scholarly journals Calculating the Equilibrium Constants for All Monoazide Lanthanide Complexes in Aqueous Solution Based on the Formation of Eu(III)/N− 3

2020 ◽  
Vol 3 ◽  
pp. 1-6
Author(s):  
Eliana Maria Aricó ◽  
Horacio Dorigan Moya
1995 ◽  
Vol 50 (4) ◽  
pp. 545-550 ◽  
Author(s):  
Masaaki Tabata ◽  
Masahiro Ide ◽  
Kentaro Kaneko

Thermochromism was observed for an aqueous solution containing zinc(II) and mercury( II) cations and N-p-nitrobenzyl-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin anion (NO2Bz(Htpps)4-) in the temperature range 10 to 70 °C. The equilibrium constants and the thermodynamic parameters of Zn(NO2Bztpps)3- and Hg(NO2Bztpps)3- have been determined spectrophotometrically to elucidate the thermochromism at 10, 15, 20, 25 and 30 °C in 0.1 mol dm-3 NaNO3. The protonation and metalation constants of NO2Bz(Htpps)4- are defined as K2 = [H2P][H+]-1[HP]-1, K3 = [H3P][H+]-1[H2P]-1 and KMP = [M P][H+][M2+]-1[HP]-1, where HP and MP denote the free base form of the prophyrin and the metalloporphyrins of zinc(II) and mercury(II), respectively. Charges of the prophyrin and metalloporphyrins are omitted for simplicity. The following values were found: logK2 = 7.75 ±0.02 (25 °C), ΔH°/kJmol-1 = -21.2±0.5 and ΔS°/Jmol-1K-1 = 77±1, logK3 = 2.55±0.02 (25 °C), ΔH°/kJmol-1 = -25±0.8 and ΔS°/Jmol-1K-1 = -35±3 and log KZnP = 0.63±0.03 (25 °C), ΔH°/kJmol-1 = 31.0±0.8 and ΔS°/Jmol-1K-1 = 116±3, logKHgP = 6.22±0.03 (25 °C), ΔH°/kJmol-1 = 4.5±0.7 and ΔS°/Jmol-1K-1 = 134±2. The distribution curve calculated from the thermodynamic parameters sufficiently agrees with the observed metal exchange reaction between the metalloporphyrins.


Clay Minerals ◽  
2012 ◽  
Vol 47 (4) ◽  
pp. 429-440 ◽  
Author(s):  
S. Gamoudi ◽  
N. Frini-Srasra ◽  
E. Srasra

AbstractThe use of organoclays as adsorbents in the remediation of polluted water has been the subject of many recent studies. In the present work, a Tunisian smectite modified with two cationic surfactants was used as an adsorbent to examine the adsorption kinetics, isotherms and thermodynamic parameters of fluoride ions from aqueous solution. Various pH values, initial concentrations and temperatures have been tested. Two simplified kinetic models, first-order and pseudo-second-order, were used to predict the adsorption rate constants. It was found that the adsorption kinetics of fluoride onto modified smectites at different operating conditions can best be described by the pseudo-second-order model. Adsorption isotherms and equilibrium adsorption capacities were determined by the fitting of the experimental data to well known isotherm models including those of Langmuir and Freundlich. The results showed that the Langmuir model appears to fit the adsorption better than the Freundlich adsorption model for the adsorption of fluoride ions onto modified smectites. The equilibrium constants were used to calculate thermodynamic parameters, such as the change of free energy, enthalpy and entropy. Results of this study demonstrated the effectiveness and feasibility of organoclays for the removal of fluoride ions from aqueous solution.


1962 ◽  
Vol 40 (3) ◽  
pp. 363-372 ◽  
Author(s):  
R. W. Burley ◽  
W. H. Cook

The effect of pH, temperature, ionic strength, and lipoprotein concentration on the reversible dissociation of α- and β-lipovitellin in aqueous solutions above pH 6 has been examined by ultracentrifugal measurements. Under otherwise similar conditions α- and β-lipovitellin are 50% dissociated at pH 10.5 and 7.8, respectively. Both lipovitellins undergo an irreversible aggregation above about pH 11; β-lipovitellin is sometimes converted to a non-dissociable form upon aging. Dissociation of both lipovitellins decreases with increasing ionic strength and increasing temperature. Although the ultracentrifugal method has limitations, provisional equilibrium constants and thermodynamic data were obtained from it that are comparable with those obtained for certain protein systems.


Author(s):  
R. WALTER ◽  
C.W. SMITH ◽  
K.P. SARATHY ◽  
R.P. PILLAI ◽  
N.R. KRISHNA ◽  
...  

1986 ◽  
Vol 64 (6) ◽  
pp. 1267-1272 ◽  
Author(s):  
Oswald S. Tee ◽  
Jana Pika ◽  
M. Judith Kornblatt ◽  
Michael Trani

The kinetics of bromination of the title compound (1) have been measured in aqueous solutions of pH 0–6. The change in the order of reaction which occurs around pH 2.5 is explained by 1 reacting via its covalent hydrate, 3. Furthermore, there is sufficient 3 present at equilibrium that the kinetics of its equilibration with 1 were also measured. From these two studies the extent of covalent hydration of 1 is estimated to be 5%.Kinetic studies of the bromination of the dimethyl cation 5 and of its equilibration with the pseudobase 6 were also carried out for the purposes of comparison.The present results for 1, 3, 5, and 6 are compared to earlier results for 2-pyrimidinone and analogous derivatives.


1975 ◽  
Vol 53 (6) ◽  
pp. 898-906 ◽  
Author(s):  
J. Peter Guthrie

Equilibrium constants for hydrate–hemiacetal interconversion in aqueous solution at 25° have been measured for four fluorinated carbonyl compounds: compound, alcohol, K4 (M−1): CF3CHO, C2H5OH, 2.3; CF3COCH3, CH3OH, 1.0; CF3COPh, CH3OH, 3.5; CF3COCF3, CH3OH, 0.14. These values, combined with values from the literature, permit an examination of substituent effects upon the equilibrium constant for[Formula: see text]The free energy change for this process, corrected for symmetry and steric effects, follows the equation[Formula: see text]Thus electronic effects upon this equilibrium are generally small and in fact are often smaller than steric effects.This analysis permits and justifies the calculation of free energies of formation of [Formula: see text] compounds from the (more generally measurable) free energies of formation of the analogous [Formula: see text] compounds.


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