22 22.1 A definition of the chemical potential 282 22.2 The meaning of the chemical potential 233, 22.3 Grand partition function 285 22.4 Grand potential 236 22.5 Chemical potential as function per particle 22.6 Many types of particle 238 22.7 Particle number conserva- ion laws 239 22.8 Chemical potential and chemical reactions 240 Chapter summary 245, Further reading 245, Exercises 246 If we are dealing with discrete par- ticles, then NV is an integer and can only change by integer amounts; hence using calculus expressions like dN is a bit sloppy, but this is an indiscre tion for which we may be excused if N is lange. However, there exist aye tems such as quantum dats which are setniconductor nanocrystals whose size isa fow nanometres. Quantum dots are so small that 4. jumps discontinuous when you add one electron to the quat tum dot The chemical potential We now want to consider systems which can exchange particles with their surroundings and we will show in this chapter that this feature leads to a new concept known as the chemical potential. Differences in the chemical potential drive the flow of particles from one place to another in much the same way as differences in temperature drive the flow of heat. The chemical potential turns up in chemical reactions (hence the name) because if you are doing a reaction such as 2H + O2 > 2H20, (22.1) you are changing the number of particles in your system (3 molecules on the left, 2 on the right). However, as we shall see, the chemical potential applies to more than just chemical systems. It is connected with con servation laws, so that, particles such as electrons (which are conserved) and photons (which are not) have different chemical potentials and this has consequences for their behaviour. 22.1 A definition of the chemical potential If you add a particle to a system, then the internal energy will change by an amount which we call the chemical potential 1. Thus the first and second laws of thermodynamics expressed in eqn 14.18 must, in the case of changing numbers of particles, be modified to contain an extra term, so that aU = Tas — paV + pan, (22.2) where N is the number of particles in the system. This means that we can write an expression for jx as a partial differential of U as follows: (2) Be ON) sy However, keeping $ and V constant is a difficult constraint to apply, so it, is convenient to consider other thermodynamic potentials. Equation 22.2 together with the definitions F = U — TS and G = U + pV —TS imply that, (22.3) aP ag —paV ~ SAT + pAN, Vdp — SdT + pan, (22.4) (22.5)22.2 The meaning of the chemical potential 233 and hence we can make the more useful definitions: ne GR, or (22.6) ‘The constraints of constant p and 7’ are experimentally convenient for chemical systems and so eqn 22.7 will be particularly useful. 22.2 The meaning of the chemical potential What drives a system to form a particular equilibrium state? As we have seen in Chapter 14, it is the second law of thermodynamics which states that entropy always increases. The entropy of a system can be considered to be a function of U, V and N, so that $ = S(U,V.N) ‘Therefore, we can immediately write down ds= (i) au =) aN, (228) T) vy aa Equation 22.2 implies that i Vv pd’ as = 0, Pav _ pa (22.9) TT TF Comparison of eqn 22.8 and 22.9 implies that we can therefore make the following identifications: (ar) ay (Be )aeB (Be)ow™ Now consider two systems which are able to exchange heat or particles between them. If we write down an expression for dS, then we can use the second law of thermodynamics in the form dS > 0 to determine the equilibrium state. We repeat this analysis for two cases as follows: # Fe (22.10) © The case of heat flow Consider two systems which are able to exchange heat with each other while remaining thermally isolated from their surroundings Ty, aw T (see Fig. 22.1). Ifsystem 1 loses internal energy dU, system 2must_ |, - v, gain internal energy dU. Thus the change of entropy is 1 2 to exchange heat with each other. (22.11)234 The chemical potential TY av Ty i _ be My Np Fig. 22.2 Two systems which are able to exchange particles with each other So dU > 0, ie. energy flows from 1 to 2, when Ty > Ta. As expected, equilibrium is found when T, = Tz, i.e. when the tem- peratures of the two systems are equal. © The case of particle exchange Now consider two systems which are able to exchange