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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008 Lecture #26-27 page 1

STATISTICAL THERMODYNAMICS

Calculation of macroscopic thermodynamic results

Entropically driven examples:

Free expansion of a gas V1 vacuum V2

gas gas

Lattice model for ideal gas translation:

Molecular volume v, Total volume V
All molecular positions have equal energy trans = 0
All system microstates have equal energy Etrans = 0
V1
Calculate S = k ln in each state

Molecular degeneracy g = V/v

V2

System degeneracy = gN/N! = (V/v)N/N!

For expansion from volume V1 to V2,

N
(V v ) N!
S = kln 2 kln 1 = kln 2 = kln 2 N
1 (V1 v ) N!
V2 V
S = Nkln = nRln 2
V1 V1

V2
Should look familiar! And G = H TS = nRTln
V1
Entropy change is positive, free energy change is negative, as we expect.
5.60 Spring 2008 Lecture #26-27 page 2

NA NB N = N A + NB

Ideal gas mixture

VA VB V = VA + VB

Assume same initial (p,T) for A & B same (p,T) for mixture
Assume equal molecular volumes & lattice cell sizes.
Then initially
(V v ) (VB v )
NA NB

S1 = kln A + kln B = kln AB = kln A

NA ! NB !

After mixing: Count how many ways to distribute NA

molecules of A and NB molecules of B among the (V/v)
lattice sites

As before, the number of ways to distribute N

molecules among (V/v) sites is (V/v)N.

To correct for indistinguishability, divide by NA!NB!

So the final state entropy is

(V v )
N

S2 = kln = kln
NA !NB !

( )
(V v ) (V v ) (VB v ) ( V v)
N NA NB NA +NB
V NA V NB
S = S2 S1 = kln kln A = kln = kln
(VA v ) (VB v )
N N
NA !NB ! NA ! NB ! A B
VANA VBNB

Since the initial pressures are the same, the initial volumes must be in the ratio
of the number of molecules, i.e. VA/V = NA/N = XA and VB/V = XB, so

V NA V NB
S = kln NA NB = kln XANA kln XBNB = Nk ( XA ln XA + XB ln XB ) (> 0)
VA VB

With a simple microscopic model we can derive the macroscopic entropy change!
 5.60 Spring 2008 Lecture #26-27 page 3

Ideal liquid mixture

Lattice model is different from gas because all the cells are occupied. Then in
the pure liquid there is no disorder at all!

SA = kln A = kln1 = 0

SB = kln B = kln1 = 0

Mixture: N molecules for N sites.

First molecule has N choices, second (N 1), etc.

# ways to put the molecules into sites = N!

Correct for overcounting by dividing by NA!NB!

N!
Smix = Smix ( SA + SB ) = Smix = kln mix = kln
NA !NB !

Stirlings approximation lnN! NlnN N

(
Smix = Nkln N Nk NAklnNA NAk + NBkln NB NBk )
N N
= ( NA + NB ) kln N NAkln NA NBkln NB = NAkln + NBkln
NA NB

= Nk ( XA ln XA + XB ln XB )

Real liquid has additional states - positional disorder, molecular rotation, etc.
but these occur in both the pure and mixed liquids, so Smix is dominated by the
disorder in molecular positions that the lattice model describes reasonably well.
***********************************************************************
Combinatorics:
Simple example
Mix 2 molecules A
+ 3 molecules B

= 10 = 5!/2!3!
How many distinct
configurations ?
5.60 Spring 2008 Lecture #26-27 page 4

Energy & entropy changes

We saw one example earlier, with 4-segment polymers.

Molecular state:

Energy : 0 int int int

Degeneracy g: 1 3

Weve redefined the zero of energy as the ground state energy.

Configurational molecular partition function is

i,conf kT int kT kT kT
qconf = e
states

= e 0 kT + e + e int + e int
i

int kT int kT
ge
i kT
= i = e 0 kT + 3e = 1 + 3e
energy levels
i

For a solution of noninteracting polymer molecules,

( )
N
int kT
Qconf = qconf
N
= 1 + 3e

We can determine the thermodynamic properties:

Aconf = kT ln Qconf = NkT ln 1 + 3e ( int kT

) = NkT ln (1 + 3e int
)

ln Qconf ln 1 + 3e int ( ) 3 e int

Uconf = = N = N int
V,N 1 + 3e int
V,N

Energy scales with N: molecules are not interacting with each other so total
energy is just a sum of individual molecule energies.
5.60 Spring 2008 Lecture #26-27 page 5

Average energy per molecule is

Uconf 3int e int

conf = =
N 1 + 3e int

e i
i

0 + 3int e int
But we also know = iPi = i
= - same result
i q 1 + 3e int

Aconf Uconf 1 ln Qconf N 3int e int
Sconf =
T
+
T
= kln Qconf
T V,N
= Nkln 1 + 3e
int
+
T 1 +
3e
int
( )

Also scales with N sum over individual molecule entropy contributions

Average molecular configurational entropy is

1 3int e int
(
sconf = kln 1 + 3e
int
) +
T 1 + 3e int

In high-T (low-) limit, its kln(4) as expected. In low-T limit, its kln(1) = 0.

A ln Q
conf = = kT
N T,V

N T,V

= kT ln 1 + 3e int ( )

Chemical potential is just A per molecule, and A scales with N so its just A/N.

Uconf 1 Uconf N 3int e int

CVconf = = kT 2 = kT 2 int
T V,N V,N 1 + 3e

(
3 N 1 + 3e
= int
2
int
) ( int e )e
int int
( 3
int e
int

)
(1 + 3e )
2

kT int

Scales with N, so we can think of a configurational heat capacity per molecule.

Complicated function, but its limits are understandable:

5.60 Spring 2008 Lecture #26-27 page 6

CVconf 0 as T 0
int
Low-T
At low T, all molecules are in the lowest state. If
limit
kT increases infinitesimally, all the molecules are
still in the lowest state! So the configurational 0 kT
energy Uconf doesnt change!

CVconf 0 as T
kT

At high T, the molecules are equally distributed High-T

among all the states. If kT increases, they are limit
int
still equally distributed among all the states! So 0
Uconf doesnt change.

The low-T limit CV 0 is common to almost every degree of freedom since

ultimately a temperature is reached at which only the lowest level is occupied.

The high-T limit CV 0 is characteristic of systems or degrees of freedom

with a finite number of states, i.e. a maximum possible energy. In that case,
ultimately a temperature is reached at which the equilibrium distribution is ~
equal probability of all the levels being occupied. This is the case for molecular
configurations as discussed here and for spin states of nuclei and electrons.