Modified Solubility Parameter Models

The selectivity of a number of organic modifiers was examined using the predicted log k values of the log P — 3 models from each group in different organic modifier-water mixtures. The composition of the eluent was adjusted so that either the solubility parameter,1 polarity (Po), proton acceptor (Xa), proton donor (Xd), or dipole moment (Xn) values were kept constant to determine which parameter affected the selectivity. The results are summarized in Table 4.3. 

In this table, we provide solubility parameters for some liquid solvents that can be used as modifiers in supercritical fluid extraction and chromatography. The solubility parameters (in MPa1/2) were obtained from reference 3, and those in cal1/2cm 3/2 were obtained by application of Equation 4.1 for consistency. It should be noted that other tabulations exist in which these values are slightly different, since they were calculated from different measured data or models. Therefore, the reader is cautioned that these numbers are for trend analysis and separation design only. For other applications of cohesive parameter calculations, it may be more advisable to consult a specific compilation. This table should be used along with the table on modifier decomposition, since many of these liquids show chemical instability, especially in contact with active surfaces. 

The Flory-Huggins theory has been modified and improved and other models for polymer solution behavior have been presented. Many of these theories are more satisfying intellectually than the solubility parameter model but the latter is still the simplest model for predictive uses. The following discussion will therefore focus mainly on solubility parameter concepts. 

The semibatch model GASPP is consistent with most of the data published by Wisseroth on gas phase propylene polymerization. The data are too scattered to make quantitative statements about the model discrepancies. There are essentially three catalysts used in his tests. These BASF catalysts are characterized by the parameters listed in Table I. The high solubles for BASF are expected at 80 C and without modifiers in the recipe. The fact that the BASF catalyst parameters are so similar to those evaluated earlier in slurry systems lends credence to the kinetic model. 

Within the Parameter Study Block, the algorithm is designed to test whether solubility has been exceeded or not. As a result the same model generated by ECES can be used to predict HC1 vapor pressures over unsaturated solutions of FeC12-HCl-H20 without modifying the basic program created by ECES. In a paper by Chen (17) some limited experimental data was presented on the vapor pressure of HC1 over ferrous chloride system. 

The different mixing rules and nomenclature used are described in table 1. The simplex algorithm modified by Nelder-Mead (10) is used to fit the model parameter to experimental solubility. 

Three major approaches to the prediction of aqueous solubility of organic chemicals using Quantitative Structure Activity Relationship (QSAR) techniques arc reviewed. The rationale behind six QSAR models derived from these three approaches, and the quality of their fit to the experimental data are summarized. Their utility and predictive ability are examined and compared on a common basis. Three of the models employed octanol-water partition coefficient as the primary descriptor, while two others used the solvatochromic parameters. The sixth model utilized a combination of connectivity indexes and a modified polarizability parameter. Considering the case of usage, predictive ability, and the range of applicability, the model derived from the connectivity- polarizability approach appears to have greater utility value. 

Abstract. Polyvinylalcohol (PVA) is a polymer soluble in hot water, it has the property of film formation and it can improve the concrete performance. The effects of PVA modified with nano clay on the cement hydration reaction have been investigated by means of semiadiabatic calorimeter, FTIR spectroscopy and SEM. FTIR spectroscopy was employed to monitor chemical transformation of cement. The morphology of the different samples was compared by means of SEM micrographs. With the semiadiabatic calorimeter the hydration kinetic was measured to compare the heat rate of the admixtures materials. Fixing the water-cement ratio, w/c, in 0,45, the ratio of polymer to cement (p/c) was 2 wt% and the ratio of clay to polymer was 4 wt% (0.8wt.% related to cement). The polymer and modified polymer admixtures produced a retardation effect on the kinetic of cement hydration, but the clay acts as nucleating agent. The increase of the temperature with time was measured and a new model with four parameters was employed and the kinetic parameters were determined for each sample. 

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