Statistical thermodynamics L1-L3

Lectures 11, 12, 13 of CY101

Need for statistical thermodynamics

Microscopic and macroscopic world
Distribution of energy - population
Principle of equal a priori probabilities
Various forms of energies. {1,1}, {2,0}, {0,2}
Weight of a configuration = how many times
Configuration - instantaneous the configuration can be reached.
n1, n2,…molecules exist in states with energies ε1, ε2,…
N is the total number of molecules
{N,0,0,…} and {N-2, 2,0,…} are configurations
Second is more likely than the first

Ref. Atkins 7th or 8th edition

CY101 T. Pradeep Alberty, Silbey, Bawendi 4th edition
Energy

A configuration {N-2,2,0,0,…}
First ball of the higher state can be chosen in N ways, because there are N balls
Second ball can be chosen in N-1 ways as there are N-1 balls
But we need to avoid A,B from B,A.
Thus total number of distinguishable configurations is, ½ N(N-1)

1 2 3 4 5 6 7 8 9 10

A configuration {3,2,0,0,..} is chosen in 10 different ways

How about a general case of N molecules?
N! ways of selecting balls
n0! for the balls in first level, n1! for the second, etc.
W = N!
n0!n1!n2!....
W is the weight of the configuration.
How many ways a configuration can be achieved.
Better to use natural logarithm

ln W = ln N!
n0! n1! n2!...

= ln N!- ln(n0! n1! n2!..)

=ln N! -(ln n0! +ln n1! +ln n2!...)

=ln N! -Σiln ni!

ln x!≈ x ln x-x Stirling’s approximation

ln W = (N ln N - N) - Σi (ni ln ni – ni) = N ln N –Σini ln ni
 Which is the dominating configuration having maximum
weight?
Generalised approach is to set dW = 0
There are problems as any configuration is not valid.
1. Energy is constant. Σi ni εi = E
W
2. Constant molecules. Σi ni = N
Lagrange, method of undetermined multipliers ni
A constraint should be multiplied by a constant and then added to the variation equation

ni = e -βε
Populations in the i Boltzmann distribution
N Σ e -βε
i i
configuration of greatest i is a sum over available states
weight depends on the
energy of the state. β=1
kT

Temperature gives the most probable populations

 Boltzmann distribution – population, pi = e -βεi
q
Molecular partition function

q =Σi e -βεi There are several ways of looking at i

Another form of q: q =Σ levels i gi e-βεi
How to look at partition functions?
lim T→0 q = g0 Because, ε0 = 0
Look at limiting cases For all higher levels ε is finite.
e-βε =1. e-x is 0 when x is ∞.
lim T→ ∞ = ∞ All terms will reduce to 1.
When number of states is finite, e-x is 1 when x is 0
we will not get ∞.
1. Partition function is the number of available states.
2. Partition function is the number of thermally accessible states.
3. How molecules are ‘partitioned’ into available states.

How to look at thermodynamic properties?

Evaluation of molecular partition function ε
2ε
ε
1 + x + x2 + x3 + ….= 1/(1-x)
0
q = 1 + e –βε + e –2βε + e –3βε +…= 1 + e –βε + (e –βε)2 + (e –βε)2 +…=1/(1- e –βε)

Fraction of molecules in energy levels is,

pi = e –βεi/q = (1- e –βε) e –βεi

Discussion of figure, next slide

p
For a two level system,

po = 1/(1 + e –βε)
p1= e –βε/q = e –βε/ (1+ e –βε)

As T  ∞, both po and p1 go to ½.

