Beryllium-chrome-azurol-S complexes

1968 ◽  
Vol 21 (3) ◽  
pp. 603 ◽  
Author(s):  
WG Baldwin ◽  
DR Stranks

Complex formation between the aquated beryllium cation and the tetrabasic dyestuff chrome-azurol-S (H4CAS) has been studied by spectrophotometric, potentiometric, electrophoretic, and ion-exchange techniques. At least two complexes are shown to exist within the pH range 3-6. The major species is the anionic complex BeHCAS- for which log β11, = 4.66 � 0.08 at 25� and at ionic strength 0.lM (NaClO4) Coordination of beryllium is considered to occur at the quinonoid-,). carboxylato site in the HCAS8- ligand. The stability constant for the dinuclear species Be2CASO is shown to be log β21 = 15.8 � 0.1 under the same medium conditions. The dinuclear complex interferes with spectrophotometric measurements at beryllium concentrations exceeding 2.5 x 10-4. The acidity constants of H4CAS were determined at 25� and at an ionic strength 0.IM (NaClO,) as pK2a = 2.25 � 0.10,pK3a, = 4.88 � 0.05, pK4, = 11.75 � 0.05, whilst pK1a = -1.2 � 0.4.

1968 ◽  
Vol 46 (8) ◽  
pp. 1383-1388 ◽  
Author(s):  
M. Deneux ◽  
R. Meilleur ◽  
R. L. Benoit

Complex formation between iron(III) and oxalate, malonate, succinate, glutarate, and acetate ions has been studied by potentiométric and spectrophotométric methods at 25 °C, ionic strength 0.52 ± 0.02, and [Formula: see text] and 0.1 M H+ concentrations. The acidity constants of the dicarboxylic acids and the formation constants of the monochelates of iron(III) have been determined. The stability order is as follows: [Formula: see text].


1969 ◽  
Vol 22 (6) ◽  
pp. 1111 ◽  
Author(s):  
AW Fordham

The hydrolysis of iron(III) has been studied by spectrophotometric methods in KaClO4, NaCl, and CaCl2 solutions all of the same ionic strength 0.15M. The measured values of the hydrolysis constants, expressed in a form which allows for association of iron with the supporting medium, were 14.5 x 10-4 in NaClO4, 8.8 x 10-4 in NaCl, and 10.9 x 10-4 in CaCl2. In addition, the extent of complex formation between iron(III) and chloride ions has been measured in perchlorate solutions of the same ionic strength 0.15M. Assuming that only chloro complexes were formed in these systems, the stability constant of FeCl2+ formation was found to be 4.0. ��� All the results obtained were sufficiently consistent with each other, within experimental error, that the inclusion of terms to account for iron-perchlorate association was unwarranted. However, if iron-perchlorate association was assumed to exist and the results were treated accordingly, the stability constant of the associated complex was estimated to be 1.8.


1965 ◽  
Vol 18 (5) ◽  
pp. 651 ◽  
Author(s):  
RW Green ◽  
PW Alexander

The Schiff base, N-n-butylsalicylideneimine, extracts more than 99.8% beryllium into toluene from dilute aqueous solution. The distribution of beryllium has been studied in the pH range 5-13 and is discussed in terms of the several complex equilibria in aqueous solution. The stability constants of the complexes formed between beryllium and the Schiff base are log β1 11.1 and log β2 20.4, and the distribution coefficient of the bis complex is 550. Over most of the pH range, hydrolysis of the Be2+ ion competes with complex formation and provides a means of measuring the hydrolysis constants. They are for the reactions: Be(H2O)42+ ↔ 2H+ + Be(H2O)2(OH)2, log*β2 - 13.65; Be(H2O)42+ ↔ 3H+ + Be(H2O)(OH)3-, log*β3 -24.11.


