Search results for "CONST"
showing 10 items of 7706 documents
Binding between (Ethylene Oxide)13−(Propylene Oxide)30−(Ethylene Oxide)13 and Sodium Decanoate. Volume, Enthalpy, and Heat Capacity Studies
2002
Volume, enthalpy, and heat capacity of transfer (ΔYt) of (ethylene oxide)13−(propylene oxide)30−(ethylene oxide)13 (L64), at some concentrations, from water to the aqueous sodium decanoate (NaDec) solutions as functions of the surfactant concentration (mS) were determined at 298 K. The copolymer was studied in both the unassociated and associated forms. For a given L64 concentration (mC), the ΔYt vs mS profiles for the volume and the enthalpy are equal but different from that of the heat capacity because the latter contains also the relaxation terms. The experimental data were analyzed by assuming the distribution of L64 between the aqueous and the micellar phases and the shift of micelliza…
Heat Capacity of Transfer of (Ethylene oxide)13-(propylene oxide)30-(ethylene oxide)13 from Water to the Aqueous Anionic Surfactant Solutions at 298 …
2004
Heat capacities of transfer (ACpt) of unimeric (ethylene oxide)(13)-(propylene oxide)(30)-(ethylene oxide)(13) from water to the aqueous surfactant solutions as functions of the surfactant concentrations (m(S)) were determined at 298 K. The surfactants investigated are sodium hexanoate, sodium heptanoate, sodium octanoate, sodium undecanoate, and sodium dodecanoate. For short alkyl chain surfactants, the profiles of the DeltaCp(t) versus ms curves show maxima and minima; for long alkyl chain surfactants, the maximum becomes sharper and moved to lower ms values whereas the minimum tends to disappear. These experimental trends are different from those of the enthalpy in agreement with the fac…
Thermodynamics of Solubilization of Pentanol in Sodium Dodecyl Sulfate-Dodecyldimethylamine Oxide Mixed Micelles
1994
Abstract Heat capacity and density measurements of pentanol (PeOH)-sodium dodecyl sulfate (NaDS)-dodecyldimethylamine oxide-water mixtures were carried out at 0.03 m PeOH as a function of the total surfactants concentration (mc) at different ratios (XNaDS). From experimental data, the apparent molar volumes (VΦ,R) and heat capacities (CΦ,R) of PeOH in the surfactants mixture solutions were calculated. As a general feature, at a given mixture composition, VΦ,R increases monotonically with mt as observed in pure surfactants. In the cases of XNaDS = 0.1 and 0.3, VΦ,R drops at about 0.1 and 0.15 mt respectively. The decreasing CΦ,R VS mt curve shows peculiarities which were ascribed to the pres…
Thermodynamics of transfer of some nitroalkanes from aqueous to dodecyltrimethylammonium bromide micellar phases
1988
Abstract The enthalpies of mixing of some aqueous n-nitroalkane solutions with dodecyltrimethylammonium bromide micellar solutions were determined. The experimental data were treated by using a previously reported approach giving the enthalpies of transfer of solute from the aqueous to the micellar phases and the distribution constant of solute between the two phases at the same time. From these, the standard thermodynamic quantities of transfer (ΔtrfG°, ΔtrfH° and ΔtrfS°) are derived. In order to study the effect of the nature of both the solvent and the head group of solute, these properties are compared with those from water to octane and with those of alcohols and nitriles from aqueous …
Compounds of tungsten(VI) with citric acid: A spectrophotometric, polarimetric and hydrogen-1, carbon-13 N.M.R. study of the formation and interconve…
1986
Tungsten(VI)-citrate complexes, which occur in aqueous solution, were studied by polarimetric and absorbance measurements. The pH of the medium is the principal variable controlling complex formation and interconversion equilibria. At high pH (>6), the stable complexes are monomers with 1∶2 and 1∶1 stoichiometry, depending on the tungsten(VI)-citrate ratio, while at lower pH two different dinuclear complexes are formed. The intervals of existence of these species with the pH, the number of equivalents of acid necessary for their formation, as well as the conditional stability constant, have also been calculated. The structure of these compounds have been investigated by1H and13C-n.m.r. spec…
Complexes of molybdenum(VI) with organic diacid ligands: The molybdenum(VI)-malonic acid system
1983
Malonic acid (C3O4H4) and MoVI form in aqueous solution two dinuclear dioxo-complexes of which the stability is a function of the pH of the medium. Both complexes have a 1∶1 metal-ligand stoichiometric ratio, and the interconversion may involve a structural rearrangement. Conditional dissociation constants have been determined spectrophotometrically. Saline cryoscopy supports the spectrophotometric results. Salts of [Co(en)3]3+ have been isolated. The ligand behaviour of malonic acid differs partially from that observed for α-polyhydroxy ligands.
Complex formation equilibria between the acetazolamide ((5-acetamido-1,3,4-thiadiazole)-2-sulphonamide), a potent inhibitor of carbonicanhydrase, and…
1990
Abstract The stability constants for the equilibrium of complexation between acetazolamide and the divalent metal ions copper(II), nickel(II), zinc(II), and cobalt(II) have been determined by potentiometry both in water and in water-ethanol 50 vol. % solutions in 0.15 mol dm −3 NaNO 3 at 25°C. This mixed solvent has been used in order to obtain higher concentrations of acetazolamide in solution. For copper(II) and nickel(II), the binuclear species [Cu 2 (Acm) 2 ] and [Ni 2 (Acm) 3 ] 2− are detected in both solvents together with hydroxo species. The values of the stability constants are always higher in the mixed solvent than in water. For cobalt(II) and zinc(II), while in aqueous solution …
A simple model for barrier frequencies for enzymatic reactions.
2010
We present a simple model to rationalize the effects of environment on the reaction barrier frequencies derived from free energy profiles. These frequencies are relevant in deviations of a rate constant from its transition state theory value and in determining which environmental dynamics participate in the reaction. In particular, this simple model can be used to understand the changes in the reaction barrier frequencies of an enzymatic catalyzed reaction and the corresponding uncatalyzed process in aqueous solution, a change which has implications for dynamical environmental effects on the enzymatic reaction. Two possible cases are analyzed, in which the polarity (charge separation/locali…
Selective recognition of fluoride anion in water by a copper(II) center embedded in a hydrophobic cavity
2014
The ability of a water-soluble pentacationic calix[6]arene-based CuII complex to bind anions in water has been explored. Quite remarkably, the complex exhibits strong and selective fluoride binding in the pH range of 6–7. The binding constant at pH 5.9 was evaluated to be 85 000 M−1, which is one of the highest values ever reported for a fluoride probe in water and at this pH. The complex also binds chloride ions, but 1000 times less efficiently. The combination of the calix[6]arene hydrophobic cavity with the CuII complex, presenting its labile site in the endo position, is the reason for the selective recognition process. The single crystal X-ray structure of the organo-soluble parent com…
Speciation of low molecular weight ligands in natural fluids: protonation constants and association of open chain polyamines with the major component…
2000
Abstract The interaction of five open chain polyamines (ethylenediamine (en), diethylenetriamine (dien), trietylenetetramine (trien), tetraethylenepentamine (tetren), spermine (sper)) with the major components of seawater was studied potentiometrically at 25°C, in an artificial seawater (containing Na+, K+, Mg2+, Ca2+, Cl− and SO42−) at different salinities (5–45‰). Potentiometric data were interpreted in terms of both the apparent protonation constants of polyamines and the formation constants of complexes formed by unprotonated or protonated amines and the cation and the anion of seawater (the inorganic content of seawater being considered as a single 1:1 salt). Some empirical relationshi…