Beruflich Dokumente
Kultur Dokumente
by
Sidney Young
Department of Chemistry
University of South Alabama
Mobile AL 36688-0002
and
syoung@jaguar1.usouthal.edu
tzielins@monmouth.edu
Copyright Sidney H. Young and Theresa Julia Zielinksi, 1997. All rights reserved. You are welcome to use this
document in your own classes but commercial use is not allowed without the permission of the author.
Introduction: In this document the fundamental equations for calculating the thermodynamic
properties of molecules and equilibrium constants for reactions are presented. You will see how
the translation, rotational, vibrational and electronic states of molecules contribute to their
thermodynamic properties. After studying this document you will be able to use the Mathcad
equations as templates for determining the thermodynamic properties of molecules and
reactions of interest to you and for your own projects.
Goal: To provide students with the basic statistical thermodynamic equations for computing
thermodynamic properties of molecules and reactions.
Prerequisites:
1. Basic skills with Mathcad up to and including taking derivatives and using
evaluate from the Symbolic drop down menu.
2. Knowledge of the existence of quantum mechanical energy levels; prior study
of the classical ideas of translation, rotation, and vibrational modes that
contribute to heat capacity.
3. Be able to distinguish between linear and nonlinear molecules.
4. Knowledge of the relationship between the Gibbs free energy and the
equilibrium constant.
Performance Objectives:
1. Compute the translational, rotational, vibrational, and electronic partition functions.
2. Compute A, U, S, G, etc. thermodynamic functions from the translational, rotational,
vibrational, and electronic partition functions.
3. Compute the equilibrium constant for a reaction from the partition functions of
the reactants and products.
4. Explain the shape of heat capacity as a function of temperature curves.
5. Identify the contribution from rotation, vibration, translation, and electronic
degrees of freedom of the molecule or atom.
6. Explain the shape of heat capacity curves in terms of the degree of importance of the
rotation, vibration, translation, and electronic degrees of freedom in the atom or molecule.
stat_thermo.mcd
Part I.
Thermodynamic properties of molecular nitrogen from statistical thermodynamics
The first substance that we will study in this statistical mechanics exploration is molecular
nitrogen. We will step through the process of determining the thermodynamic functions and
heat capacity as a function of temperature. We will liberally use units in this exercise.
First define some constants:
23
6.02. 10
23.
1.38. 10
6.626. 10
.028 .
mass
Avogadro's number
joule . K
34.
k = 1.38 10
joule. sec
23
34
h = 6.626 10
kg
kg m sec
2
kg m sec
26
mass = 4.651 10
kg
Boltzman constant
Planck's constant
Mass of Nitrogen
N
8
3.00. 10 . m. sec
c
R
8.314. joule. K
c = 3 10
m sec
2
R = 8.314 kg m sec
Speed of light
1
Now set the properties of the gas, i.e. the temperature and pressure
T
300. K
1 . atm
P = 1.013 10
R. T
kg m
3
sec
V = 0.025 m
qt
2 . . mass. k. T
2
1.5
.V
30
qt = 3.561 10
stat_thermo.mcd
2.010. cm
B = 201 m
B. c. h
Thetar
k
Thetar = 2.895 K
T
.
2 Thetar
qr
qr = 51.809
2359.61 . cm
nu
nu = 2.36 10
Thetav
h. nu. c
k
3
Thetav = 3.399 10
qv
1
qv = 1
Thetav
T
stat_thermo.mcd
qe
32
q = 1.845 10
lnQ
N . ln( q )
N . ln( N )
leads to
n!
the equation on the left.
25
lnQ = 1.237 10
stat_thermo.mcd
k. T. lnQ
A = 5.119 10
kg m sec
2. Internal Energy
Thetav
T
3. .
RT
2
R. T
R. Thetav
u
E = 6.236 10
kg m sec
3. Entropy
E
A
T
S = 191.429 kg m sec
3.
Cv
2 u
R. u . e
Cv = 20.798 kg m sec
Cp
Cv
2
2
Cp = 29.112 kg m sec
R. T
H = 8.73 10
G
T. S
kg m sec
4
G = 4.87 10
kg m sec
T. S
A = 5.119 10
kg m sec
stat_thermo.mcd
qv
1
Thetav
T
2 d
E R. T . ln( qv )
dT
2 d
E R. T . ln
dT
exp
E
Thetav
T
Thetav
T
R. Thetav.
1
exp
Thetav
T
by substitution, yields
. .
. u. T. exp( u ) R u T
u
exp( u ) )
e 1
R
E
(1
stat_thermo.mcd
We can now extend the derivation to obtain the heat capacity equation.
Starting with
R. u. T
5. .
RT
2
Thetav
T
5. .
RT
2
where
Thetav
R.
exp
Thetav
Cv
5.
Thetav
R.
2
exp
2
2
Thetav
2
1 .T
. exp Thetav
T
by substitution, yields
Cv
5.
2
R.
( exp( u )
1)
. exp( u)
stat_thermo.mcd
Part III. Obtaining the equilibrium constant for N2 <---> 2 N as a function of temperature
First obtain the partition function for each component of the equilibrium. In this case we need
the partition function for both N2 and N.
