Andres Colorado

Student Id: 29525702; December 9, 2011

MAE 216: Statistical Thermodynamics; final exam

Problem 1 Describe the partition function Q, and how you can calculate all
thermodynamic properties from it. In particular, write the equation for the entropy in
terms of the partition function and indicate how this expression is consistent with the
concept of entropy as a measure of disorder.
Based on your results, discuss the entropy of a monatomic gas as compared to that of a
diatomic gas for the same number of moles N, volume V, and temperature T.

The partition function is the normalization constant for the probability that a system be in the state with
energy
j
E , and we must take into account that the probability that the system be in the state with energy
j
E depends exponentially on the energy in that state j (
T K
E
j
B
j
e p

). So as normalization factor
(constant) in the Boltzmann distribution; it follows that it is the summation of the probabilities over all the
energy states that the system has:

=
j
T K
E
B
j
e Q ; Where j represents all the states
Considered in this way the partition function can be seen as a sum of the relative occupancies of energy
states. It is for this reason that the partition function is also called the sum-over the energy states. From
this point of view, the partition function is necessary for computing probabilities.
We can see that the partition function is related to complete systems, so it is very useful to calculate the
thermodynamic properties of complete systems.
When we consider a system of independent, indistinguishable atoms or molecules, the partition function
can be written as: ( ) | | ! / , N V N q Q
N
= , where N is the number of particles (atoms or molecules) and V
is the volume. The last case can be referred as the molecular partition function. Since we have learned
that the energy of a system in the molecular range can be expressed as the sum of
rot vib rot trans total
E E E E E + + + = then the partition also can be expressed as function allows us to add up
together all the different energies.
( ) | |
( )
N
elec vib rot trans
N
N
q q q q
N V N q
!
! / , =
V
h
T Mk
q
B
trans
2 / 3
2
2
|
.
|

\
|
=


rot
rot
T
q

T
T
vib
vib
vib
e
e
q
/
2 /
1

=
T k D
e elec
B e
e g q
/
1
=

Which is interesting of this way of expressing the partition function is that each lower case q can be
expressed as functions of temperature and volume, which are some of the fundamental units of measure in
a thermodynamic system. We have to understand as well, that for example a monoatomic gas does not


Andres Colorado
Student Id: 29525702; December 9, 2011
MAE 216: Statistical Thermodynamics; final exam
have vibrational or rotational terms, since it cannot be modeled as a harmonic oscillator. Therefore for
those kinds of gases, the partition function is reduced only to the translational and electronic parts.
Other molecules more complex such as the diatomic and the polyatomic molecules include all kinds of
partition functions.

The molecular partition functions "q" are used to calculate the Q which in turn can be used to find the
internal energy "U" of the system:
V N
B
T
LnQ
T K U E
,
2
|
.
|

\
|

= = ; where
V N
T
LnQ
,
|
.
|

\
|

becomes:
( )
V N
N
elec vib rot trans
T
N
q q q q
Ln
,
!
|
|
|
|
|
.
|

\
|

|
|
.
|

\
|

After deriving de natural logarithm of Q and using the Sterlings approximation (to get rid of N!) we end
up with the molar internal energyU that is expressed as a summation of all the kind of energies (trans,
vib, rot, elec) in the system. This is consistent with the fact that the average ensemble energy is equal to
the observed energy of a system.
elec vib rot tyrans
E E E E U E + + + = =
Also, the pressure of a system can be found from the partition function through the next equation:
V N
B
T
LnQ
T K P
,
|
.
|

\
|

=
So pressure is related to systems and cant be imagined for a single molecule or atom. Then defining the
pressure as a partition function for a complete system makes sense.

For the entropy (S) we know that it is the force that governs the direction towards which a spontaneous
process occurs, and the second law of thermodynamics implies that all the systems tend to the disorder or
chaos; this is an interesting result because if all the systems tend to the chaos it means that eventually
there is not going to be any more organized systems from where we can get work. In general terms, it is
related to the level of disorder of a system, therefore the higher the entropy the higher the level of disorder
of the system; the entropy can be expressed in terms of the partition function, which allows us to know
which kind of molecular partition function q generates more disorder in a system. Knowing that the
expression for the entropy of a system is defined by:
LnQ k
T
LnQ
T k S
B
V N
B
+
|
.
|