Author(s):  
Ghusoon Faidhi Hameed ◽  
Fawzi Yahya Waddai ◽  
Nahla Shakir Salman

The paper reports the study of the complex formation of cobalt (II) with diethylenetriaminepentaacetic acid (DTPA, H5L) based on spectrophotometric (SF) and potentiometric data (pH). Complexes of different compositions were found, and equilibrium constants, as well as the stability constants of these complexes, were determined. Accumulation of complexes in proportion is calculated based on the acidity of the medium. The experimental data have been carried out by using mathematical models to assess the solution's possible existence with a wide spectrum of complex particles and to point out those which are quite sufficient to copy the experimental data. In addition, thermodynamic parameters (ΔG°, ΔH°, and ΔS°) for the studying complexes were calculated according to the values of stability constant (KST) at 25 °C obtained from the temperature dependence of stability constant by using van’t Hoff equation.


Author(s):  
A.B. Naik ◽  
M.S. Poharkar

The stability constant on complexation of rare earth metal ions Eu (III), Gd (III), Nd (III) and Tb (III) with substituted thiazole in 70% Dioxane (Dx)-water mixture have been determined by a pH and spectrophotometric method at 298.15K and ionic strength 0.1mol.dm-3(sodium perchlorate). At constant temperature, the stability constant of the formed complexes decreases in the order Tb (III), Gd (III), Eu (III), Nd (III). The dissociation process is non-spontaneous, endothermic and entrophically unfavorable while formation of metal complexes has been found to be spontaneous, endothermic and entrophically favorable.


1967 ◽  
Vol 45 (14) ◽  
pp. 1643-1647 ◽  
Author(s):  
P. G. Manning

Stepwise stability constants have been determined for the 1:1 and 1:2 Eu3+:mandelate− and Eu3+:tartronate2− complexes in water. Measurements were made at low ionic strength and the temperature was 25 °C. The solvent-extraction–radiotracer method was used.For the mandelate system at an ionic strength of 0.104, K1 = 5.0 × 102, K2 = 1.58 × 102, and K1:K2 = 3.1. The K1:K2 ratios suggest monodentate ligandcy.The stepwise stability constants for the two stages of tartronate ion association are: K1 = 7.1 ( ± 15%) × 104 and K1K2 = 4.2 ( ± 5%) × 108. The magnitudes of the stability constants suggest that tartronate is a tridentate ligand. The stability constant ratios are discussed with reference to the ratios for piperidinedicarboxylate and iminodiacetate complexes.


2009 ◽  
Vol 6 (1) ◽  
pp. 270-272 ◽  
Author(s):  
J. J. Vora ◽  
D. R. Patel ◽  
Asha D. Patel ◽  
Kanu Patel ◽  
Sangita Sharma ◽  
...  

To study the metal ligand equilibrium in aqueous solution, the well known Irving-Rossotti titration method was used. The temperature selected is 30±0.10C at ionic strength 0.2 M (NaClO4) which was maintained constant through out the work. The binary metal complex (ML2) formation was studied. The metals selected are Sm3+, Gd3+, Dy3+and Yb3+. The diamine ligands taken are ethylenediamine, 1,2 diamino propane, 1,3 diamino propane,N-Ndiethyl ethylenediamine andN-N -dimethyl ethylenediamine. Factors that affected the stability of the complexes are size and ionic potential of lanthanone ions, basicity of ligands, ring size and steric effect of ligands.