Consequences?
Low temperature High temperature
 Approximations: Partition functions are often complex. Analytical expressions
cannot be obtained in several cases. Approximations become very useful.
For example, partition function for one dimensional motion

En = n2h2
8 mX2 n =1,2….

h2
εn = (n2-1)ε ε = 8mX2

qx = Σ∞n=1 e -(n2-1)βε

qx = ∫∞1 e -(n2-1)βε dn energy levels are close, sum becomes an integral

No big difference, if we take the lower limit to 0 and replace n2-1 to n2.
1/2
qx = 1 2 1
1/2 ╥ 1/2
2 ╥m 1/2
βε ∫0 e dx =
∞ -x
= h2β X
βε 2

Substitute, X2 = n2βε, dn = dx/(βε)1/2 1/2 Substitute for ε

qx = 2╥ m
h2β X
Independent motion in three dimensions

εn1n2n3 = εn1 (X) + εn2 (Y) +εn3 (Z) Energy is a sum of independent terms

q =Σ all n e -βε(X)n1 –βε(Y)n2 -βε(Z) n3

= Σn1 e- βε(X)n1 Σn2 e -βε(Y) n2 Σn3e -βε(Z) n3

= qxqyqz
3/2
2╥ m
q = h2β XYZ

1/2
q=V β h
= h ╥ = has dimensions of length,
3 2 m 1/2
(2╥mkT) thermal wavelength
J =kg m-2 s-2
Question: How many more quantum states will be accessible for 18O2 compared to
16O , if it were to be confined in a box of 1 cm3?
2
How to get thermodynamics?
All information about the thermodynamic properties of the system is contained
in the partition function. Thermal wavefunction.
Total energy
E = Σi niεi
N Most probable configuration is dominating.
E = q Σiεi e-βεi
We use Boltzmann distribution.
We know, εie –βεi = - d e-βεi
dβ

dq
E = -N Σi d e –βεi = -N d Σ e-βεi= N
q dβ dβ i q dβ
q
1. All E’s are relative
U = U(0) + E
E is the value of U relative to T = 0.
2. Derivative w.r.t. β is partial
U = U(0) -N ∂q
q ∂β as there are other parameters
v
(such as V) on which energy
U = U(0)- N ∂lnq depends on.
∂β v

Partition function gives internal energy of the system.

 Partition function is the number of thermally
Statistical entropy accessible states.
Entropy is the distribution of energy
S = k ln W The two must be related
W is the most probable configuration of the system.

ln W = N ln N –Σini ln ni

N = Σi ni

S = k Σi (ni ln N –Σini ln ni )
= - k Σi ni ln ni /N
=- Nk Σi pi ln pi
pi = ni/N

ln pi = -βεi – ln q [definition of pi]

S = -Nk(-β Σi pi εi – Σi pi ln q)= -kβ [U – U(0)] + Nk ln q

We used, Σi pi = 1 and NΣi pi εi = Σi Npi εi = Σi ni εi = E

S = 1/T[U – U(0)] + Nk ln q
 Canonical partition function
Particles are interacting.
Closed System Concept of ensemble

Canonical Ensemble: Imaginary

replication of the closed system in
different microstates
corresponding to the same
macrostate “N, V, T”
Microcanonical Ensemble: Imaginary replication of the isolated
system in microstates corresponding to the same macrostate
“N, V, E”
Grand canonical Ensemble: Imaginary replication of the isolated
system in microstates corresponding to the same macrostate
“μ, V, T”

N molecules, Ń imaginary replications

Number of members in the state with
energy Ei is ńi. Total energy of all the
replications Ė
Total energy of the isolated ensemble is constant.
 Dominating configuration
{ń0, ń1….} has a weight, Ẃ
Ẃ = Ń!
ń0! ń1! ń2!...
Configuration of greatest weight, with conditions of total energy, Ė and number of
members, Ń is called cannonical distribution.
ńi = e -βEi Q = Σi e -βEi
Ń Σ e -βEi
i

Q is called cannonical partition function.

Q is more important than q as the former talks about
interacting particles.

Total energy of the ensemble is E and there are Ń members. Average energy of a
member, E is Ė/ Ń. Let us calculate U when Ń (and therefore Ė) reaches infinity.