\
|

=
,

We can see that the higher the temperature we can expect more disorder, which is reasonable since more
molecules moving faster and randomly can be seen as a more disordered system. And it would be
expected that a higher temperature system would create more disorder in the surroundings, as
T
q
ds

=
and q passed to the surrounding would result in pure irreversible heat. Also, as the Q is dependent on
the power of the partition function to the number of molecules over all the possible ways of organize
those molecules in the system. When increasing the number of particles the power of the partition
function increases faster than the possible ways of organizing them as a result a system that contains more
molecules tends to be a more disorganized system. We can see that when increasing the number of
Andres Colorado
Student Id: 29525702; December 9, 2011
MAE 216: Statistical Thermodynamics; final exam
molecules in the system the result is a higher the Q, hence a higher LnQ. For the derivative
T
LnQ

it is
related to the internal energy. And as presented before, a positive increment of the partition function
(more possible energy states) respect to T results in a higher internal energy of a system, therefore a
higher disorder.
So, using the pressure (P), the internal energy (U), and the entropy (S) we can derive all the
thermodynamic properties that are not measureable such us the Helmholtz energy (A), Gibbs Energy (G),
Enthalpy (H) The internal energy. This derivation can be obtained using the Maxwell relations as
presented below:

TS U A = (Helmholtz)
TS PV U G + = (Gibbs)
PV U H + = (Enthalpy)

In order to solve for the entropy of a monoatomic and diatomic it is necessary to derive the expression for
T
LnQ

and solve for the LnQ; after that we can get the following expressions:

(
(

|
.
|

\
|
+ =
A
e B
gas ideal monoatomic
N
g V
h
T mk
Ln
R
S
1
2 / 3
2
) (
2
2
5

1
2 / 5
1
2 / 3
2
) (
ln
1
1 ln
2
e
vib
vib
vib
rot A
e B
gas diatomic
g
T
T
T
LnTe
N
g V
h
T Mk
Ln
R
S
+

+
|
.
|

\
|
+

+
(
(

|
.
|

\
|
=

For a monatomic gas, the possible ways of store energy are less than those of a diatomic gas since the
monoat omi c particles do not spin or rotate. As a result, more ways of storing energy has the
consequence of higher probabilities of being chaotic or more entropic.
In this case for the same number of moles N, volume V, and temperature T the diatomic gas entropy will
result in a higher level of disorder. Since it will distribute its possible ways of organize the energy in four
different energy ways while the monoatomic only in two ways (that is more organized). That fact causes
that an increase in internal energy of a diatomic gas result in a higher increase of its entropy.

Problem 2 The hydroxyl radical OH is one of the most important molecules in
atmospheric chemistry and combustion. The Chemkin II thermodynamic database
provides a 4th order polynomial fit to C
p
/R for OH (see the attached page). The fit has two
ranges (high temperature and low temperature, with a match temperature where they are
equal). Using the fit for C
p
/R, answer the following questions:
(a) Is the value of C
p
/R at 300K (the bottom of the range) what you expect? Why or
why not?

Using the equation provided by Chemkin II and its coefficients. For C
p
/R as a function of the temperature
(see the equation below)
Andres Colorado
Student Id: 29525702; December 9, 2011
MAE 216: Statistical Thermodynamics; final exam
4
5
3
4
2
3 2 1
T a T a T a T a a
R
C
p
+ + + + =
We can get the complete plot over the analyzed range of temperatures (300K - 5000K). Using Matlab, we
get the plot of C
p
/R as a function of the temperature (see Figure 1).

Figure 1. Cp/R as a function of temperatures. Approach to the CP/R using the Chemkin database.
We can see that the predicted value of C
p
/R at 300K is around 3.6. This is an expectable result for an
ideal diatomic gas at moderate temperatures. The constant for a monoatomic gas is Cv3/2R, while for a
diatomic gas it is Cv5/2R.
As for Ideal gases R C C
v p
+ = we can get that 1 + =
R
C
R
C
v
p
, therefore at lower temperatures it is
expectable a C
p
/R around 5/2+1=3.5.

For sure the Chemkin software introduces corrections and empirical relations in order to adjust the curve.
However we could say the OH behaves approximately as an Ideal gas around the lower range of
temperature.

(b) Use the behavior of C
p
/R in the middle range of temperature to compute the
characteristic Temperature for vibration
vib
, for OH; for a bonus, give the
frequency of light that would interact with the associated fundamental vibration
frequency?

