Solubility parameter experimental

Table 2.16 Solubility parameters, experimental and calculated, for various common polymers at 298 K. All 5 values are in (J/mL) the calculated values have a nominal error of 0.8 (J/mL) ...

Appendices are provided that include Maxwell s relations, the five laws of thermodynamics, and group contributions to calculate solubility parameters. Experimental methods to measure the binary interaction parameters, solubility parameters and heat capacity changes at glass transition are discussed. 

When viscometric measurements of ECH homopolymer fractions were obtained in benzene, the nonperturbed dimensions and the steric hindrance parameter were calculated (24). Erom experimental data collected on polymer solubiUty in 39 solvents and intrinsic viscosity measurements in 19 solvents, Hansen (30) model parameters, 5 and 5 could be deterrnined (24). The notation 5 symbolizes the dispersion forces or nonpolar interactions 5 a representation of the sum of 8 (polar interactions) and 8 (hydrogen bonding interactions). The homopolymer is soluble in solvents that have solubility parameters 6 > 7.9, 6 > 5.5, and 0.2 < <5.0 (31). SolubiUty was also determined using a method (32) in which 8 represents the solubiUty parameter... 

The solubility parameter is thus an experimentally determinable property although special methods are necessary with polymers, which cannot normally be vaporised without decomposition. Such methods are discussed in Section 5.3.3. 

Tseng et al. [164] suecessfully used UNIFAC to optimize polymer-solvent interactions in three-solvent systems, determining polymer activity as a function of the solvent eomposition. The composition yielding the minimum in polymer aetivity was taken as the eriterion for optimum interaetion, and it eompared well with experimental measurements of dissolution rate and solution clarity. Better agreement was obtained using UNIFAC than using solubility parameter methods. 

In this approach, connectivity indices were used as the principle descriptor of the topology of the repeat unit of a polymer. The connectivity indices of various polymers were first correlated directly with the experimental data for six different physical properties. The six properties were Van der Waals volume (Vw), molar volume (V), heat capacity (Cp), solubility parameter (5), glass transition temperature Tfj, and cohesive energies ( coh) for the 45 different polymers. Available data were used to establish the dependence of these properties on the topological indices. All the experimental data for these properties were trained simultaneously in the proposed neural network model in order to develop an overall cause-effect relationship for all six properties. 

Experimental data for Van der Waals volumes Molar volumes Heat capacities Solubility parameter and glass transition temperature... 

The solubility parameter is thus an experimentally determinable property, at least for low molecular weight materials, and a number of methods have been reviewed by Burrell". In the case of polymers which cannot normally... 

Calculated Solubility Parameter and Experimental Oil Swell for a Variety of Rubbers... 

The promising approach taken by Vandenburg et al. [37,489] is to use initially a solvent with a Hildebrand solubility parameter several MPa1/2 different from the polymer (i.e. a poor , nonswelling solvent for the polymer) to determine experimentally the maximum... 

The most important aspect of the simulation is that the thermodynamic data of the chemicals be modeled correctly. It is necessary to decide what equation of state to use for the vapor phase (ideal gas, Redlich-Kwong-Soave, Peng-Robinson, etc.) and what model to use for liquid activity coefficients [ideal solutions, solubility parameters, Wilson equation, nonrandom two liquid (NRTL), UNIFAC, etc.]. See Sec. 4, Thermodynamics. It is necessary to consider mixtures of chemicals, and the interaction parameters must be predictable. The best case is to determine them from data, and the next-best case is to use correlations based on the molecular weight, structure, and normal boiling point. To validate the model, the computer results of vapor-liquid equilibria could be checked against experimental data to ensure their validity before the data are used in more complicated computer calculations. 

Although being qualitatively in agreement with experimental results, disagreements between experiment and theory remain. Besides the composition, /a, and the total degree of polymerization, N, all theoretical works refer to the segmental interaction parameter x This parameter can be estimated from a relationship to the solubility parameters. The ODT as a thermodynamic measure of the incompatibility was used to compare a set of symmetrically composed diblock copolymers from different hydrocarbons, polydimethyl-siloxane and poly(ethylene oxide) (PEO) [33]. While the behaviour of hydrocarbon diblock copolymers was successfully described by a consistent set of solubility parameters, this procedure failed for systems containing PEO. The... 

Once the local parameters have been fitted to a limited set of data then solubilities can be calculated in a representative set of solvents. Plotting the experimental and predicted data against the Hildebrand solubility parameter of the solvent gives a veiy good indication of behaviour with solvent type, figure 19. The application of the SoluCalc method to Cimetidine is briefly presented in Section 6. 

Knowing the fullerene molar volume, either the experimental or the calculated value, it is quite straightforward the calculation of the solubility parameter by substituting the tabulated group increments in equation (13.6). 

The calculated solubility parameter derived from the Van Krevelen approach has been compared with the experimental solubility parameters of C60 and C70 reported in the literature and derived experimentally. An excellent agreement has been found between the calculated and the experimental <5d values. A comparison with the calculated solubility parameter of the vegetable oils, under certain conditions, permits to show that a good solubility of fullerenes in glycerol esters of fatty acids can be expected. Fulleiene solubility in molten free fatty acids can be predicted on the basis of solubility parameters comparison and it has been verified by dissolving C60 and C70 in molten fatty acids. 

Experimental data on Op and On for different polymer materials exhibit unique correlations with (hydrogen bonding) and 6(j (dispersion) components respectively of solubility parameter 6gp of polymer (53,60) which can be calculated from data on structural group contributions to and available in the literature (61). The existence of such correlations (Figures 9(a) and 9(b)) indicate that LSC data can be used to characterize the chemical nature of polymeric membrane materials. 

The solubility parameter concept predicts the heat of mixing liquids and amorphous polymers. It has been experimentally found that generally any nonpolar amorphous polymer will dissolve in a liquid or mixture of liquids having a solubility parameter that generally does not differ by more than 1.8 (cal/cc) /. The Hildebrand (H) is preferred over these complex units, giving as a general difference 1.8 H. 

The selection of a solvent for a new separation problem, even today, is a matter of trial and error. The application of theory (2) with the additional application of the solubility parameters (6J-65) makes it possible to estimate the composition of appropriate solvent mixtures for the separation of relatively simple compounds. In order to calculate the necessary solvent strength, however, a set of experimental data concerning the behavior of the sample components, the adsorbent, and the elution strength of the eluents with the specific adsorbent are necessary. Others (J5) recommend a graphical method as a time-saving alternative to bi th calculation and the trial-and-error approach to obtain a first approximation of the eluent composition appropriate for the separation of a givin sample. 

Values of the activity coefficients are deduced from experimental data of vapor-liquid equilibria and correlated or extended by any one of several available equations. Values also may be calculated approximately from structural group contributions by methods called UNIFAC and ASOG. For more than two components, the correlating equations favored nowadays are the Wilson, the NRTL, and UNIQUAC, and for some applications a solubility parameter method. The fust and last of these are given in Table 13.2. Calculations from measured equilibrium compositions are made with the rearranged equation... 

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