EXPERIMENT E2

INFRARED SPECTRUM OF HCl / DCl

Introduction
Absorption spectra of molecules result from the promotion of molecules from one state to
another of higher energy. The difference in energy levels in a molecule is equal to the
energy of the photons that can be absorbed. In the infrared region it is the rotational and
vibrational energies that change and thus infrared spectra give direct information on these
energy levels. Further, since theory relates the rotational and vibrational states of a
molecule to its structure (i.e., its size, shape and the strength of its bonds), structural
information may be deduced. In this experiment the infrared spectrum of hydrogen
chloride (HCl) is obtained, and from it properties of the molecule are deduced. HCl has
been chosen as the subject of this spectroscopic investigation since the theory is simplest
for diatomic molecules. Also, gas samples give the simplest spectra since there is no
solvent with which the molecules may interact.
Objectives
The aims of this experiment are to:
(1) Record the infrared spectrum of a mixture of HCl and DCl gases;
(2) Determine from the spectrum the energy levels available in the two types of molecules;
(3) Calculate the relative populations of these energy levels;
(4) Find the structural parameters of hydrogen chloride; and,
(5) Examine the effects of the isotopic substitution.
Theoretical Background
Properties of Light
The wave nature of electromagnetic radiation associates with light, sinusoidally varying
the electric and magnetic fields perpendicular to each other and to the direction of
propagation. A schematic is given in Figure 1.
The frequency of the radiation, , is related to its wavelength, by:
) Hz (
c

(1)
where c is the velocity of light. The dual particle-wave nature of light associates with light
of frequency, , a photon energy h, where h is the Planck constant.
Infrared light is that part of the electromagnetic spectrum from ~3 10
12
Hz to ~3 10
14
Hz
lying between the visible and microwave regions of the spectrum. Infrared radiation is
traditionally and conveniently described by its wavenumber, , given by:

1
c
(2)
which has units of cm
-1
and is thus the number of wavelengths in 1 cm. In wavenumbers,
the infrared region extends from ~100 cm
-1
to ~12,500 cm
-1
of which the part below ~500
cm
-1

is called the far infrared and that above 4,000 cm
-1
the near infrared.
Figure 1: The Wave Nature of Light
Quantized Energy Levels
The rotational, vibrational and electronic energies that a molecule possesses are
quantized and a molecule can only absorb radiation of frequency , if a stationary state of
the molecule exists which has energy h higher than an initial state of the molecule. Thus
the frequencies of radiation absorbed by molecules reflect the energy differences between
their various stationary states. It is found that for transitions between rotational states, the
frequencies lie in the microwave and far infrared regions while for those between
vibrational states the frequencies mostly cover the infrared region. The energy differences
between electronic states are greater again, the frequencies lying in the visible and
ultraviolet regions.
Electromagnetic radiation interacts with molecules through either of its oscillating electric
or magnetic fields. The interaction for infrared radiation is found to be through the electric
field. For rotational transitions, quantum mechanical treatment shows that such transitions
can be brought about by the emission or absorption of radiation only if the molecule
possesses a permanent dipole. A dipole, rotating say in the plane of the paper:
produces an oscillating field in that plane. The interaction between the molecule and the
radiation occurs through their oscillating electric fields.
The quantum mechanical treatment of vibrational transitions shows that the emission or
adsorption of radiation occurs only if the molecule has a dipole moment which fluctuates
with molecular vibrations. Then the molecule generates an oscillating electric field with
which it may interact with that of the radiation. A diatomic molecule can only have a dipole
moment which fluctuates with vibration if it is a permanent dipole. Thus, for a diatomic
molecule to give rise to either a rotational or vibrational spectrum, it is necessary for it to
be heteronuclear. Homonuclear diatomic molecules do not absorb or emit infrared
radiation but, of course, they possess quantized rotational and vibrational energies.
Rotational Energy Levels
If a diatomic molecule is regarded as a rigid rotor (i.e., two atomic masses, m
1

and m
2
),
separated by a fixed distance, r, then its moment of inertia, I is given by:
) m . kg : Units ( r I
2 2
(3)
where, , the reduced mass is given as:
) kg : Units (
m m
m m
2 1
2 1
+