2006 ◽  
Vol 71 (1) ◽  
pp. 55-65 ◽  
Author(s):  
Jasmina Brboric ◽  
Mirjana Jovanovic ◽  
Gordana Popovic ◽  
Vera Kapetanovic ◽  
Sote Vladimirov

The acid-base equilibria of a novel hepatobiliary imaging agent, 2,4-diiodo-6-methylphenylcarbamoylmethyl iminodiacetic acid (DIIODIDA) were studied. The potentiometrically determined acidity constants of the second carboxylic group, amino and amide groups were pK2 = 2.52 ? 0.02; pK3 = 5.86 ? 0.06 and pK4 = 10.9 ? 0.1. The determinations were performed at 25 ?C and an ionic strength of 0.1 mol/dm3 (NaCl). The acidity constants (pK1 = 1.3 ? 0.4) corresponding to the first carboxylic group was determined indirectly, on the basis of equilibrium constants obtained in a heterogeneous system, at 25 ?C and an ionic strength 1 mol/dm3 (HCl, NaCl). DIIODIDA was labeled with technetium-99m, and the influence of pH on the yield of labeling was investigated. It was found that labeling within the pH range from 5.5 to 6.5 provided a radiopharmaceutical of high radiochemical purity (>98 %).


2021 ◽  
Vol 56 ◽  
pp. 97-105
Author(s):  
Theresa Hennig ◽  
Michael Kühn

Abstract. The simulation of uranium migration through the Swiss Opalinus Clay is used as an example to quantify the influence of varying values of a stability constant in the underlying thermodynamic database on the migration lengths for the repository scale. Values for the stability constant of the neutral, ternary uranyl complex Ca2UO2(CO3)3 differ in literature by up to one order of magnitude. Within the studied geochemical system, either the neutral or the anionic complex CaUO2(CO3)32- is the predominant one, depending on the chosen value for the neutral complex. This leads to a changed interaction with the diffuse double layers (DDL) enveloping the clay minerals and thus can potentially influence the diffusive transport of uranium. Hence, two identical scenarios only differing in the value for the stability constant of the Ca2UO2(CO3)3 complex were applied in order to quantify and compare the migration lengths of uranium on the host rock scale (50 m) after a simulation time of one million years. We ran multi-component diffusion simulations for the shaly and sandy facies in the Opalinus Clay. A difference in the stability constant of 1.33 log units changes the migration lengths by 5 to 7 m for the sandy and shaly facies, respectively. The deviation is caused by the anion exclusion effect. However, with a maximum diffusion distance of 22 m, the influence of the stability constant of the Ca2UO2(CO3)3 complex on uranium migration in the Opalinus Clay is negligible on the host rock scale.


2015 ◽  
Vol 68 (5) ◽  
pp. 731 ◽  
Author(s):  
Mark A.W. Lawrence ◽  
Yvette A. Jackson ◽  
Willem H. Mulder ◽  
Per Martin Björemark ◽  
Mikael Håkansson

The synthesis and crystal structures of bis-N-(2,5-dimethoxyphenyl)pyridine-2,6-dicarbothioamide (dicarbothioamide I) and 6-(4,7-dimethoxy-2-benzothiazolyl)-N-(2,5-dimethoxyphenyl)-2-pyridinecarbothioamide (L1) as well as the syntheses of the palladium(ii) chloride and acetate pincer complexes are reported. The stability constant for the palladium complex formation at 25°C was found to be (2.04 ± 0.26) × 104 dm3 mol–1 and (2.30 ± 0.19) × 104 dm3 mol–1 with ΔfH = 8 ± 1 kJ mol–1, ΔfSθ = 108 ± 10 J K–1 mol–1, and ΔfH = 17 ± 4 kJ mol–1 and ΔfSθ = 140 ± 20 J K–1 mol–1 for the PdClL1 and Pd(OAc)L1, respectively. The kinetics of formation of the palladium(ii) complexes were investigated and the mechanism is proposed to be associative in nature (ΔH1‡ = 34 ± 2 kJ mol–1 and ΔS1‡ = –113 ± 8 J K–1 mol–1, and ΔH1‡ = 37 ± 3 kJ mol–1 and ΔS1‡ = –100 ± 8 J K–1 mol–1 for the PdClL1 and Pd(OAc)L1 species, respectively). The electrochemical measurements of the acetonitrile solutions revealed irreversible electron transfers consistent with the electrochemical decomposition of the ligand and its coordination complexes.


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