U = U(0) + E = U (0) + Ė/ Ń Ń ∞
 The fraction, ṕi of members of the ensemble in state i with energy Ei is,

ṕi = ńi = e -βEi
Ń Q

Internal energy, U = U(0) + E = U(0) + Σi ṕi Ei = U(0) + 1/Q Σi Ei e -βEi

U =U(0) - 1 ∂Q
Q ∂β v

U = U(0) - ∂lnq
∂β v

Entropy

Weight of a configuration, Ẃ of the ensemble is the product of the average

weight W of each member within the ensemble so that, Ẃ =WŃ

S = k ln W = k ln Ẃ1/Ń = (k/ Ń) ln Ẃ

This as in the case of molecular partition function, S = 1/T[U – U(0)] + k ln Q

 Molecular partition function and cannonical partition function
When molecules are independent, total energy of state, i is
Ei = εi(1) + εi(2) + εi(1) +… + εi(N)
εi (1) is the energy of molecule 1 for the system is in state i. Sum is for all the N
molecules constituting the state i.

Q   e   i (1)   i ( 2 ) ....  i ( N )
i
Instead of summing over states of the system, we can sum over all the states, i of the
molecules 1, 2, 3….

     
Q    e    e   e
  i
   i
   i 
 
 i (1)   i ( 2)   i( N ) 
q  e   i

Q  qN
 Limitations
This discussion was for molecules which are distinguishable. Every possible
state of individual molecule is counted in determining Q. But this is not the case
when molecules are alike. In such cases, several states are counted in excess.
The correction factor is N!, the number of permutations possible for a N
member system to create a state.

Q distinguishable qN

Q indistinguishable q N !
N

1
Q  qN Single species, ideal gas
N!
What is distinguishable: Similar molecules in the lattice as each one can be
assigned a coordinate
Indistinguishable: Even when they are similar as in rare gases
Sackur-Tetrode equation
S = 1/T[U – U(0)] k ln Q distinguishable molecules
1/2
V β h
Q= qN/N! indistinquishable molecules q= = h ╥ =
3 2 m (2╥mkT)1/2
S = 1/T[U – U(0)] + Nk ln q – k ln N!
U = U(0) + 3/2 nRT
Number of molecules is large, N = nNA as well as Sterling approximation

S = 1/T[U – U(0)] + nR ln q – nR ln N + nR

S = 3/2nR + nR [ln V/Λ3 – ln nNA + 1] = nR [ln e3/2 + ln V/Λ3 – ln nNA + ln e]

S = nR ln [e5/2V/nNA 3]

Gas is perfect. V = nRT/p

Equation can be expressed in terms of pressure.

Implications: Higher molar mass – higher entropy

Expansion of gas leads to grater entropy. ΔS = nR ln aVf – nR ln aVi = nR ln Vf/Vi
Same as classical. a is a collection of terms
Relations for various thermodynamic quantities

  ln Q 
U  U (0)    S  U U (0)  k ln Q
   V T
Substitute Q = qN or qN/N! as in the case may be.

U and S relate to other functions.

A = U-TS
dA = dU-TdS-SdT
1. Helmholtz function dU = TdS – pdV + Σ μi dni
dA = -SdT – pdV + Σ μi dni
p = -(∂A/ ∂V)T,ni
A = U – TS which means A(0) = U(0)

A - A(0) = -kTInQ
2. Pressure
  ln Q 
p  kT  
  V T
p = -(∂A/ ∂V)T

Valid for all substances.

This is a relation between p, V, T amount of substance. An equation of state.

Equation of state for independent particles:

p = kT (∂lnQ/∂V)T = kT (∂ln(qN/N!)/∂V)T = NkT/q (∂q/∂V)T (1)

= (NkTΛ3/V) (1/Λ3) = NkT/V = nRT/V (2)

For (1) we have used, Q =qN/N!

For (2) (∂q/∂V)T = (∂(V/Λ3)/∂V)T = 1/ Λ3 and NkT = nNAkT = nRT

3. Enthalpy
H = U + pV
  ln Q    ln Q 
H  H (0)      kTV  
   v  V T
 3
U  U ( 0 )  nRT
2
pV  nRT
5
H  H ( 0 )  nRT
2
4. Gibbs free energy
G = H – TS = A + pV = A + nRT
  ln Q 
G  G ( 0 )   kT ln Q  kTV  
  V T
G  G (0)   kT ln Q  nRT
 Q = qN/N! ln Q = N lnq – ln N! = N lnq – (N lnN – N)

G  G ( 0 )   NkT ln q  kT ln N ! nRT
 nRT ln q  kT ( N ln N  N )  nRT
q
 nRT ln  
N
Gibbs free energy is proportional to the logarithm of the average number of
thermally accessible states.

