous Variation ◽  
A Cell

Measurements are reported on the formation of complex ions in solutions containing cupric and chloride or bromide ions, and solutions of nickel or cobalt with chloride. In each case the halide was present in very low amount. With copper a spectrophotometric method was used, and a cell voltage method with nickel and cobalt. The ionic strength was kept constant, but the temperature was varied. The data show difficulties of interpretation if it is assumed that only MX+ ions (M is the metal, X is the halogen) are formed, the difficulties arising from the anomalous variation of the equilibrium constant with temperature, and from the general drift of the calculated constants from the e.m.f. measurements. Various explanations are considered and it is shown that postulation of M2X+3 ions is at least a possible explanation.

scholarly journals Synthesis of Mn(II)-containing paratungstate B from aqueous solutions acidified by acetic acid

2021 ◽  
pp. 39-48
Keyword(s):  
Thermal Analysis ◽  
Acetic Acid ◽  
Aqueous Solutions ◽  
Equilibrium Constants ◽  
Background Electrolyte ◽  
Equilibrium Processes ◽  
Transformation Processes ◽  
Paratungstate B ◽  
Solution Acidity ◽  
Tungstate Anion

The method of pH-potentiometric titration and mathematical simulation were used to study the equilibrium processes in aqueous solutions of the WO42––CH3COOH–H2O system in the acidity range Z=(CH3COOH)/(Na2WO4)=0.8–1.7 at СW=0.01 mol L–1 and T=2980.1 K, a constant ionic strength being maintained by sodium nitrate as a background electrolyte ((NaNO3)=0.10 mol L–1). We developed the models of polyoxotungstate anions formation and the equilibrium transformation processes, which adequately describe experimental pH vs. Z dependences. It was found that acetic acid using to create the solution acidity that is necessary for the formation of isopoly tungstate anion contributes only to the formation of protonated paratungstate B anions Нх[W12O40(ОН)2](10–х)– (where x=0–4). We calculated the logarithms of the concentration equilibrium constants of the polyanion formation and plotted the distribution diagrams. Double sodium-manganese(II) paratungstate B Na8(H2O)28Mn(H2O)2[H2W12O42]4H2O was synthesized at Z=1.00 to confirm the results of the mathematical modeling. The chemical composition of the prepared salt was established by chemical elemental analysis, thermal analysis, FTIR spectroscopy, and single crystal X-ray analysis. The stepwise process of salt dehydration was studied by means of differential thermal analysis.

scholarly journals Formation of carboxylic acids during degradation of monosaccharides

2008 ◽  
Vol 26 (No. 2) ◽  
pp. 113-131 ◽  
Author(s):  
O. Novotný ◽  
K. Cejpek ◽  
J. Velíšek
Keyword(s):  
Free Radicals ◽  
Aqueous Solutions ◽  
Carboxylic Acids ◽  
Sodium Hydroxide Solution ◽  
Model Systems ◽  
Alkaline Solutions ◽  
Hydroxycarboxylic Acids ◽  
Acid Type ◽  
Cannizzaro Reaction ◽  
Benzilic Acid

The formation of low molecular carboxylic and hydroxycarboxylic acids as well as sugar and deoxysugar acids from monosaccharides (D-glucose, D-fructose, D-arabinose, DL-glyceraldehyde, and 1,3-dihydroxyacetone) was studied in three different model systems: aqueous and alkaline solutions of potassium peroxodisulfate (K<sub>2</sub>S<sub>2</sub>O<sub>8</sub>), and sodium hydroxide solution. In total, 3 low molecular carboxylic acids (formic, acetic and propionic), 24 hydroxycarboxylic acids, and 12 corresponding lactones were identified and quantified by GC/MS. Formic, acetic, and propionic acids were isolated by extraction with diethyl ether and directly analysed by GC/MS; hydroxycarboxylic acids and their lactones were monitored as their trimethylsilylated derivatives using the same method. Formic, acetic, L-lactic, glycollic, DL-2,4-dihydroxybutanoic acids and aldonic acids derived from the parent sugars were the most abundant compounds in all model systems. Within the models investigated, the yield of carboxylic acids and hydroxycarboxylic acids (together with their lactones) ranged between 9.3–22.2% (n/n) and between 3.6–116.9% (n/n), respectively. The amount of acids was significantly lower in aqueous solutions of K<sub>2</sub>S<sub>2</sub>O<sub>8</sub> than in the alkaline solutions. The data obtained indicate that lower carboxylic acids are formed by both subsequent reactions (oxidation and/or intramolecular Cannizzaro reaction) of the sugar fragmentation products and direct decomposition of some intermediates such as uloses or hydroperoxides derived from the parent sugars. The acids possessing the original sugar skeleton are formed as a result of sugar oxidation or benzilic acid type rearrangement of deoxyuloses. Lower acids may also be formed by a recombination of free radicals.

Aqueous nonelectrolyte solutions — Part XX: Formula of structure I methane hydrate, congruent dissociation melting point, and formula of the metastable hydrate

2003 ◽  
Vol 81 (12) ◽  
pp. 1443-1450 ◽  
Author(s):  
David N Glew
Keyword(s):  
Melting Point ◽  
Equilibrium Constant ◽  
Methane Hydrate ◽  
Equilibrium Constants ◽  
Stability Range ◽  
Congruent Melting Point ◽  
Quadruple Point ◽  
Dissociation Equilibrium ◽  
Metastable Structure ◽  
The Stability

Sixteen new measurements of high precision for structure I methane hydrate with water between 31.93 and 47.39 °C are shown to be metastable and exhibit higher methane pressures than found by earlier workers. Comparison of earlier measurements between 26.7 and 47.2 °C permit positive identification of the structure II and the structure I hydrates. Forty-nine equilibrium constants Kp(h1[Formula: see text]l1g) for dissociation of structure I methane hydrate into water and methane, 32 between –0.29 and 26.7 °C for the stable hydrate and 17 between 31.93 and 47.39 °C for the metastable hydrate, are best represented by a three-parameter thermodynamic equation, which indicates a standard error (SE) of 0.63% on a single Kp(h1[Formula: see text]l1g) determination. The congruent dissociation melting point C(h1l1gxm) of metastable structure I methane hydrate is at 47.41 °C with SE 0.02 °C and at pressure 505 MPa. The congruent equilibrium constant Kp(h1[Formula: see text]l1g) is 102.3 MPa with SE 0.2 MPa. ΔH°t(h1[Formula: see text]l1g) is 62 281 J mol–1 with SE 184 J mol–1, and the congruent formula is CH4·5.750H2O with SE 0.059H2O. At the congruent point, ΔV(h1[Formula: see text]l1g) is zero within experimental precision, and its estimate is 1.3 with SE 1.6 cm3 mol–1. The stability range of structure I methane hydrate with water extends from quadruple point Q(s1h1l1g) at –0.29 °C up to quadruple point Q(h1h2l1g) at 26.7 °C, and its metastability range with water extends from 26.7 °C up to the congruent dissociation melting point C(h1l1gxm) at 47.41 °C. Key words: methane hydrate, clathrate structure I, metastability range, dissociation equilibrium constant, formula, congruent melting point, metastability of structure I hydrate.

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