Hydrolysis of the thorium(IV) ion in sodium nitrate medium

1982 ◽  
Vol 60 (11) ◽  
pp. 1298-1303 ◽  
Author(s):  
Nikola B. Milić ◽  
Terezija M. Šuranji
Keyword(s):  
Sodium Nitrate ◽  
Metal Ion ◽  
Linear Free Energy Relationship ◽  
Emf Method ◽  
Nitrate Medium ◽  
Linear Free Energy ◽  
Metal Ion Hydrolysis ◽  
Stability Constants Of Complexes ◽  
The Stability ◽  
Hydrolysis Of

The hydrolysis of the thorium(IV) ion in sodium nitrate medium was studied by the emf method at 25 °C. The data show that the extent of the thorium hydrolysis depends both on the concentration of thorium and the sodium nitrate medium. Thus, at a definite pH, the extent of the hydrolysis of thorium increases with increasing its concentration, but decreases with increasing concentration and the hydration energy of the medium ions. The stability constants of complexes Th2(OH)26+, Th3(OH)57+, and Th6(OH)159+ also slightly differ going from one concentration of sodium nitrate to another. The observed effect of the medium is in agreement with the linear free energy relationship proposed for the metal ion hydrolysis.

Hydrolysis of aluminum(III) ion in sodium nitrate medium

1991 ◽  
Vol 69 (1) ◽  
pp. 28-32 ◽  
Author(s):  
Nikola B. Milić ◽  
Živadin D. Bugarčić ◽  
Predrag T. Djurdjević
Keyword(s):  
Least Squares ◽  
Key Words ◽  
Sodium Nitrate ◽  
Emf Method ◽  
Nitrate Medium ◽  
Aluminium Concentration ◽  
Hydrolysis Products ◽  
The Stability ◽  
Ph Range ◽  
Hydrolysis Of

Hydrolysis of aluminum(III) ion in 3.0 M (Na)NO3 medium was studied by emf method at 25° C. Data cover the range 1–78 mM Al(III) within the pH range of 2.0–4.5. At a definite pH, the extent of hydrolysis increases with increasing aluminium concentration, thereby indicating the presence of polynuclear hydrolysis products. The least squares treatment of the data indicates the formation of polynuclear hydrolytic complexes [Formula: see text] [Formula: see text] and [Formula: see text] With the reactions written in the form[Formula: see text]the stability constants obtained were log (β2,2 = −7.55 ± 0.21, log β2,4 = −16.41 ± 0.13, and log (β3,4 = −13.24 ± 0.08. Distribution curves indicate that the complex [Formula: see text] is predominant. Key words: hydrolysis, aluminum(III) ion, hydrolytic complexes, aluminum(III) ion hydrolysis.

scholarly journals Kinetics of alkoxysilanes hydrolysis: An empirical approach

2019 ◽  
Vol 9 (1) ◽  
Author(s):  
Ahmed A. Issa ◽  
Marwa El-Azazy ◽  
Adriaan S. Luyt
Keyword(s):  
Reaction Mechanisms ◽  
Hydrolysis Reaction ◽  
Hydrolysis Rate ◽  
Coupling Agents ◽  
Linear Free Energy Relationship ◽  
Acidic Media ◽  
Linear Free Energy ◽  
Primary Materials ◽  
Kinetics Of ◽  
Hydrolysis Of

AbstractAlkoxysilanes and organoalkoxysilanes are primary materials in several industries, e.g. coating, anti-corrosion treatment, fabrication of stationary phase for chromatography, and coupling agents. The hydrolytic polycondensation reactions and final product can be controlled by adjusting the hydrolysis reaction, which was investigated under a variety of conditions, such as different alkoxysilanes, solvents, and catalysts by using gas chromatography. The hydrolysis rate of alkoxysilanes shows a dependence on the alkoxysilane structure (especially the organic attachments), solvent properties, and the catalyst dissociation constant and solubility. Some of the alkoxysilanes exhibit intramolecular catalysis. Hydrogen bonding plays an important role in the enhancement of the hydrolysis reaction, as well as the dipole moment of the alkoxysilanes, especially in acetonitrile. There is a relationship between the experimentally calculated polarity by the Taft equation and the reactivity, but it shows different responses depending on the solvent. It was found that negative and positive charges are respectively accumulated in the transition state in alkaline and acidic media. The reaction mechanisms are somewhat different from those previously suggested. Finally, it was found that enthalpy–entropy compensation (EEC) effect and isokinetic relationships (IKR) are exhibited during the hydrolysis of CTES in different solvents and catalysts; therefore, the reaction has a linear free energy relationship (LFER).