N = nNA

We can also define a molar partition function, qm = q/n

 qm 
G  G (0)   nRT ln  
 NA 
Molecular partition function

εi= εiT+εiR+εiV+εiE

q=Σie-βεi=Σi (all states)e-βεiT-βεiR-βεiV-βεiE

=(Σie-βεiT) (Σie-βεiR) (Σie-βεiV) (Σie-βεiE) =qTqRqVqE

Trans Rot Vib Elec

1. Translational
  
12
V h
q  3
T Λ = h  
  2 m  (2mkT )1/ 2
2. Rotational

qR=ΣJ(2J+1)e-βhcBJ(J+1)
For linear rotors (A-B),
kT T
qR   Characteristic rotational temperature
hcB R T>>ΘR

kT T Linear, symmetric molecules

qR  A-A, counting states twice
2 hcB 2  R CH=CH

qR  kT
σ Symmetry number
 hcB
qR= ∫∞0 (2J+1)e-βhcBJ(J+1)dJ

We can simplify

d/dJ [eaJ(J+1)] = d/dJ [aJ(J+1)] eaJ(J+1) = a(2J+1)eaJ(J+1)

qR = (1/βhcB) ∫∞0 d/dJ [e-βhcBJ(J+1)] dJ

qR = - (1/βhcB) [e-βhcBJ(J+1)] ∞0 = 1/βhcB

= kT/ hcB
3. Vibrational

 1 ~
Ev = v  hc
 2
qv=Σve-βvhcṽ =Σv(e-βhcṽ)v = 1/(1-e-βhcṽ)
1
qv 
1  e   hcv
4. Electronic

qE = gground = 1

NO  …π1
Gives 2Π1/2 and 2Π3/2
Each state is doubly degenerate
Gap is small between these two

qE =Σlevels gE e-βεi = 2 + 2e-βε

Leads to occupancy in all the states.

Overall partition function

 V   T   1 
q = gE  3     ~
      R   1 e hcv

 V   T   1 
q =g E      
  3
    R   1 eT / 

 Using statistical theromodynamics

Mean energies

Mean energy for each mode, M

Rest of the material in this file is as in Atkins.

(a) The mean translational energy
One–dimensional system of length X, for which qT = X/Λ, with Λ =
h(β/2m)1/2 . Λ is a constant times β1/2
For a molecule free to move in three dimensions:

Classical equiparition theorem

1. Mean energy of each quadratic contribution to the energy is
1/2kT
2. Mean energy is independent of the size of the container
3. Consistent with the thermodynamic result that the internal
energy of a perfect gas is independent of its volume
(b) The mean rotational energy

When the temperature is low (T < θR), we get:

Hence
 At high temperature (T >> θR), qR is given by qR = T/2θR

(qR is independent of V, so the partical derivatives have been replaced

by complete derivatives).

The high-Temperature result is also in agreement with the

equipartition theorem, for the classical expression for the energy of a
linear rotor is EK = 1/2Іωa2 + 1/2Іωb2 = 2 x ½ kT = kT
(c) The mean vibrational energy

and hence from

At high temperatures, when T >> θv, or βhcv << 1, the exponential
function can be expanded (ex = 1 + x + ….) and all but the leading
terms are discarded.
This result is in agreement with the value predicted by the
classical equipartition theorem, because the energy of a one –
dimensional oscillator is E =1/2mv2x + 1/2kx2 and the mean energy
of each quadratic term is 1/2kT.

Heat capacities

The constant-volume heat capacity is defined as Cv = (U/T)v .

The derivative with respect to T is converted into a derivative
with respect to β by using:
Because the internal energy of a perfect gas is a sum of
contributions, the heat capacity is also a sum of contribution from
each mode. The contribution of mode M is,
The individual contributions

The temperature is always high enough (provided the gas is above

its condensation temperature) for the mean translational energy to
be 3/2 kT, the equipartition value. Therefore, the molar constant-
volume heat capacity is:

CP- CV = R