(4)
Solutions of the Schrdinger equation for this system show that the stationary states (or
energy levels)

of the system have energies, E
J
, also called eigenvalues. These are given
by:
J) : (Units 2,... 1, 0, J ) 1 J ( J
I 8
h
E
2
2
J
+

(5)
where J is called the rotational quantum number and its restriction to integral values
confers discrete energy values on the system and so E
J
is said to be quantized. It can be
shown that there are ) 1 J 2 ( + states which each have the energy E
J
and the E
J

energy
level is said to be
) 1 J 2 ( +
-fold degenerate. Further, it is found that transitions between
energy levels brought about by the absorption or emission of radiation are only permitted
for a change of unity in the rotational quantum number, i.e., J=1. This is called a
selection rule.
Equation (5) may be written as:
) 1 J ( hcBJ E
J
+
(6)
where B is the rotational constant and is given by:
) cm : Units (
Ic 8
h
B
1
2

(7)
The energy difference, E, between adjacent energy levels may be calculated by noting:
) 2 J )( 1 J ( hcB E
1 J
+ +
+
(8)
) 1 J ( hcB 2
E E E
J 1 J
+

+
(9)
(10)
and the wavenumber, ,of the radiation required to bring about the transition JJ+1 is:
) cm : Units (
) 1 J ( B 2
hc
E
1
+

(11)
(12)
The rigid rotor is a "good" but not completely adequate approximation to a diatomic
molecule. At high rotational energies the angular velocity of the rotating molecule is high
and the bond stretches. It can be shown that for a non-rigid rotor, is given by:
3
) 1 J ( D 4 ) 1 J ( B 2 + + (13)
where D is the distortion constant. The final term of equation (13) is only significant at high
values of J.
Energy Level Populations and Absorption Intensities
A rigid rotor clearly gives rise to a spectrum consisting of equally spaced absorption lines
given by equation (12) whereas for the non-rigid rotor, the absorption lines given by
equation (13) become slightly closer together as J increases. However for an absorption
line to be observed which corresponds to the change of energy from E
J
to E
J+1
, there
must, of course, be molecules in the system which possess the rotational energy, E
J
.
Further, the more molecules with that energy the more intense the absorption line will be.
The Boltzmann equation may be written:

,
_

kT
E
exp
N
N
J
0
J
(14)
where N
0
and N
J
are the number of molecules in the ground state (J=0) and in a state of
energy E
J
above the ground state respectively, and k is Boltzmanns constant. Equation
(5) shows that the ground rotational state has zero energy.
However, what is required is the number of molecules in the energy level E
J
which
contains 2J+1 states and which is given by:

,
_

+
kT
E
exp ) 1 J 2 (
N
N
J
0
J
(15)
Here N
J
is the number of molecules in energy level E
J
and N
0
is identical to N
0
since the
ground level is not degenerate. Substituting equation (6) into equation (15) yields:

,
_

+
+
kT
) 1 J ( hcBJ
exp ) 1 J 2 (
N
N
0
J
(16)
A plot of N
J
/N
0
against J for a typical value of B, say 5 cm
-1
, shows that the population of
the rotational energy levels passes through a maximum at about J=4 and is still significant
at J>10. The intensities of the absorptions follow this population curve as shown in Figure
2.
Figure 2: Rotational energy levels, population and spectrum conditions: B = 5.0 cm
-1
; D =
5.0 10
-4
cm
-1
; T = 298 K.
Vibrational Energy Levels
The simplest model of a diatomic molecule is that of two atomic masses held together by
a bond which, like a spring, obeys Hooke's law. The molecule undergoes simple harmonic
motion with a frequency,
0
, given by:
1 6.9%
3 12.7%
5 12.9%
4 13.4%
6 11.4%
7 9.4%
8 7.2%
2 10.4%
J Population
Rotational
Energy
Level
0
500
% Transmission
) s : Units (
' k
2
1
1
0
2
1

