Solubility parameter and the cohesive energy density

Here V" is the partial molar volume of the solute gas, and 8 and 8b are the solubility parameter values of the solute and the bulk liquid. The solubility parameter is also cohesive-energy density, a measure of the forces between the molecules given by... 

Table 8.2 Values of the Cohesive Energy Density (CED) for Some Common Solvents and the Solubility Parameter 6 for These Solvents and Some Common Polymers...

Hansen [137-139], and later van Krevelen [114] proposed the generalization of the solubility parameter concept to attempt to include the effects of strong dipole interactions and hydrogen bonding interactions. It was proposed that the cohesive energy density be written as the sum of three terms, viz. 

We encountered the quantity AE ap/V in Eq. (8-35) it is the cohesive energy density. The square root of this quantity plays an important role in regular solution theory, and Hildebrand named it the solubility parameter, 8. 

This expression is known as the cohesive energy density and in S.I. is expressed in units of megapascals. The square root of this expression is more commonly encountered in quantitative studies and is known as the solubility parameter and given the symbol 6, i.e. ... 

Figure 3.4 shows a fair correlation between vo-2ot and the Hildebrand solubility parameter 8 (linear correlation coefficient = 0.930) which makes intuitive sense. The Hildebrand parameter, which is often used to characterize liquids, is defined as the square root of the cohesive energy density (Barton 1991), while vcr2o( can be viewed as reflecting how strongly a molecule interacts with others of the same kind (Murray et al. 1994). 

The three kinds of forces described above, collectively known as the cohesive forces that keep the molecules of liquids together, are responsible for various properties of the liquids. In particular, they are responsible for the work that has to be invested to remove molecules from the liquid, that is, to vaporize it. The energy of vaporization of a mole of liquid equals its molar heat of vaporization, Ay//, minus the pressure-volume work involved, which can be approximated well by Rr, where R is the gas constant [8.3143 J K" mol" ] and T is the absolute temperamre. The ratio of this quantity to the molar volume of the liquid is its cohesive energy density. The square root of the cohesive energy density is called the (Hildebrand) solubility parameter of the liquid, 8 ... 

Solvent-polymer compatibility problems are often encountered in industry, such as in the selection of gaskets or hoses for the transportation of solvents. A rough guide exists to aid the selection of solvents for a polymer, or to assess the extent of polymer-liquid interactions. A semi empirical approach has been developed by Hildebrand based on the principle of like dissolves like. The treatment involves relating the enthalpy of mixing to a solubility parameter, S, and its related quantity, 8, called the cohesive energy density. 

FBZ precursor and can therefore be attributed to the segregated PFPE moiety. This kind of behavior is quite general for copolymers containing PFPE macromers and also in the Z1072 and Z1073 resins themselves. The driving force is the relevant difference in solubility parameters between fluorinated and nonfluorinated macromers, since the cohesive energy density (CED) of the perfluorocopolyethers is one of the smallest known. ... 

The square roots of the cohesive energy densities are given the designation have been labeled solubility parameters by Hildebrand (Hildebrand, 1949 Hildebrand and Scott, 1962). The... 

The volatility, viscosity, diffusion coefficient and relaxation rates of solvents are closely connected with the self-association of the solvents, described quantitatively by their structuredness. This property has several aspects that can be denoted by appropriate epithets (Bennetto and Caldin 1971). One of them is stiffness expressible by the internal pressure, the cohesive energy density, the square of the solubility parameter, see Chapter 3, or the difference between these two. Another aspect is openness expressible by the compressibility or the fluidity, the reciprocal of the viscosity, of the solvent (see Chapter 3). A further... 

Clearly, an objective and quantitative measure for the polarity of compounds of chromatographic interest is needed. Such a quantitative measure may be found in the solubility parameter introduced by Hildebrand [206]. The solubility parameter is defined as the square root of the cohesive energy density (c) ... 

As early as 1916 Hildebrand pointed out that the order of solubility of a given solute in a series of solvents is determined by the internal pressures of the solvents. Later Scatchard (1931) introduced the concept of "cohesive energy density" into Hildebrand s theories, identifying this quantity with the cohesive energy per unit volume. Finally Hildebrand (1936) gave a comprehensive treatment of this concept and proposed the square root of the cohesive energy density as a parameter identifying the behaviour of specific solvents. In 1949 he proposed the term solubility parameter and the symbol S. 

The Rao function has the same form as the Sugden function or Molar Parachor (Ps = My1/4/p), derived by Sugden in 1924, which correlates the surface tension with the chemical structure. Also the Small function or Molar Attraction Function, which correlates the cohesion energy density, ecoh, and the solubility parameter, 8, with the chemical structure, has this form ... 

Diffusion Theory. The diffusion theory of adhesion is mostly applied to polymers. It assumes mutual solubility of the adherend and adhesive to form a true interpliase. The solubility parameter, the square root of the cohesive energy density of a material, provides a measure of the intemiolecular interactions occurring witliin the material. Thermodynamically, solutions of two materials are most likely to occur when the solubility parameter of one material is equal to that of the other. Thus, the observation that "like dissolves like." In other words, the adhesion between two polymeric materials, one an adherend, the other an adhesive, is maximized when the solubility parameters of the two are matched ie, the best practical adhesion is obtained when there is mutual solubility between adhesive and adherend. The diffusion theory is not applicable to substantially dissimilar materials, such as polymers on metals, and is normally not applicable to adhesion between substantially dissimilar polymers. 

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