Physics 347 Problem Set 3 due: Oct.

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11. The Gibbs Free Energy:
There is another “free energy,” which I did not discuss in class. The Gibbs free energy
and is defined as G " E # TS + PV = G (T,P, N ) and has T,P,N as its natural variables.
Note: For a system in contact with both a thermal reservoir and a pressure reservoir
(i.e., one kept at constant T and P) the Gibbs free energy tends to a minimum.
(a) Starting from the basic properties of the entropy, S(E,V,N),
1! P µ
dS = dE + dV " dN , show that dG = "SdT + VdP + µdN .
T T T
(b) Using the Euler relation and the Gibbs-Duhem relation (Lect. 14.2), show that
G(T,P, N ) = Nµ (T,P ) .
(c) Now, suppose that there!are several types of particles in the system, N1, N 2 ,....
!
Show that these results generalize to dG(T,P,{N k }) = "SdT + VdP + # µ k dN k and
k
! G(T,P,{N k }) = " N k µ k (T,P,{N k }) .
k !
Note that the chemical potential µ k for the kth type of particle can now depend on the
numbers {N k } (in addition!to T and P) but only on ratios like N1/N2, etc., since
! chemical potential is intensive.
(d) Using class results, find the formula for the Gibbs free energy for the ideal
!
classical monatomic gas and verify that it has the derivatives implied by (a).
!
12. Ligand-Receptor binding for the ideal gas.
In class (Lect. 12), I solved for you the problem of ligand-receptor binding in a
simplified lattice model. The result (at low densities) was that the probability of
[L] N
binding could be written PB = where [ L ] " L is the ligand density and
1 "#$ V
e + [ L]
v0
v0 is the volume per cell.
In this problem, I want you to treat the NL ! ligand molecules as an ideal monatomic
classical gas in which there are two classes of states, those with all ligands moving
!
freely in the volume V and those with only NL-1 free and one bound to the receptor
with a binding energy "# = $# B (# B > 0) . Show for this situation that
[L]
PB = , where instead of the cell volume v0 there appears the cube of the
1 #$%
e + [L]
"3t !
$ 2 #h 2 '1/2
“thermal wavelength” defined by " t = && )) (see Lect. 14.4).
mk
% B ( T
! 13. Maxwell Distribution for an ideal gas in an external potential.
Consider an ideal gas of N particles in a box of volume V whose molecules are subject
r
to a spatially non-uniform potential U (r ) . Assume that the whole system is in contact
!
 with a thermal reservoir at temperature T, so it can be described page 2
by the canonical distribution. Because of the potential, the particles will no longer be
distributed uniformly over V.
(a) Starting from the full N-particle canonical distribution, show that the probability
distribution for observing a particular particle (say, particle “1”) in the volume (d3r)
1 # p2 r &
" %% +U ( r )((
r r r r k B T $ 2m
( )( )
and with momentum in (d3p) is P(r , p) d 3r d 3 p with P (r , p) ~ e ' .
What is the normalization factor?
(b) Specialize this result to particles in a box of volume V=AH (H is the height and A
r
s the base area) which sits in a gravitational potential
! U (r ) = mgz so that z=0 is the
!
bottom of the box and z=H is the top. Show that the density of particles inside the box
as a function of the height is
N H e#z /H 0 k T
n( z ) = " " , where H 0 = H !0 (T ) $ B is called the scale height.
V H 0 1 # e#H /H 0 mg
Note: This is called the “gravitational distribution.” You can see that the gas is denser
at the bottom of the box than at the top. When T is large and/or m is small so H0
becomes >>H, n(z) approaches the uniform distribution N/V.
! (c) Calculate the scale height for the atmosphere at 0o C (take m to be the mass of an
N2 molecule).
14. PKT Problems.
(a) PKT Problem 5.5(a) (p. 212)
(b) PKT Problem 5.7 (p. 213)
15. An atom has three possible states which we label n = 0,1,2 with corresponding
energies " n = n# . Consider a set of N (distinguishable) atoms of this type. Such a set
of atoms can have a total energy between E = 0 (all atoms in the n=0 state) and
E = 2N" (all atoms in the n=2 state).
!
(a) To get a feeling for what is going on, suppose N=4 and consider a microcanonical
!ensemble with a known total energy E = 4" . What is the average number of atoms
!
N n in each of the three states n = 0,1,2 ?
!
(b) Now, suppose that N>>1. What are the averages N n , if it is known that
E = N" ? Again, assume a!microcanonical ensemble.
Note: Assume that N ! is divisible by 4 for simplicity.
!
Hint: Just as in part (a), you will need to figure out the combinatorial expression for
the number of different “microstates” with N! 1,N2,N3 and then use the Stirling formula
!
to simplify for large N.
(c) Redo part (b) using the “equivalent” canonical ensemble.
Hint: This is much simpler than (b).
Note: As long as N is large, the two ensembles are equivalent, so you will get the
same answer as in (b) provided, of course, that you choose the right temperature to
match the microcanonical energy.