particles with each other, but remain isolated from their surroundings (see Fig. 22.2), If system 1 loses dV particles, system 2 must gain dV particles. Thus the change of entropy is » _ (a . dS, as = (Fer), (See) ( 0 (so that particles flow from 1 to 2) when pty > plz. Similarly, if ji < yu, then dN < 0. Hence equilibrium is found when jy = p12, ie. when the chemi- cal potentials are the same for each system. This demonstrates that chemical potential plays a similar réle in particle exchange as 1/temperature does in heat. exchany oOo Example 22.1 Find the chemical potential for an ideal gas, Solution: We use eqn 22.6 (11 = (9F/AN)v,r), which relates ps to F, together with eqn 21.36, which gives an expression for F, namely F = NkpT[n(nd3,) — (22.13) Recalling also that n = N/V, we find that w= kpT[ln(nd§,) — 1] + NkpT ( (22.14) and hence 1 = kT n(n.) (22.15) In this case, comparison with eqn 21.38 shows that yu = G/N. We will see in Section 22.5 that this property has more general applicability than juust this specific case. ee oOoOoOw22.3. Grand partition function In this section we will introduce a version of the partition funetion we met in Chapter 20 but now generalized to include the effect of variable numbers of particle, To do this, we have to generalize the canonical ensemble we met in Chapter 4 to the case of both energy and particle exchange. Let us write the entropy $ as a function of internal energy U and particle number V. Consider a small system with fixed volume V and with energy ¢ and containing V particles, connected to a reservoir with energy U—e and A’—N particles (see Fig, 22.3). We assume that U > and NV > N. Using a Taylor expansion, we can write the entropy of the reservoit as ran as as . (2) (Dey ; (yy (2236) and using the differentials defined in eqn 22.10, we have that S(U-¢N-N) nd S(U~6.N-N) = SUN) ~ 7(e~ HN) (22.17) ‘The probability P(c, N) that the system chooses a particular macrostate is proportionality to the number (2 of microstates corresponding to that microstate, and using S = ky In? we have that P(6,N) 0x eU#N NI 3c saN=8) (22.18) This is known as the Gibbs distribution and the situation is known as the grand canonical ensemble. In the eas to the Boltzmann distribution (the canonical ensemble). Normalizing this distribution, we have that the probability of a state of the system with energy B; and with N, particles is given by in which ju = 0, this reverts (22.19) where Z is a normalization constant. The normal known as the grand partition function Z, which we write as follows: Z= Lown which is a sum over all states of the system. ‘The grand partition function Z can be used to derive many thermodynamic quantities, and we write down the most useful equations here without detailed proof? T (32). (22.21) (22.22) ation constant is (22.20) 22.3 Grand partition function 236 € U-e N N-n pO reservoir system, Fig, 22.3 A small system with energy ¢ and containing NV particles, connected to a reservoir with energy U —¢ and NN particles. See Rxercise 22.4236 The chemical potential and S=—ky DO PinP; -l (22.23) For convenience, let us summarize the various ensembles considered in statistical mechanics, (1) The microcanonical ensemble: an ensemble of systems which ) all have the same fixed energy. The entropy S is related to the number of microstates by $= kg ln, and hence by (22.24) The canonical ensemble: an ensemble of systems, each of which can exchange its energy with a large reservoir of heat. As we shall see, this fixes (and defines) the temperature of the system. Since F = —kgT'lnZ, the partition function is given by ZaeFF, (22.25) where F is the Helmholtz function, ‘The grand canonical ensemble: an ensemble of systems, each of which can exchange both energy and particles with a large reser- voir. This fixes the system’s temperature and chemical potential. By analogy with the canonical ensemble, we write the grand par- tition function as Zae hte (22.26) ss in the next where ®q is the grand potential, which we dis section 22.4 Grand potential Using eqn 22.26, we have defined a new state function, the grand poten- tial Bq, by Oo = ky Tn (22.27) Rearranging eqn 22.23, we have that pT InZ TS (22.28) and hence Bq =U-TS—pN=F- (22.29) ‘The grand potential has differential d&q given by d&g = dF — dN — Nap, (22.30) and, substituting in eqn 22.4, we therefore have dBq = —SaT — paV — Nap, (22.31)