,
_

(17)
where k' is the Hooke's law constant or force constant of the bond. Solutions of the
Schrdinger equation for this system reveal the stationary states of the system to have
energies, E
v
, given by:
( )
0
2
1
v
h v E + (18)
where v is the vibrational quantum number which can take only integral values (v = 0, 1, 2,
). Further, transitions between the vibrational states of the system are restricted to
those for which v = 1. Note that in the ground vibrational state, v = 0, the molecule still
possesses vibrational energy of
0
2
1
h which is called the zero point energy.
The potential energy curve for a harmonic oscillator is a perfect parabola centred around
the equilibrium bond length. Real bonds, however, have potential energies which follow
the familiar Morse curve and give rise to anharmonic oscillations. Quantum mechanics
gives the energies of the anharmonic oscillator as:
( ) ( )
0
2
2
1
0
2
1
v
h v h v E + +
(19)
where the last term, containing the anharmonicity constant, , only becomes important at
high values of v. In addition to the v = 1 transition, the v = 2, 3, etc. transitions are
also permitted for the anharmonic oscillator. However the latter transitions will be ignored
in this treatment because they are of low probability and hence result in weak absorptions.
Further, for HCl, their frequencies lie outside the range of the spectrometer used.
The treatment of vibrational energy levels is further simplified by considering the
population of the vibrational energy levels. Typically the first excited vibrational state has
an energy ~4 10
-20
J above the ground state. A Boltzmann equation calculation shows
that the percentage of molecules in the ground state exceeds 99.99%. Thus transitions
from the v = 1, 2, ... vibrational states can be neglected. The outcome of these
considerations is that the absorption spectrum for HCl results from the transition from the
ground state to the first excited vibrational state which is traditionally designated as v"v'.
Rotational-Vibrational Spectra
If it is assumed that there is no interaction between the simultaneous rotation and
vibration of a molecule then the total rotational-vibrational energy levels of a diatomic
molecule, E
v,J
, may be given as the sum of equations (5) and (18); i.e.,
( )
0
2
1
J , v
h v ) 1 J ( h c B J E + + + (20)
Here the small rotational distortion and anharmonicity terms have been neglected.
However, rotation and vibration are not independent. This is because the value of B
depends on the vibrational state since the amplitude of the vibration increases with
increasing vibrational energy. It has been found that this interaction can be accounted for
by the introduction of a cross-coupling term into (20); i.e.,
( ) ) J : U n i t s ( h c ) 1 J ( J ) v ( h v ) 1 J ( h c B J E
2
1
0
2
1
J , v
+ + + + + (21)
where is the small rotation-vibration coupling constant in units of cm
-1
. Dividing both
sides of (21) by hc yields an expression for the energy levels in wavenumber units; i.e.,
( ) ) c m : U n i t s ( ) 1 J ( J ) v ( v ) 1 J ( B J E
1
2
1
0
2
1
J , v

+ + + + +
(22)
At room temperature, diatomic molecules are typically in their ground vibrational state but
spread over a range of rotational states. For diatomic molecules, the selection rule for
pure rotational transitions also applies to rotational-vibrational transitions. Thus, the
transition from the ground vibrational state, v", to the first excited vibrational state, v', is
accompanied by a change of rotational state corresponding to J = 1. The permitted
transitions are shown in Figure 3.
Figure 3: Transitions between rotational-vibrational energy levels.
The absorption wavenumbers, , are given by:
" J , " v ' J , ' v
E E
(23)
For v"=0 and v'=1 the absorption wavenumbers form two sets,
R
and
P
corresponding
to J'=J"+1 and J'= J"-1, respectively. These two sets are called the R and P branches and
it is easy to show, using equations (22) and (23) that:
2
0 R
" J " J ) 4 B 2 ( ) 3 B 2 ( + + J=0, 1, 2, (24)
2
0 P
" J " J ) 2 B 2 ( J=1, 2, 3, (25)
Making the substitutions:
1 " J m +
R branch (26)
R
4
R
2
R
3
R
0
R
1
P
2
P
1
P
3
P
4
P
5
0
3
2
4
1
5
0
3
2
4
1
5
J values
J values
v
(v=0)
v
(v=1)
" J m
P branch (27)
as shown in Figure 4, (24) and (25) both become:
2
0 m
m m ) 2 B 2 ( + (28)
where m has positive and negative integer values except zero. The separation between
adjacent absorption lines,
m
, is given by:
m 2 3 B 2
m 1 m m


