Polymer solutions, thermodynamics

Chemical process rate equations involve the quantity related to concentration fluctuations as a kinetic parameter called chemical relaxation. The stochastic theory of chemical kinetics investigates concentration fluctuations (Malyshev, 2005). For diffusion of polymers, flows through porous media, and the description liquid helium, Fick s and Fourier s laws are generally not applicable, since these laws are based on linear flow-force relations. A general formalism with the aim to go beyond the linear flow-force relations is the extended nonequilibrium thermodynamics. Polymer solutions are highly relevant systems for analyses beyond the local equilibrium theory. 

Before concluding this section, there is one additional thermodynamic factor to be mentioned which also has the effect of lowering. Since we shall not describe the thermodynamics of polymer solutions until Chap. 8, a quantitative treatment is inappropriate at this point. However, some relationships familiar from the behavior of low molecular weight compounds may be borrowed for qualitative discussion. The specific effect we consider is that of chain ends. The position we take is that they are foreign species from the viewpoint of crystallization. 

We shall discuss three types of phenomena for polymer solutions thermodynamic properties in Chap. 8, frictional properties in Chap. 9, and lightscattering properties in Chap. 10. A common feature of virtually all phenomena in these areas is that they all depend on the molecular weight of the solute. Thus observations of these properties can be interpreted to yield values for M we shall use this capability as a unifying theme throughout these chapters. 

In Chap. 8 we discuss the thermodynamics of polymer solutions, specifically with respect to phase separation and osmotic pressure. We shall devote considerable attention to statistical models to describe both the entropy and the enthalpy of mixtures. Of particular interest is the idea that the thermodynamic... 

The title of this chapter is somewhat misleading. In one sense it is too broad, in another sense too restrictive. We shall really discuss in detail only the phase separation and osmostic pressure of polymer solutions a variety of other thermodynamic phenomena are ignored. In this regard the chapter title would better read Some aspects of. . . . Throughout this volume only a small part of what might be said about any topic is actually presented, so this modifying phrase is taken to be understood and is omitted. 

In addition to thermodynamic appUcations, 62 values have also been related to the glass transition temperature of a polymer, and the difference 62-61 to the viscosity of polymer solutions. The best values of 6 have been analyzed into group contributions, the sum of which can be used to estimate 62 for polymers which have not been characterized experimentally. 

L. Schafer, T. A. Witten. Renormalization field theory of polymer solutions. I. Scaling laws. J Chem Phys 66 2121-2130, 1977 A. Knoll, L. Schafer, T. A. Witten. The thermodynamic scaling function of polymer solution. J Physique 42 161-m, 1981. 

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