1.5
2 . . mass. k. T
qN2( T )
. V.
2 . Thetar
1
.014 .
massN
Thetav
T
.1
kg
N
Now compute the atomic partition function for atomic N
1.5
2. . massN . k. T
qN( T )
.V . 4
6. e
27658.7. K
T
4. e
27671.7. K
T
6.e
41492.4. K
T
lnQN2( T )
lnQN( T )
N . ln( qN2( T ) )
N . ln( qN( T ) )
N
N
k. T. lnQN( T )
GN2( T )
GN( T )
N . ln( N )
k. T. lnQN2( T )
AN2( T )
AN( T )
N . ln( N )
AN2( T )
AN( T )
R.T
R. T
stat_thermo.mcd
Delta_G( T )
GN2( T ) )
9.756. 1.6 . 10
19.
N . joule
The third term in the expression for the change in Gibbs free energy is
necessary because the bottoms of the potential energy functions of the
products and reactants do not match. One is displaced from the of the
other by the dissociation energy Do.
Keq( T )
Delta_G( T )
R. T
159
44
8000 . K
Given
Keq( T ) 1
Tout
Find( T )
Tout = 8.628 10
Keq( Tout ) = 1
stat_thermo.mcd
293. K
3.
1997 . K
3380 . K
2
Thetav
Cvr
Thetavi
3
Cvv
Thetav
Thetav
e
2
Cvt
Cvr
2
i
.e
R.
i=0
Cvtot
960. K
960. K
Cvv
2
Lit: 28.09
stat_thermo.mcd
Cvt
2
2
Cvr
3.
2
2
5254 . K
2995 . K
Thetav
5404 . K
2
Cvv
Thetavi
Thetav
.e
R.
Thetav
i=0
e
Cvtot
Cvt
Cvr
Cvv
Lit: 25.28
stat_thermo.mcd
Part VI. The strange case of NO: The effect of a low-lying electronic
energy level on the heat capacity of NO.
3.
Cvt
2
Cvr
R
1
1904.20 . cm . c. h
Thetav
k
3
Thetav = 2.743 10
K
2
Cvv( T )
Thetav
R.
exp
Thetav
2
1 .T
. exp Thetav
T
T
Now we will consider the electronic partition function for the NO molecule. This molecule has
one unpaired electron in the highest occupied molecular orbital. The molecular term symbol is a
doublet. Also there is a low lying excited state molecular orbital. This level is sufficiently low so
that a significant population of molecules have the single electron in this energy level. This
energy level will be singly occupied and thus have a doublet molecular term symbol. Since both
of these levels are doublets they have a degeneracy of 2. Higher energy molecular orbitals are
not populated so they do not contribute to the partition function.
qe
qe( T ) 2
2. e
174.2. K
T
2.e
174.2. K
T
stat_thermo.mcd
Ue( T )
174.2
2 348.4. K .
R. T .
exp
2
T
T
2
2. e
174.2. K
T
Select the equation above and choose Symbolic Simplify to get the following:
174.2
exp
Ue( T ) 174.2. R. K.
exp 174.2.
1.
K
T
differentiation yields (Verify the result shown here by using the appropriate Mathcad
procedure.)
exp 174.2.
K
d
Ue( T ) 30345.64. R. .
2
dT
T
exp 174.2.
T
1.
exp 174.2.
2
30345.64. R. K .
K
1.
K
exp 174.2.
T
. T2
simplifies to
exp 174.2.
K
T
d
2
Ue( T ) 30345.64. R. K .
dT
1.
exp 174.2.
. T2
T
Cut and paste to create the
numeric heat capacity equation
exp 174.2.
Cve( T )
K
T
2
30345.64. R. K .
1.
exp 174.2.
. T2
stat_thermo.mcd
Now compute the total heat capacity and each of the contributing terms.
2
1
2
kg m sec
2
Cv( T )
Cvt
Cvr
Cvv( T )
2
Cve( T )
2
Cvne( T )
Cvt
Cvr
Cvv( T )
Cvnv( T )
Cvt
Cvr
Cve( T )
stat_thermo.mcd
Now we systematically vary the temperature and examine the results graphically.
20 , 40 .. 1000
30
Figure legend.
Cv( i . K )
20
10
Cvne( i. K )
Cvnv( i. K )
Cve( i. K )
500
1000
Mastery Exercise:
The energy levels for an electron constrained to move on a ring with a diameter of 0.4 nm
are given by E n
2 2
hbar . n
where n is the quantum number identifying the energy level, m is the mass
2
2 . m. d
of the electron and d is the diameter of the ring. Write the expression for the partition function for the
electron on the ring. At room temperature would the electronic partition function for this system
contribute significantly to the heat capacity. Explain by providing graphical or arithmetic evidence.
Acknowlegment: The authors acknowledges the National Science Foundation for support of the 1997
NSF-UFE Workshop on "Numerical Methods in the Undergraduate Chemistry Curriculum Using the
Mathcad Software" and the organizers (Jeff Madura, Andrzej Wierzbicki and Sidney Young, University of
South Alabama).
stat_thermo.mcd