+
(29)
(30)
from which B and may be readily evaluated. Equation (28) then permits
0

to be
determined, from which the force constant of the bond can be found.
Wavenumber (cm
-1
)
0
1
1
2
3
4
2
3
4
5
6
7
5
6
7
8
1
-1
3
-3
2
-2
4
-4
6
-6
5
-5
7
-7
J" values
m values
R branch P branch
Figure 4: Rotational-vibrational spectrum of a diatomic substance.
Isotopic Substitution
Isotopic substitution does not affect the force constant of a bond or its length. However,
the rotational and vibrational levels are both changed because the reduced mass is
changed. Using an asterisk to distinguish one isotopic species from the other, it can be
shown using equations (3), (4) and (7) that:

*
B
* B
(31)
and from (17) that:
2
1
*
*
0
0

,
_

(32)
These relations permit the experimentally determined ratios,
B * B
and
0 0
* to be
compared to the theoretical values calculated from atomic masses. Equation (4) reveals
that changes substantially on the substitution of deuterium into hydrogen chloride
whereas is almost independent of the chloride isotope,
35
Cl or
37
Cl, involved. Hence the
isotope effect is investigated using DCl and because the isotopic shift in
0

is substantial,
the spectra of DCl and HCl can be recorded without overlap using a mixture of the two
gases.
The Rotational Partition Function
It has previously been noted that N
J
/N
0
, given by equation (16), is the ratio of the number
of molecules of energy E
J
to the number in the ground state. Hence:
r
0
T
J
0 J 0
J
q
N
N
N
N

(33)
where N
T
is the total number of molecules in the system and q
r
is called the rotational
partition function. Here, the significance of q
r
is that it permits the fraction of molecules
with energy E
J
to be calculated thus:
r 0
J
T
J
q N
N
N
N

(34)
Substituting (16) yields:
1
]
1

+ +

kT
) 1 J ( hcBJ
exp
q
) 1 J 2 (
N
N
r T
J
(35)
The rotational partition function may be evaluated as follows:
1
]
1

+

1
]
1

+
+

kT
) 1 J ( hcBJ
exp
hcB
kT
dJ
kT
) 1 J ( hcBJ
exp ) 1 J 2 (
dJ
N
N
N
N
0
0
0
J
J
0 J 0
J
(36)
(37)
(38)
hcB
kT
q
r
(39)
Substituting (39) into (35) yields:
1
]
1

+ +

kT
) 1 J ( hcBJ
exp
kT
hcB ) 1 J 2 (
N
N
T
J
(40)
Experimental Section
General
(a) Outline: At room temperature, essentially all HCl molecules (>99.99%) are in their
ground vibrational energy level corresponding to a vibrational quantum number, v, equal
to zero. However, the molecules are distributed over a range of rotational energy levels
from the ground level (rotational quantum number, J, equal to zero) to quite high rotational
energy levels corresponding to J=10 or more. This is a consequence of the large energy
separation between vibrational levels, the small energy separation between rotational
levels and the fact that the rotational levels are (2J+1)-fold degenerate; i.e., there are
(2J+1) rotational states with quantum number J and hence with the same energy.
HCl molecules have the requisite physical properties to be able to absorb infrared
radiation of characteristic wavelengths and undergo rotational-vibrational transitions.
These transitions correspond to combined changes of v=+1 and J=1. Thus the
rotational-vibrational spectrum consists of two series of absorption peaks; one
corresponding to J=+1 called the R branch and the other corresponding J=-1 called the
P branch. The R and P branches occur on the high and low frequency sides respectively
of the frequency
0
, which corresponds to the straight vibrational transition, v=+1, but for
which no actual absorption occurs because the J=0 rotational transition is forbidden for
HCl. The distinctive appearance of the spectrum makes it easy to assign J values to the
absorption peaks.
The infrared spectrum of an approximately 1:1 mixture of HCl and DCl is recorded in a cell
fitted with NaCl windows. Some spurious peaks due to water vapour and adsorbed water
may be observed but the rotational-vibrational peaks of HCl and DCl will be readily
identifiable by their characteristic R and P branches.
Carrying out this treatment on both HCl and DCl spectra provides the data to test the
predictions of the isotope effect. All the information required to construct the rotational-
vibrational energy level diagrams of hydrogen chloride and deuterium chloride has then
been obtained.
(b) Apparatus: The vacuum system consists of a two stage rotary oil pump preceded by a
trap cooled in liquid nitrogen. A manifold permits various vessels to be connected to the
system and the pressure in the system can be measured with a U-tube manometer.
Safety glasses must be worn when operating the system.
A vacuum tight gas cell fitted with NaCl windows is kept in a desiccator when not actually
in the spectrometer or on the vacuum line. This minimizes the adsorption of water vapour.
Do not touch the NaCl windows.
(c) Reagents: A dry, air-free sample of an approximately 1:1 mixture of HCl and DCl is
supplied in a tap vessel of ~1 L capacity at ~0.8 atm pressure. This is sufficient to give a
pressure in the cell greater than the ~0.5 atm required for an acceptable spectrum. After
the spectrum has been recorded the gas in the cell must be vacuum transferred back to
its tap vessel.
(d) Spectrometer: See demonstrators. The spectrometer operates over a spectral range of
400-4000 cm
-1
.
Experimental Procedure
The demonstrator will advise you of all the procedures needed for using the vacuum
frame to fill the IR cell with the HCl/DCl gas. Assistance with running the spectra on the
FT-IR will also be given.
Analysis of Results
1. Label each of the peaks on the spectra of the HCl and DCl as shown in Figure 4.
Determine the wavenumber of each peak. Record the data in a table with the following
columns J", m and .
2. From plots using equation (30) determine values of and B for HCl and DCl.
3. Determine the value of
0

