A9.1 A Statistical Mechanical Interpretation of the Entropy of Mixing in an Ideal Mixture CDA9.

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Appendix A9.1 A Statistical Mechanical Interpretation of the Entropy of Mixing in an Ideal Mixture
The entropy change of mixing for an ideal binary gaseous or liquid mixture,
mix S IM

= R

x i ln x i (A9.1-1)

= R (x 1 ln x 1 + x 2 ln x 2 )

(cf. Eq. 9.1-8 and the appropriate entry in Table 9.3-1) has a very simple statistical mechanical interpretation. To demonstrate this, we consider a collection of N1 molecules of species 1 and N2 molecules of species 2 maintained at constant total internal energy U and constant volume V . Furthermore, it is assumed either that the molecules do not interact (this is the case for an ideal gas mixture) or that the molecules do interact, but the interaction energy function is the same for all species; that is, the species 1species 1, species 2 species 2, and species 1species 2 interactions are all alike (this is the assumption that underlies the ideal mixture model). In courses on advanced physical chemistry and statistical mechanics, it is shown that the entropy function for a binary mixture at constant internal energy, volume, and number of particles is S = N1 S1,intra + N2 S2,intra + Sconf (A9.1-2)

Here Si,intra is the entropy of one molecule of species i due to its intramolecular structure (which can be calculated from detailed structural and spectroscopic information on the species), and Sconf is the entropy contribution due to the conguration of the system, that is, the way species 1 and 2 are distributed in the mixture. The statistical mechanical expression for the congurational entropy for a specic macroscopic state of the mixtures being considered here is Sconf = k ln (A9.1-3)

where is the number of different arrangements of the molecules that result in the desired macroscopic state and k is the Boltzmann constant. Our interest here is in computing the value of Sconf for different distributions of the two species within the system. To compute Sconf we will imagine that within the volume V there is a three-dimensional lattice with N = N1 + N2 equally spaced lattice points. Different macroscopic states for this model system correspond to different arrangements of the N1 molecules of species 1 and the N2 molecules of species 2 among the N lattice points. By the ideal mixture assumption, each distribution of molecules among the lattice points has the same energy as any other. The number of ways of distributing the N1 identical molecules of species 1 and the N2 identical molecules of species 2 among the N1 + N2 lattice sites in a completely random fashion is, from simple probability theory, equal to ( N1 + N2 )! N1 ! N2 ! Therefore, the congurational entropy of the completely random mixture is Sconf ( N1 + N2 )! random = k ln mixture N1 ! N2 ! (A9.1-4)

CDA9.1-2 Chapter 9: Estimation of the Gibbs Energy and Fugacity of a Component in a Mixture This equation can be simplied by using Stirlings approximation for the logarithm of a factorial number, ln M ! = M ln M M which is valid for large M . Using Eq. A9.1-5 in Eq. A9.1-4 yields Sconf random mixture = k [ln( N1 + N2 )! ln N1 ! ln N2 !] = k [( N1 + N2 ) ln( N1 + N2 ) ( N1 + N2 ) N1 ln N1 + N1 N2 ln N2 + N2 ] N1 N2 + N2 ln = k N1 ln N1 + N2 N1 + N2 = k ( N1 + N2 )[x 1 ln x 1 + x 2 ln x 2 ] (A9.1-6) (A9.1-5)

Now dividing by the sum of N1 and N2 and multiplying by Avogadros number N 23 ( = 6.022 10 ), we obtain an expression for the congurational entropy per mole of mixture S conf random mixture k [x 1 ln x 1 + x 2 ln x 2 ] = N = R [x 1 ln x 1 + x 2 ln x 2 ] (A9.1-7)

k is the gas constant of Table 1.4-1. where R = N Now consider the completely ordered conguration in which the molecules of species 1 are restricted to the rst N1 lattice sites and the molecules of species 2 to the remaining N2 lattice sites; that is, the two species are not mixed. The number of different ways in which this can be accomplished is N1 ! N2 ! =1 N1 ! N2 ! so that S conf completely = R ln 1 = 0 ordered (A9.1-9) (A9.1-8)

Therefore, the entropy change on going from the completely ordered (unmixed) state to the randomly ordered (completely mixed) state is
mix S

= S conf

random completely S conf mixture ordered

(A9.1-10)

= R [x 1 ln x 1 + x 2 ln x 2 ] which is in agreement with Eq. A9.1-1. One can easily establish, though we will not do so here, that any partially ordered state will have a molar congurational entropy intermediate to the randomly mixed and completely ordered states. Therefore, the randomly mixed state is the state of highest entropy. Since the criterion for equilibrium at constant internal energy and volume is that the entropy of the system achieve a maximum, the randomly mixed or completely disordered state is the equilibrium state in an ideal mixture. It is tempting to try to generalize this result by suggesting that the completely disordered state is always the equilibrium state. However, this is not correct! In a mixture

A9.1 A Statistical Mechanical Interpretation of the Entropy of Mixing in an Ideal Mixture CDA9.1-3 in which not all interactions are alike, different distributions of molecules among the lattice sites will result in different total energies of the system. In this case, energetic, as well as entropic, effects are important in determining the equilibrium state. Thus, in a system at constant internal energy and volume, the equilibrium state will be the state of maximum entropy (or maximum randomness) among only those states that have the required internal energy. For systems at constant temperature and volume, the equilibrium state is a state of minimum Helmholtz energy. Since A = U T S , it is evident that increasing the entropy (or disorder) in the system decreases the Helmholtz energy only if it does not simultaneously increase the internal energy of the system. For example, consider the lattice model used here, but now let u ii be the interaction energy of a species ispecies i interaction, where u 11 = u 12 = u 22 , so the mixture is not ideal. Clearly, if u 12 is greater than the arithmetic average of u 11 and u 22 , that is, if u 12 > 1 2 (u 11 + u 22 ) increasing the randomness of the mixture (and the number of 12 interactions at the expense of 11 and 22 interactions) increases both the entropy and the internal energy of the system. Therefore, the equilibrium state for this system will be that compromise between energetic and entropic effects for which the Helmholtz energy is a minimum. In real mixtures this balance between energetic and entropic effects is illustrated, for example, in liquid-liquid phase equilibrium (to be discussed in Chapter 11), in which the equilibrium state of some liquid mixtures is as two coexisting phases of different composition, a distinctly ordered rather than random state. The equilibrium state is not a single phase of uniform composition, since the increase in randomness (and hence decrease in T S ) of producing such a state from the two-phase mixture would be less than the increase in the internal energy of the system. Consequently, the random singlephase mixture would have a higher Helmholtz energy than the more ordered two-phase mixture, and therefore would not be a stable equilibrium state.