ChemInform Abstract: Hydrolysis of Aluminum(III) Ion in Sodium Nitrate Medium.

ChemInform ◽  
2010 ◽  
Vol 22 (22) ◽  
pp. no-no
Author(s):  
N. B. MILIC ◽  
Z. D. BUGARCIC ◽  
P. T. DJURDJEVIC
Keyword(s):  
Sodium Nitrate ◽  
Nitrate Medium ◽  
Hydrolysis Of

scholarly journals Binding energy and catalysis. Fluorinated and deoxygenated glycosides as mechanistic probes of Escherichia coli (lacZ) β-galactosidase

1992 ◽  
Vol 286 (3) ◽  
pp. 721-727 ◽  
Author(s):  
J D McCarter ◽  
M J Adam ◽  
S G Withers
Keyword(s):  
Escherichia Coli ◽  
Transition State ◽  
Kinetic Parameters ◽  
Parent Compound ◽  
Order Rate Constant ◽  
Linear Free Energy Relationship ◽  
Electronic Effects ◽  
Linear Free Energy ◽  
Covalent Intermediate ◽  
Hydrolysis Of

Kinetic parameters for the hydrolysis of a series of deoxy and deoxyfluoro analogues of 2′,4′-dinitrophenyl beta-D-galactopyranoside by Escherichia coli (lacZ) beta-galactosidase have been determined and rates found to be two to nine orders of magnitude lower than that for the parent compound. These large rate reductions result primarily from the loss of transition-state binding interactions due to the replacement of sugar hydroxy groups, and such interactions are estimated to contribute at least 16.7 kJ (4 kcal).mol-1 to binding at the 3, 4 and 6 positions and more than 33.5 kJ (8 kcal).mol-1 at the 2 position. The existence of a linear free-energy relationship between log(kcat./Km) for these compounds and the logarithm of the first-order rate constant for their spontaneous hydrolysis demonstrates that electronic effects are also important and provides direct evidence for oxocarbonium ion character in the enzymic transition state. A covalent intermediate which turns over only extremely slowly (t1/2 = 45 h) accumulates during hydrolysis of the 2-deoxyfluorogalactoside, and kinetic parameters for its formation have been determined. This intermediate is nonetheless catalytically competent, since it re-activates much more rapidly in the presence of the transglycosylation acceptors methanol or glucose, thereby providing support for the notion of a covalent intermediate during hydrolysis of the parent substrates.

Substituent Effects on the Chymotrypsin-Catalyzed Hydrolysis of Specific Ester Substrates

1971 ◽  
Vol 49 (2) ◽  
pp. 210-217 ◽  
Author(s):  
R. E. Williams ◽  
M. L. Bender
Keyword(s):  
Free Energy ◽  
Rate Constants ◽  
Substituent Effects ◽  
Phenyl Group ◽  
Linear Free Energy Relationship ◽  
Acylation Reaction ◽  
General Base ◽  
Linear Free Energy ◽  
Base Mechanism ◽  
Hydrolysis Of

The substituent effect on the chymotrypsin-catalyzed hydrolysis of several phenyl esters of specific substrates has been studied. The second-order acylation rate constants (kcat/Km(app)) obey a linear free energy relationship with ρ = +0.63 for phenyl hippurates and ρ = +0.46 for phenyl N-benzyloxycarbonyl-L-tryptophanates when substituents are introduced into the phenyl group of the ester function. These results further support the previously proposed general acid – general base mechanism for the acylation reaction and the formation of a tetrahedral intermediate in the course of the reaction.

