Search results for "Solution theory"
showing 10 items of 90 documents
Chain Connectivity and Conformational Variability of Polymers: Clues to an Adequate Thermodynamic Description of Their Solutions, 1
2003
This is the first of two parts investigating the Flory-Huggins interaction parameter, χ, as a function of composition and chain length. Part 1 encompasses experimental and theorical work. The former comprise the synthesis of poly(dimethylsiloxane)s with different molar mass and the measurements of their second second osmotic virial coefficients, A 2 , in solvents of diverse quality as a function of M via light scattering and osmotic pressures. The theorical analysis is performed by subdividing the dilution process into two clearly separable steps. It yields the following expression for χ ο , the χ value in range of pair interaction : χ ο = α - ζ λ. The parameter α measures the effect of con…
Spinodal lines and Flory-Huggins free-energies for solutions of human hemoglobins HbS and HbA
1991
Gelation of deoxygenated solutions of sickle-cell human Hemoglobin (HbS) is of high theoretical interest and it has serious pathological consequences. For this reason HbS is probably the most studied protein capable of self-organization. This notwithstanding, the location in the T, c plane of the region of thermodynamic instability of solutions of deoxy-HbS (as bounded by the spinodal line and as distinct from the gelation region) has remained unknown, along with related values of Flory-Huggins enthalpies and entropies. In the present work this information is derived from experiments for the two cases of (deoxy) HbS and of human adult hemoglobin (HbA). Experiments also show critical exponen…
Über die möglichkeiten zur bestimmung von mischungsenthalpien und -volumina aus der molekulargewichtsabhängigkeit der kritischen entmischungstemperat…
1977
Cloud-point curves and critical curves (Tc = f(p)) have been measured for the system trans-decahydronaphthalene/polystyrene and three different molecular weights of the polystyrene component (2,5 · 106; 3,9 · 105; 1,1 · 105). It turned out that by variation of the pressure the metastable region can be investigated up to the spinodal curve. A comparison of the theta-temperatures and the enthalpy contributions χH (to the Flory-Huggins interaction parameter χ) resulting from the measured critical temperatures according to Shultz-Flory, with the corresponding directly obtained literature data, demonstrates that, although the extrapolation of Tc to infinite molecular weight is feasible, χH obtai…
Solution properties of polyelectrolytes XII. Semi-quantitative approach to mixed electrostatic and hydrophobic polymer-gel interactions
1996
Abstract Aqueous size-exclusion chromatography of polyanions, where secondary effects affect the total separation mechanism, was investigated. For elution of polyelectrolytes on inorganic silica-based supports, the electrostatic polymer-gel repulsive interactions were evaluated through the values for a hypothetical repulsion layer, X e , according to the model developed by other workers. Using a similar procedure, the existence of an effective barrier defined as X e − X h is proposed for those systems in which electrostatic repulsion and hydrophobic interactions take place simultaneously as secondary mechanisms. X h can be viewed as a measure of the “enlargement” of the geometrical pore rad…
Viscometric study of mixtures of neutral and charged polymers in aqueous solution
1997
The viscosity behaviour of aqueous mixtures formed by a polyelectrolyte (A) and a neutral polymer (B) such as polystyrene sulfonate (PSS)-polyvinylpyrrolidone (PVP) and polylysine (PLL)-PVP has been studied at 25°C. The intrinsic viscosity and viscosity interaction parameter of each polymer in water have been determined and have served us to estimate the compatibility of the different mixtures according to two different methodologies: (i) mixtures of two polymers in water as solvent and (ii) mixtures of either polymer A OFB in a solvent formed by either polymer B or A in water ("polymer solvent method"). By comparing the experimental and theoretical viscosity data it is clearly seen that: m…
Joint Aqueous Solutions of Dextran and Bovine Serum Albumin: Coexistence of Three Liquid Phases
2014
The phase diagram of the system water/dextran (DEX)/BSA was measured as well as modeled. On the experimental side, cloud points were determined and the coexisting phases were analyzed. The theoretical calculations use an approach capable of describing solutions of chain polymers and of globular proteins with the same formalism. The required thermodynamic input comes from experiments concerning the binary subsystems, except for the polymer blend for which one interaction parameter had to be adjusted. Both sources of information yield the same essential features: the existence of a large composition area of immiscibility, starting from the subsystem DEX/BSA and extending well into the region …
Influence of Polymer Molecular Weight on Drug–polymer Solubility: A Comparison between Experimentally Determined Solubility in PVP and Prediction Der…
2015
ABSTRACT: In this study, the influence of polymer molecular weight on drug–polymer solubility was investigated using binary systems containing indomethacin (IMC) and polyvinylpyrrolidone (PVP) of different molecular weights. The experimental solubility in PVP, measured using a differential scanning calorimetry annealing method, was compared with the solubility calculated from the solubility of the drug in the liquid analogue N-vinylpyrrolidone (NVP). The experimental solubility of IMC in the low-molecular-weight PVP K12 was not significantly different from that in the higher molecular weight PVPs (K25, K30, and K90). The calculated solubilities derived from the solubility in NVP (0.31–0.32 …
Thermodynamics of copolymer solutions: how the pair interactions contribute to the overall effect.
2014
Vapor pressure measurements were performed for solutions of poly(methyl methacrylate-ran-tert-butyl methacrylate) with different weight fractions of tert-butyl methacrylate units, and their parental homopolymers in chloroform at 323 K, over a large domain of concentrations. The Flory–Huggins interaction parameters obtained from these experimental investigations show complex dependences of the Flory–Huggins interaction parameter on concentration and copolymer composition. This behavior can be modeled by taking into account an approach which considers the ability of the polymers to rearrange in a response to changes in their molecular surroundings [Adv. Polym. Sci. 2011, 238, 1–66]. According…
Solvent quality as reflected in concentration- and temperature-dependent Flory-Huggins interaction parameters
2001
Flory-Huggins interaction parameters (χ) between poly(dimethylsiloxane) (weight-average molecular weight = 152 kg/mol) and various solvents (methyl ethyl ketone, toluene and n-octane) were determined as a function of composition and temperature with vapor-pressure measurements. These data, complemented by independent information for dilute and very concentrated solutions, serve as the basis for a discussion of solvent quality via different theoretical relations. Regardless of polymer concentration, the χ values fall from methyl ethyl ketone via toluene to n-octane, the ketone being the worst solvent and the hydrocarbon being the best solvent. The variation of χ with composition and temperat…
Quick and reliable routes to phase diagrams for polyethersulfone and polysulfone membrane formation
2000
Phase diagrams were measured and calculated for the ternary membrane forming systems DMF/water/polysulfone and DMF/water/polyethersulfone at different temperatures. Customary experiments yielded cloud point curves, tie lines, and critical compositions. The theoretical computation starts from the Flory-Huggins theory and employs binary interaction parameters g ij that vary with the composition. This information was mainly obtained by means of Headspace-Gas Chromatography (HSGC, yielding the partial pressures of the volatile components); these data were complemented by light scattering and swelling experiments. The calculation of binodals, spinodals, tie lines, and critical points avoids the …