Search results for "dilution"
showing 10 items of 242 documents
An Alternate Interpretation of Polymer/Solvent Jump Size Units for Free-Volume Diffusion Models
1996
Polystyrene/toluene mutual-diffusion coefficients have been measured as a function of temperature in the limit of infinite solvent dilution. The solvent to polymer jump size unit ratio (ξ) was determined from the Vrentas−Duda free-volume diffusion model for polymer self-diffusion and is in excellent agreement with values evaluated from solvent self- and binary mutual-diffusion coefficient data. Comparison of the free-volume model to a version of the Kirkwood−Riseman theory, modified for diffusion at infinite dilution under non-ϑ conditions, suggests that ξ follows the temperature dependence of the root-mean-squared end-to-end distance of the polystyrene and can be estimated without the use …
Multivalent ion-exchange model of biopolymer chromatography for mass overload conditions
1991
Abstract The simple model of multivalent ion-exchange biopolymer chromatography is analyzed on the basis of classical quasi-chemical temperature. The rigorous isotherm equation deduced from the stoichiometric displacement model (SDM) was used to stimulate the migration of a solute through the chromatographic column in the isocratic and gradient elution modes. The peak profiles generated for various sample sizes were compared with those obtained on the basis of a Langmuir isotherm. Peak tailing increases with the value of the exponent Z, defined as the ratio of the protein valency to the displacing counter-ion valency. For large Z the asymmetries due to the non-linearity of the isotherm are …
Polyelectrolytes Revisited: Reliable Determination of Intrinsic Viscosities
2007
The linear extrapolation of (hh0)/(h0c) towards c !0 constitutes the basis of traditional methods to determine intrinsic viscosities (h), where h is the viscosity of polymer solutions of concentration c and h0 is the viscosity of the pure solvent. With uncharged macromolecules this procedure works well; for polyelectrolytes it fails because of the pronounced non-linearity of the above dependence at high dilution resulting from the increasing electrostatic inter- actions. This contribution presents a new method for the determination of (h). It rests upon the application of the laws of phenomenological thermodynamics to the viscosity of polymer solutions and introduces a generalized intrinsic…
Interrelation between the thermodynamic and viscometric behaviour of aqueous solutions of hydrophobically modified ethyl hydroxyethyl cellulose
2000
Abstract Aqueous solutions of a commercial sample of hydrophobically modified ethyl hydroxyethyl cellulose (HC, Mw=100 kg/mol, nonylphenol substitution ca. 1.7 mol%) were studied with respect to their demixing behaviour and flow characteristics. Phase separation temperatures were measured turbidimetrically and by determining the first discernible macroscopic phase separation. In some cases demixing was also monitored viscometrically. Phase volume ratios yielded a critical polymer concentration of 1.87 wt.% HC (displaced considerably out of the minimum of the demixing curve towards higher polymer concentrations) and a lower critical solution temperature of 47°C. Model calculations of the spi…
Thermodynamics of binary mixtures: Volumes, heat capacities, and dilution enthalpies for then-pentanol+2-methyl-2-butanol system
1983
The densities, heat capacities, and dilution enthalpies ofn-pentanol+2-methyl-2-butanol mixtures have been measured, in many cases as a function of temperature, over the complete mole fraction range. Excesses thermodynamic properties, apparent and partial molar heat capacities, volumes and expansibilities were derived. The concentration and temperature dependences of these functions are discussed in terms of the variations of the structure of the system caused by the participation of the two alcohol molecules (with quite different steric hindrance of the alkyl chain around the-OH group) in the dynamic intermolecular association process through hydrogen bonding.
Determination of zirconium traces in polymers by ICP-IDMS - a powerful and fast method for routine testing of zirconium residues in polyolefins
1999
Zirconium trace analyses play an important role for polyolefins produced by modern catalytic processes with zirconium metallocenes. A reliable and fast routine testing method by inductively coupled plasma isotope dilution mass spectrometry (ICP-IDMS) was therefore developed, which allows the determination of zirconium in polymers down to the low ng/g level. With respect to its precision, accuracy, and time-consumption this method is suitable for routine testing of production processes. A spike solution, enriched in the stable isotope 91Zr, was prepared and used for the isotope dilution procedure, which has the advantage of being an internal “one point” calibration method. The polyolefin sam…
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…
Validation of Methylmercury Determinations in Aquatic Systems by Alkyl Derivatization Methods for GC Analysis Using ICP-IDMS
2001
Isotope dilution mass spectrometry (IDMS), using an inductively coupled plasma quadrupole mass spectrometer (ICPMS) and a species-specific methylmercury spike was applied to validate the commonly used GC method for methylmercury (MeHg+) determination, which is based on the formation of volatile methylethylmercury by derivatization with NaBEt4. The spike compound, Me201Hg+, was synthesized by reaction of 201Hg-enriched mercury chloride with methylcobalamin. By analyzing different environmental aquatic samples, it was found that in most cases, transformation of MeHg+ into elemental mercury (Hg0) took place. From investigations of synthetic solutions, it could be followed that halide ions are …