Chemical Engineering

Phase Equilibria by Arnold Reisman (Eds.)

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By Arnold Reisman (Eds.)

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Example text

CHOICE OF SYSTEMS AND THE REDUCED PHASE RULE Under any set of experimental conditions where one or more of the parameters, T, p, or one or more of the compositions is maintained constant, it is obvious that the variance of a system is reduced appro­ priately. In many experiments it is convenient to consider the state of a D . VAPOR PRESSURE AND EVAPORATION RATE 33 system under conditions of constant pressure. Since the pressure is not varied, the number 2 in the phase rule is reduced to the number 1 and V = C-P+\.

It is indeed the slope of the curve on a graph of free energy versus composition of component z. This variation of free energy with component quantity is termed a partial molar free energy, or chemical potential, and is generally designated μ\α). Using this notation we may rewrite Eq. (6) as dFd) = ^s^dT + V™dp + μ™ dm^ + μ£ dm^ + ···. (7) At constant T and p this reduces to dF™ = μ™ dm™ + μ™ dm™ + '" =Σ tia) dm a) \ - (8) i In a system at equilibrium made up of several phases containing i components, dF system = 0.

T h e rate of such evaporation re , 34 4 . THE THERMODYNAMIC BASIS OF THE PHASE RULE in number of evaporating particles per unit time, will be proportional to the total number of particles exposed to the environment at the surface, ne , at a given time, and a probability factor ke defining the number per unit time per unit area that will leave the surface. ke may be termed the evaporation rate coefficient or constant; r e may be termed the evaporation or volatility rate of the material. This rate, assuming that nG is a constant (the surface area is assumed constant), is the steady-state rate at which particles leave the surface of a condensed phase and enter a vapor available region.

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