Hydrolysis of haloacetonitriles: LINEAR FREE ENERGY RELATIONSHIP, kinetics and products

1999 ◽  
Vol 33 (8) ◽  
pp. 1938-1948 ◽  
Author(s):  
Victor Glezer ◽  
Batsheva Harris ◽  
Nelly Tal ◽  
Berta Iosefzon ◽  
Ovadia Lev
Keyword(s):  
Free Energy ◽  
Linear Free Energy Relationship ◽  
Linear Free Energy ◽  
Hydrolysis Of

scholarly journals Studies on biologically important copper(II) / manganese(II) / uranyl(II) – norvaline binary complexes

2008 ◽  
Vol 27 (2) ◽  
pp. 157 ◽  
Author(s):  
Brij Bhushan Tewari
Keyword(s):  
Stability Constants ◽  
Coordination Compounds ◽  
Metal Ion ◽  
Background Electrolyte ◽  
Binary Complex ◽  
Paper Strip ◽  
Ph Values ◽  
Binary Complexes ◽  
Stability Constants Of Complexes ◽  
The Stability

In coordination compounds studies, a knowledge of the magnitude of the stability constants of complexes is necessary for preliminary quantitative treatment. Described herein is a method that involves the use of advanced ionophoretic technique for the study of the equilibria in binary complex systems in solution. This method is based upon the migration of a spot of the metal ion on a paper strip at different pH values of background electrolyte containing 0.1 M perchloric acid and 0.01 M norvaline. A graph of pH against mobility provides information about the nature of the complexation and helps in calculating stability constants. Using this method, the stability constants of binary complexes metal(II) – norvaline have been determined to be (8.11 ± 0.02, 7.03 ± 0.09); (3.77 ± 0.11, 2.39 ± 0.07) and (7.59 ± 0.05, 6.17 ± 0.04) (log K values) for Cu(II), Mn(II) and UO2(II) complexes, respectively, at 35 ºC.

Hydrolysis of the uranyl ion in sodium nitrate medium

1982 ◽  
Vol 489 (1) ◽  
pp. 197-203 ◽  
Author(s):  
Nikola B. Mili? ◽  
Terezija M. ?uranji
Keyword(s):  
Sodium Nitrate ◽  
Uranyl Ion ◽  
Nitrate Medium ◽  
Hydrolysis Of

Using Linear Free Energy Relationship to Predict the Stability Constants of Aqueous Complexes of Metal-Organic Ligands

2004 ◽  
Vol 824 ◽  
Author(s):  
Huifang Xu ◽  
Yifeng Wang
Keyword(s):  
Free Energy ◽  
Metal Complexes ◽  
Stability Constants ◽  
Metal Cation ◽  
Dissociation Constants ◽  
Natural Environments ◽  
Linear Free Energy Relationship ◽  
Free Energies ◽  
Linear Free Energy ◽  
The Stability

AbstractThe Sverjensky-Molling linear free energy relationship was originally developed to correlate the Gibbs free energies of formation of an isostrutural family of solid phases to the thermodynamic properties of aqueous cations. In this paper, we demonstrate that the similar relationship also exists between metal complexes and simple metal cations in aqueous solutions. We extend the Sverjensky-Molling relationship to predict the Gibbs free energies of formation or dissociation constants for a family of metal complexes with a given complexing ligand. The discrepancies between the predicted and experimental data are generally less than 1.5 kcal/mol (or one log unit for stability constants). The use of this linear free energy correlation can significantly enhance our ability to predict the speciation, mobility, and toxicity of heavy metals in natural environments. According the obtained results, Gibbs free energies of formation of cations (δG0f, Mn+) can be used as an indicator for the hardness/softness of a metal cation (acid). The higher negative value of a metal cation, the harder acid it will be. It is logical to postulate that the coefficient a*ML characterizes the softness of a complexing ligand (base).

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