Using the equation that describes the heat capacity for a diatomic gas, and assuming that it behaves as an
ideal gas we can
2
2
1
2
5
|
|
.
|

\
|

|
.
|

\
|
+ =

T
T
vib v
vib
vib
e
e
T R
C

0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
3.4
3.6
3.8
4
4.2
4.4
4.6
4.8
5
Temperature (K)
C
p
/
R


lower range of temperature
higher range of temperature
Andres Colorado
Student Id: 29525702; December 9, 2011
MAE 216: Statistical Thermodynamics; final exam
2
2
1
2
7
|
|
.
|

\
|

|
.
|

\
|
+ =

T
T
vib
p
vib
vib
e
e
T R
C


Solving for
vib
at 1000K with our equation and using an iterative process in excel we get that
R
C
p
=3.69028 and the corresponding
vib
=4821.64K
While using the Chemkin II database we get for the same temperature 3.69025

The variation of the
vib
is relatively small around the middle temperature. For example at 900K and
using the Cp/R predicted by Chemkin II at that temperature the vibrational temperature becomes
K
vib
57 . 4856 =
For 1100 K--- K
vib
4783 =
However it is advisable to use the Chemkin II database to estimate the Cp/R instead of the rigid rotator
harmonic oscillator approach, since using this method we would have to look up for the
vib
as a function
of temperature.

Bonus:
Give the frequency of light that would interact with the associated fundamental vibration
frequency:

B
vib
k
hv
=

Using the
vib
that we got at the middle temperature of 1000K and given the Boltzmann and Plancks
constants
B
k and, h respectively.
We can get the respective wave number at those conditions:

h
k
v
B vib

=

s J
JK K
v
. 10 6260755 . 6
10 380658 . 1 64 . 4821
34
1 23

=


Hz v
14
10 004666 . 1 =

This frequency corresponds to the infrared portion of the light spectrum, which is related to changes in
vibrational levels due to the vibration of the flexible bonds.

Problem 3 Spectroscopy can be used to determine system temperature from the
distribution of molecular population among the energy states available. Under
equilibrium conditions, it is possible to use the population distribution among vibrational
energy levels or rotational energy levels to determine temperature. The height of the
lines in the experimental image below for HBr can be assumed to show the populations
in the energy levels for the associated rovibrational energy transition. The lines to the left
Andres Colorado
Student Id: 29525702; December 9, 2011
MAE 216: Statistical Thermodynamics; final exam

of the central gap are the P-branch (J = -1); the lines to the right are the R-branch (J =
+1). This means that the first line to the right of the gap is for the transition from =0 to
=1 in vibration and J=0 to J=1 in rotation. Hence, the height of that line represents the
population in the =0, J=0 energy level. Similarly, the next line to the right approximately
represents the population in the =0, J=1 energy level, and so on. Using the R-branch
energy identified on the abscissa (or if you want to look up the rotational constant for
HBr, you can get the energy from that) and the relative population as determined by
measuring the heights of the lines, create a Boltzmann plot, and from that plot estimate
the temperature of the sample. Dont forget that the reason the lines peak is that there is
2J+1 degeneracy of the rotational energy states.


Figure 2. spectroscopy of the Hbr


A Boltzmann plot is where you look at a bunch of spectral lines of some species (in this case Hbr atoms),
use that to calculate the populations of the states, and then plot those populations versus the energies of
the states, to see if they follow Boltzmanns distribution, and if they do, to calculate the temperature.
We know that the populations should be proportional to exp(-E/kT), where T is the excitation
temperature. Then the total relative population at an energy E is thus given by:
( )
T k E
B
e J p
/
1 2

+
( )
T k E
J
p
Ln
B
/
1 2
=
(

+

The populations can be assumed as the measured highs of the lines, while the energy can be taken directly
from the x axis of the sketch. Thus the relative intensities in these lines can be used to give a measure of the
temperature using a Boltzmann plot with slope 1/kT.
In order to plot the Boltzman plot we use the data shown in the following table:

Andres Colorado
Student Id: 29525702; December 9, 2011
MAE 216: Statistical Thermodynamics; final exam

