Chemical potential Polymer solutions

The subscripts 1,2,3 refer to the main solvent, the polymer, and the solvent added, respectively. The meanings of the other symbols are n refractive index m molarity of respective component in solvent 1 C the concentration in g cm"3 of the solution V the partial specific volume p the chemical potential M molecular weight (for the polymer per residue). The surscript ° indicates infinite dilution of the polymer. 

The computational problem of polymer phase equilibrium is to provide an adequate representation of the chemical potentials of each component in solution as a function of temperature, pressure, and composition. 

We have seen above in two instances, those of liquid-liquid phase separation and polymer devolatilization that computation of the phase equilibria involved is essentially a problem of mathematical formulation of the chemical potential (or activity) of each component in the solution. 

The first qualitatively correct attempt to model the relevant chemical potentials in a polymer solution was made independently by Huggins (4, ) and Flory [6). Their models, which are similar except for nomenclature, are now usually called the Flory-Huggins model ( ). 

The approach of Rory and Krigbaum was to consider an excess (E) chemical potential that exists arising from the non-ideality of the polymer solution. Then ... 

The term 6 is important it has the same units as temperature and at critical value (0 = T) causes the excess chemical potential to disappear. This point is known as the 6 temperature and at it the polymer solution behaves in a thermodynamically ideal way. 

Differentiation of Eq. (22) with respect to ri2 yields for the chemical potential of the polymeric solute relative to the pure liquid polymer as standard state... 

Fig. 120.—The chemical potential of the solvent in a binary solution containing polymer at low concentrations vi). Curves have been calculated according to Eq. (XII-26) for a = 1000 and the values of dicated with each curve. ...

The temperature at which this condition is satisfied may be referred to as the melting point Tm, which will depend, of course, on the composition of the liquid phase. If a diluent is present in the liquid phase, Tm may be regarded alternatively as the temperature at which the specified composition is that of a saturated solution. If the liquid polymer is pure, /Xn —mS where mS represents the chemical potential in the standard state, which, in accordance with custom in the treatment of solutions, we take to be the pure liquid at the same temperature and pressure. At the melting point T of the pure polymer, therefore, /x2 = /xt- To the extent that the polymer contains impurities (e.g., solvents, or copolymerized units), ixu will be less than juJ. Hence fXu after the addition of a diluent to the polymer at the temperature T will be less than and in order to re-establish the condition of equilibrium = a lower temperature Tm is required. 

With a three-component system, such as a polymer in an aqueous salt solution, preferential adsorption of one component to the polymer can affect the analysis of light-scattering data.199 Such interactions can affect the SRI. Therefore, measurements of the SRI must be made at constant chemical potential. Constant chemical potential is achieved experimentally by dialyzing the solvent and polymer solution to equilibrium through a membrane permeable to the solvent but impermeable to the polymer.199... 

Suspension Model of Interaction of Asphaltene and Oil This model is based upon the concept that asphaltenes exist as particles suspended in oil. Their suspension is assisted by resins (heavy and mostly aromatic molecules) adsorbed to the surface of asphaltenes and keeping them afloat because of the repulsive forces between resin molecules in the solution and the adsorbed resins on the asphaltene surface (see Figure 4). Stability of such a suspension is considered to be a function of the concentration of resins in solution, the fraction of asphaltene surface sites occupied by resin molecules, and the equilibrium conditions between the resins in solution and on the asphaltene surface. Utilization of this model requires the following (12) 1. Resin chemical potential calculation based on the statistical mechanical theory of polymer solutions. 2. Studies regarding resin adsorption on asphaltene particle surface and... 

Vapour pressure osmometry is the second experimental technique based on colligative properties with importance for molar mass determination. The vapour pressure of the solvent above a (polymer) solution is determined by the requirement that the chemical potential of the solvent in the vapour and in the liquid phase must be identical. For ideal solutions the change of the vapour pressure p of the solvent due to the presence of the solute with molar volume V/1 is given by... 

The crucial question is at what value of <)> is the attraction high enough to induce phase separation De Hek and Vrij (6) assume that the critical flocculation concentration is equivalent to the phase separation condition defined by the spinodal point. From the pair potential between two hard spheres in a polymer solution they calculate the second virial coefficient B2 for the particles, and derive from the spinodal condition that if B2 = 1/2 (where is the volume fraction of particles in the dispersion) phase separation occurs. For a system in thermodynamic equilibrium, two phases coexist if the chemical potential of the hard spheres is the same in the dispersion and in the floe phase (i.e., the binodal condition). 

The next problem is to find an expression for Asg. This entropy difference is a function of the particle volume fractions in the dispersion ( ) and in the floe (<(> ). As a first approximation, we assume that Ass is independent of the concentration and chain length of free polymer. This assumption is not necessarily true the floe structure, and thus < >f, may depend on the latter parameters because also the solvent chemical potential in the solution (affected by the presence of polymer) should be the same as that in the floe phase (determined by the high particle concentration). However, we assume that these effects will be small, and we take as a constant. 

It is fortunate that theory has been extended to take into account selective interactions in multicomponent systems, and it is seen from Eq. (91) (which is the expression used for the plots in Fig. 42 b) that the intercept at infinite dilution of protein or other solute does give the reciprocal of its correct molecular weight M2. This procedure is a straightforward one whereby one specifies within the constant K [Eq. (24)] a specific refractive index increment (9n7dc2)TiM. The subscript (i (a shorter way of writing subscripts jUj and ju3) signifies that the increments are to be taken at constant chemical potential of all diffusible solutes, that is, the components other than the polymer. This constitutes the osmotic pressure condition whereby only the macromolecule (component-2) is non-diffusible through a semi-permeable membrane. The quantity... 

The chemical potential of the polymer is affected by "impurities" such as solvents or copolymerized units. For an equilibrium condition in the presence of water as the diluent, the melting temperature of starch (Tm) would be lower because p in the presence of diluent is less than pi). For the starch-water system at equilibrium, the difference between the chemical potentials of the crystalline phase and the phase in the standard state (pure polymer at the same temperature and pressure) must be equal to the decrease in chemical potential of the polymer unit in solution relative to the same standard state (Flory, 1953). By considering the free energy of fusion per repeating unit and volume fraction of water (diluent), the... 

For simplicity, we have taken the volume of each segment to be the same for both types of polymers, so that 4)j and 2 volume fractions. The case of polymer solutions is the special case of A i = 1. It follows from Eq. (1.9) that the chemical potential of the second component (assumed to be crystalhzable) is given by... 

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