Search results for "CONSTANT"

Complexation of phosphine ligands with peracetylated β-cyclodextrin in supercritical carbon dioxide: spectroscopic determination of equilibrium const…

2007

The interaction between peracetylated beta-cyclodextrin and several triphenyl phosphine derivatives was studied in supercritical carbon dioxide (scCO2) by UV-visible spectroscopy. The equilibrium constant for a 1:1 complexation reaction was obtained from titration spectra and calculated using two established mathematical models. The values of the equilibrium constants are 1-3 orders of magnitude smaller than those obtained in aqueous solution with analogous phosphines. This is likely due to the absence in scCO2 of the hydrophobic effect, which is replaced by a corresponding, but weaker, CO2-phobic effect. The largest value of Kf was found for complexes of diphenyl(4-adamantylphenyl)phosphin…

Review: Solution equilibria of ternary complexes formed from copper(II), aliphatic amines, and bioligands

2014

This review provides a summary of the coordination chemistry of ligands in the ternary system: copper(II)–aliphatic amine–bioligand, where amine = ethylenediamine – En, diethylenetriamine – Dien, or N, N, N′, N″, N″-pentamethyldiethylenetriamine – Me5dien, and bioligand = selected amino acid, aminohydroxamic acid, or aminophosphonic acid, in aqueous solution. We would like to show the specific interactions of copper(II) in ternary systems in the context of complex equilibria chemistry.

Heat capacities of butanol and pentanol in aqueous dodecyltrimethylammonium bromide solutions

1987

Heat capacities of the ternary systems water-dodecyltrimethylammonium bromide (DTAB)-butanol and water-DTAB-pentanol were measured at 25°C. The standard partial molar heat capacities of pentanol in micellar solutions show a maximum at about 0.35 mol-kg−1 DTAB that has been attributed to a micellar structural transition. This maximum tends to vanish by increasing the alcohol concentration and by decreasing the alcohol alkyl chain length; in the case of butanol it was not detected. The behavior of the standard partial molar heat capacities of alcohols in micellar solutions in the region above the cmc and below the structural transition was explained using a previously reported mass-action mod…

Kinetics in a Double Antibody Radioimmunoassay (RIA): Diffussion Control

2012

Competitive protein binding radioimmunoassay (CPB-RIA) is a principal method for quantifying serum C Peptide concentration. The accuracy of this method is critically dependent on factors that influence the reaction between anti-C Peptide antibody (P) with 125I-C Peptide (M). We studied the influence of initial concentration of M, ionic strength, and viscosity on the reaction between M and P. A kinetic model for the the reaction between. Such model adjusts satisfac- torily to the results. Bi-exponential and irreversible kinetics is determined. The results of the viscosity analysis show clear negative influence on the direct reaction rate. The ionic strength shows scarce influence on equilibr…

1976

Polyoctenylenes and polydodecenylenes prepared by the methathesis reaction exhibit a bimodal molecular weight distribution. The low molecular weight fraction consists of cyclic oligomers, the high molecular weight fraction is assumed to contain linear polymers. The distribution of cyclic oligomers together with the polymer material indicates a ring-chain equilibrium. The slope of the plot log Kx (molar cyclization equilibrium constant) vs. log x (degree of polymerization) is close to −2,5 as predicted by the Jacobson and Stockmayer theory for unstrained macrocycles. Polyoctenylene und Polydodecenylene, dargestellt mit Hilfe der Metathese-Reaktion, weisen eine bimodale Molekulargewichtsverte…

1977

Methacryloyloxyalkyltrimethylammonium chlorides (1a–c) with different alkyl chain lengths were synthesized and polymerized radically with 4,4′-azobis(4-cyanovalerianic acid) and K2S2O8 as initiators. With K2S2O8 as initiator, reaction orders of 0,5 and 1 with respect to initiator and monomer, were found. For the ionic monomers with longer alkyl chains the ratio of rate constants kp(2fkd/kt)0,5 was determined over a wide concentration range. It was found that with decreasing monomer concentration the ratio of rate constants increases, which is caused by a diminished termination rate because of an increased electrostatic repulsion of the ionic polymer radicals in dilute solution (increase of …

Polymere Charge-transfer-Komplexe auf der Basis von Polyvinylalkoholacetalen

1978

Poly[2-(1-naphthyl)-1,3-dioxan-4,6-diylmethylene] (3), poly[2-(2-naphthyl)-1,3-dioxan-4,6-diylmethylene] (5), 1-naphthalenecarbaldehydetrimethyleneacetal (7) and 2-naphthalenecarbaldehydetrimethyleneacetal (8) were synthesized and characterized by UV- and fluorescencespectroscopy. In addition triplet-triplet absorption maxima and triplet-lifetimes were determined by flash technique. The naphthalene derivates were found to act as donors in the charge-transfer complex formation with such electron acceptors as tetracyanoethylene, 2,5-cyclohexadien-1,4-diylidenedimalonodinitrile and 2,4,5,7-tetranitro-9-fluorenone. The equilibrium constants of the charge-transfer complexes were determined spect…

A Novel Zeolite-Induced Population of a Planar Viologen Conformation. New Viologen Charge Transfer Complexes and Alkene/Viologen/Zeolite Arrays

2004

A rare example of a novel zeolite-induced conformational change and a mechanism for this process are suggested in order to rationalize an unexpected spontaneous intrazeolite reduction observed during preparation of a new viologen (MQ2+)-doped zeolite (NaY). In addition, the formations of six new alkene/viologen/ zeolite charge transfer (CT) arrays using NaMQY and the previously reported NaMVY are also reported. The binding constants between MQ2+ and MV2+ and 2,3-dimethyl-2-butene (TME) were determined using the Benesi-Hildebrand approach, and the stabilities of these CT complexes are compared to their intrazeolite analogue.

Speciation of trialkyltin(IV) cations in natural fluids

2004

The hydrolysis of (CH(3))(3)Sn(+), (C(2)H(5))(3)Sn(+) and (C(3)H(7))(3)Sn(+) has been studied in a Synthetic Seawater (SSW) ionic medium simulating the major composition of natural seawater, at different salinities (5 less than or equal to S less than or equal to 45), and at t = 25 degreesC. Interactions with anionic components of SSW, considered as single sea salt, are determined by means of a complex formation model. By potentiometric measurements (ISE-H(+) and ISE-F(-) electrodes), the model has been extended to also consider interactions of organotins with carbonate and fluoride ions, which are other important components of seawater. Literature and new values of hydrolysis constants in …

Intrinsic Viscosities of Polyelectrolytes: Determination and Modeling of the Effects of Extra Salt

2011

Based on early measurements of J. J. Hermans and co-workers (D. T. F. Pals, J. J. Hermans, Recl. Trav. Chim. Pays-Bas 1952, 71, 513-520; D. T. F. Pals, J. J. Hermans, J. Polym. Sci. 1950, 5, 733-734; D. T. F. Pals, J. J. Hermans, J. Polym. Sci. 1948, 3, 897-898), the present contribution demonstrates how primary data should be evaluated in order to obtain reliable intrinsic viscosities. This procedure yields detailed information on the changes of the intrinsic viscosities and of the corresponding viscometric interaction parameters caused by an increasing salinity of water. Both quantities decline from a maximum value in the pure solvent to a minimum value, which is approached in the limit o…