for both gases from a plot using equation (28).

4. The experimentally determined values of
0

and B permit scaled diagrams to be

drawn of the rotational-vibrational energy levels of hydrogen chloride and deuterium
chloride. The energy levels are determined using equation (22). The diagrams, similar to
Figure 3, should show all the J values for which J" has a significant population (i.e., strong
absorptions).
5. The fraction of molecules in each of the J" levels is calculated as a Boltzmann
distribution using equation (40). For either the P or the R branch it is possible now to plot
a diagram similar to that of Figure 2. (You should do this only for one branch of one of the
gases). Note: The argument of an exponential function is unitless. Make sure the units
cancel in exponential function of equation (40).
6. Using the value of B determined above it is now possible to calculate the values of I,
the moment of inertia, from equation (7). From this value, a value of the bond length r can
be determined with equation (3).
7. Use the values of B and
0

for HCl and DCl to test the predictions of the isotope

effect using equation (31) and (32).
Points that need to be included in the Discussion
1. Compare the data obtained with literature values (Note: You can obtain literature
values for HCl and DCl from the internet and from references below). How accurate is the
experiment?
2. Does the experiment highlight the isotope effect? What is this effect?
3. Comment on the observed population distributions for the systems examined.
4. Discuss the sources of error for this experiment. How could the results accuracy be
improved?
Note: If these points are not included in the Discussion section of your report, your report
will be given a lower mark.
References
P.W. Atkins, "Physical Chemistry", 3rd ed., pp. 432-53; Oxford University Press, Oxford
(1986).
C.N. Banwell, "Fundamentals of Molecular Spectroscopy", 3rd ed., pp. 1-35, 40-58, 72-91,
118-20; McGraw-Hill, London (1983).
F.C. Strong, J. Chem. Ed., 56, 681 (1979).
Partial List of Symbols
Symbol Meaning Units
B Rotational constant cm
-1
c Velocity of light m s
-1
, cm s
-1
D Rotational distortion constant cm
-1
E
J
Energy of rotational level J J
E
v
Energy of vibrational level v J
h Planck's constant J s
I Moment of inertia kg m
2
J Rotational quantum number Unitless integer
J' Rotational quantum number associated with first
excited vibrational level Unitless integer
J" Rotational quantum number associated with the
ground vibrational level Unitless integer
k Boltzmann's constant J K
-1
k' Bond force constant N m
-1
m Function of J defined by (26) and (27) Unitless integer
m
1
, m
2
Atomic masses kg
N
J
Number of molecules in rotational energy level of
quantum number J
N
0
Number of molecules in ground rotational energy level
q
r
Rotational partition function
r Bond length m
v Vibrational quantum number Unitless integer
v' Upper vibrational state Unitless integer
v" Lower vibrational state Unitless integer
Rotation-vibration coupling constant cm
-1
Wavelength m, cm
Reduced mass of rigid rotator kg
Frequency Hz
Frequency in cm
-1
cm
-1

0
Frequency of bond oscillation Hz
0

Frequency of bond oscillation in cm

-1
cm
-1