Table 1. Data for the HBr extracted from figure 2 and used for plotting the Boltzmann distribution.
J
level
highs of the
lines in the
R branch relative populations degeneracy
Energy of
every
population
eVolts Energy in J LN(Populations/(degeneracy))
0 2.1 0.102941176 1 0.31875 5.10694E-20 0.322219295
1 2.4 0.117647059 3 0.320625 5.13698E-20 -0.096910013
2 2.5 0.12254902 5 0.3225 5.16702E-20 -0.301029996
3 2.5 0.12254902 7 0.324375 5.19706E-20 -0.447158031
4 2.4 0.117647059 9 0.32625 5.2271E-20 -0.574031268
5 2.2 0.107843137 11 0.3278125 5.25214E-20 -0.698970004
6 1.8 0.088235294 13 0.3296875 5.28218E-20 -0.858670847
7 1.4 0.068627451 15 0.33125 5.30721E-20 -1.029963223
8 1.1 0.053921569 17 0.3325 5.32724E-20 -1.189056236
9 0.8 0.039215686 19 0.334375 5.35728E-20 -1.375663614
10 0.6 0.029411765 21 0.335625 5.37731E-20 -1.544068044
11 0.4 0.019607843 23 0.3371875 5.40234E-20 -1.759667845
12 0.2 0.009803922 25 0.338125 5.41736E-20 -2.096910013


Figure 3. Boltzman plot

We can see that the slope from the plot is -6.51E
+20 .
Then dividing by the -1/K
B
we get the temperature for
the given spectrum.
K T
Slopek
B
25 . 111
1
= =

This is a very low temperature; however we must know other conditions of the experiment in order to say
why the spectrum observed gave the temperature that we just found.
Also, when we compare this temperature with the one of the population with the highest rotational level
we can see that goes through a maximum for a certain J value, Jmax which is given by
y = -6.51E+20x + 3.34E+01
-2.5
-2
-1.5
-1
-0.5
0
5.1E-20
L
n
(
P
o
p
u
l
a
t
i
o
n
s
/
d
e
g
e
n
e
r
a
c
y
)

Energy

(J)

Andres Colorado
Student Id: 29525702; December 9, 2011
MAE 216: Statistical Thermodynamics; final exam

2
1
5896 . 0
max
=
B
T
J
T
J
B =
|
|
|
|
.
|

\
|
+
2
max
5896 . 0
2
1
With Jmax= 2, T=152.27K
Still the temperature is very low however the HBr is not a very common substance as water vapor or CO
2
,
so understanding its behavior at given temperatures its very difficult to understand for any human being
that look at the spectroscopy and who does not know the experimental conditions in advance.

Problem 4 (extra credit) Briefly describe Maxwells Demon and its significance.

It was a very interesting to read in the story about how Maxwell tried to demonstrate than when analyzing
the second law of the thermodynamics from a molecular point of view or from the probabilistic
interpretation that is involved at the atomic level; he tried to show that everything was possible, even to
break the rules and go against the second law. For that case he set an example to show that from the
probabilistic point of view it is possible that a molecule or particle that is part of cold system be
transferred to a hotter system. The system explained by Maxwell consisted of two chambers divided by a
gate. One of the chambers was a higher temperature and the other one was at lower temperature.
However, this theory caused a lot of controversy and in order to break the rules as Maxwell was
proposing it was necessary certain specific conditions that were out of the real world. That was why other
scientist started mocking at Maxwell and they said that in order to go against the second law, Maxwell
would need literally a demon to open the gate in the exact moment that the particle at a lower
temperature was traveling towards the gate that divides the system, and that the demon must be extremely
fast and extremely smart in order to do that at the exact time that Maxwell required to go against the
second law.
Maxwell explained that by opening the gate at the exact moment a particle in a colder energy state could
be transferred to a system in a hotter state, this statement could be possible in a probabilistic world and it
was Maxwells main argument to support his theory, however that assumption obviously goes against the
second law and from a global perspective like the one that Carnot had at his time was certainly
impossible.
Nevertheless the controversy that Maxwells arguments caused at that time, it was very interesting to see
the second law from a molecular perspective, even knowing that his theory never was developed. But the
importance of the article lies in the fact that it allows us to imagine a complete new world defined by
molecules, atoms and particles and how that world is ruled by probabilities and statistics. That is
something that as a mechanical engineer is very far from my perspective, but when analyzing the article it
gave me more insight of the molecular approach.