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The phase behavior of polymer solutions is an important property involved in the development and design of most polymer-related processes. Partially miscible polymer solutions often exhibit two solubility boundaries, the upper critical solution temperature (UCST) and the LCST, both of which depend on the molar mass and the pressure. At ...
Mixture of polymers and solvent on a lattice. Flory–Huggins solution theory is a lattice model of the thermodynamics of polymer solutions which takes account of the great dissimilarity in molecular sizes in adapting the usual expression for the entropy of mixing.
If external pressure bears on the volume as the only external parameter, this relation is: = Since both internal energy and entropy are monotonic functions of temperature , implying that the internal energy is fixed when one specifies the entropy and the volume, this relation is valid even if the change from one state of thermal equilibrium to ...
As a result, the entropy decreases in the system, ΔS p < 0 for nearly all polymerization processes. Since depolymerization is almost always entropically favored, the ΔH p must then be sufficiently negative to compensate for the unfavorable entropic term. Only then will polymerization be thermodynamically favored by the resulting negative ΔG p.
Figure 1. A thermodynamic model system. Differences in pressure, density, and temperature of a thermodynamic system tend to equalize over time. For example, in a room containing a glass of melting ice, the difference in temperature between the warm room and the cold glass of ice and water is equalized by energy flowing as heat from the room to the cooler ice and water mixture.
where T is temperature, S is entropy, P is pressure, μ is the chemical potential, N is the number of particles in the gas, and the volume has been written as V=Ax. Since the system is closed, the particle number N is constant and a small change in the energy of the system would be given by: = +
The internal energy of an ideal gas depends only on its temperature, and not on the volume of its containing box, so it is not an energy effect that tends to increase the volume of the box as gas pressure does. This implies that the pressure of an ideal gas has an entropic origin. [5] What is the origin of such an entropic force?
The entropy of a closed system, determined relative to this zero point, is then the absolute entropy of that system. Mathematically, the absolute entropy of any system at zero temperature is the natural log of the number of ground states times the Boltzmann constant k B = 1.38 × 10 −23 J K −1.