Microwave (Rotational) Spectroscopy spectroscopy BSc-Lect-2.pdf · Effect of isotopic substitution...
Transcript of Microwave (Rotational) Spectroscopy spectroscopy BSc-Lect-2.pdf · Effect of isotopic substitution...
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Microwave (Rotational)
Spectroscopy
Prof. Tarek A. Fayed
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Microwave Spectroscopy It is concerned with transitions between rotational energy levels
in the molecules, the molecule gives a rotational spectrum only
If it has a permanent dipole moment:
A‾
B+
B+
A‾
Rotating molecule H-Cl, and C=O give rotational spectrum (microwave active).
H-H and Cl-Cl don't give rotational spectrum (microwave inactive).
Which of the following molecules would show rotational spectrum:
Br2 , HBr and CS2? Why?
Rotational spectroscopy is only really practical in the gas phase
where the rotational motion is quantized. In solids or liquids the
rotational motion is usually quenched due to collisions between their
molecules.
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Rotational energy of a diatomc molecule
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General features of rotating system:
1- Rotational motion in classical mechanics
Rigid Rotors: molecules in which bonds don't
distort under the stress of rotation.
Linear velocity (v) = ---------- Time
Distance Angular velocity (ω) = ------------
Radians
Time
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Linear momentum (P) = m . v
Angular momentum (J) = I . ω
Where; the moment of inertia for a molecule (I) =
Then; I = m .r2
= Σ m .r2
i i i
Where: ri is the perpendicular distance of the atom i
from the axis of rotation (bond length).
Moment of inertia (I), also called mass moment of
inertia which is a measure of an object's resistance to
changes in its rotation rate. It is the rotational analog
of mass.
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A molecule can have three different moments of
inertia Ia, Ib and Ic ,according to the axis of
rotation.
Ia
Ib
Ic
H
Cl
In HCl, Ia = 0, Ib= Ic.
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Rigid rotors are classified into four groups:
1- Linear rotors: such as diatomic or linear molecules, as
H-Cl, O=C=S, acetylene and O=C=O, have; Ia=0 and Ib= Ic.
2- Spherical tops rotors: e.g. CH4, SiH4
and SF6 have three equals moment of
inertia.. Ia= Ib= Ic.
3- Symmetric tops rotors: e.g.
NH3, CH3CN and CH3Cl, have
two equal moments of
inertia. , Ia= Ib ≠ Ic.
(3)
4- Asymmetric tops rotors: e.g. H2O,
CH3OH, vinyl chloride CH2=CHCl and
formaldehyde, have three different
moments of inertia. Ia ≠ Ib ≠ Ic.
Ia
Ic
Ib
(4)
Ia
Ib
Ic(2)
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Classes of Rotating Molecules
Molecules can be classified into five main groups depending
on their moments of inertia.
1. IC = IB , IA = 0 Linear molecules
2. IC = IB = IA Spherical top
3. IC = IB > IA Symmetric top
5. IC > IB > IA Asymmetric top
Homonuclear diatomic molecules (such as H2, O2, N2 , Cl2) – have zero
dipole (non polar) - have zero change of dipole during the rotation,
hence NO interaction with radiation - hence homonuclear diatomic
molecules are microwave inactive
Heteronuclear diatomic molecules (such as HCl, HF, CO) – have
permanent dipolemoment (polar compound) - change of dipole occurs
during the rotation – hence interaction with radiation takes place –
Therefore, heteronuclear diatomic molecules are microwave active.
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H H
O
52.3o
θ
2
HH
2
HH
2
i
i
i rm0rmrmI
= 2×(1.67×10-27 kg) × (95.7×10-12)2 × Sin2 52.3
=1.91× 10-47 kg m2
= 2 m r2 sin2 θ
• Calculate the moment of inertia of water molecule
around the axis defined by the bisector of HOH bond.
bond angle (HOH) = 104.5o and bond length (OH) = 95.7
pm ? (H = 1.0079, Atomic mass unit = 1.6606 x 10-27
kg).
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From the moment of inertia one can calculate
the bond length as well as the atomic masses
For linear diatomic molecules, the moment of inertia
can be calculated as follows;
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Simplest Case: Diatomic or Linear Polyatomic molecules
Rigid Rotor Model: Two nuclei are joined by a weightless rod
EJ = Rotational energy of rigid rotator (in Joules)
J = Rotational quantum number (J = 0, 1, 2, …)
I = Moment of inertia = mr2
m = reduced mass = m1m2 / (m1 + m2)
r = internuclear distance (bond length)
m1
m2
r
1 JJI8
E2
2
J
h
Rotational Spectra of Linear Rigid Rotators
From solution of
Schrodinger equation;
m2
m1
r
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1 JJI8
E2
2
J
h
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From microwave spectroscopy, bond lengths can be
determined with a correspondingly high precision, as
illustrated in this example. From the rotational microwave
spectrum of 1H35Cl, we find that B = 10.59342 cm-1.
Given that the masses of 1H and 35Cl are 1.0078250 and
34.9688527 amu, respectively, determine the bond
length of the 1H35Cl molecule.
Example
2 2
0
34
0 2
2 27
10
8
6.6260755 10
8 1.0078250 34.96885278 1.66054 10 10.59342
1.0078250 34.9688527
1.274553 10
hB
cr
hr
cBc
m
m
m
We have;
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Rotational transitions in rigid diatomic molecule.
Selection rules:
1- μ 0
molecule gives a rotational
spectrum only if it has a
permanent dipole moment
2- Δ J = ± 1
+1 absorption.
-1 emission.
Allowed transitions
Separation between adjacent levels:
EJ = E(J) – E(J-1) = 2BJ
and B can be obtained from the
spacing between rotational lines in
the spectra of molecules.
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Transitions observed in the rotational spectrum
1J0J n; transitioFor the *
10
1
01 202
jj
jjj
spectrumtheinlinefirsttheofposition
cmBBEEE
2J1J n; transitioFor the *
21
1
12 426
jj
jjj
spectrumtheinlinesecondtheofposition
cmBBBEEE
3J2J n; transitioFor the *
32
1661223
jjspectrumtheinlinethirdtheofposition
cmBBBjEjEjE
1 JJIc8
E2J
hSince;
Then;
and;
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Since, The allowed rotational energies are given by;
The wave numbers of the different rotational levels will
be; 0, 2B, 6B, 12B, 20B, 30B (cm-1),… and so on
1
1 )1(2
cmJBEEE jjj
And for two adjacent rotational states, the energy
difference is given by;
Hence, the wave number of the lines observed in the
rotational spectrum will be; 2B, 4B, 6B, 8B (cm-1), …… and
so on.
And the various lines in the rotational spectra will be equally
spaced (separation between lines = 2B)..
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Microwave spectrum of rigid rotator
Separation between adjacent lines = 2B
So, B can be obtained from the spacing between
rotational lines.
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Examples of rotational spectra of rigid diatomic molecules
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Rotational Spectrum of CO
J. Michael Hollas, Modern Spectroscopy, John Wiley & Sons, New York, 1992.
J” → J’ E(J’)-E(J”)
3 → 4 2(1.91)(4) 15.3 cm-1
4 → 5 2(1.91)(5) 19.1 cm-1
5 → 6 2(1.91)(6) 22.9 cm-1
6 → 7 2(1.91)(7) 26.7 cm-1
7 → 8 2(1.91)(8) 30.6 cm-1
8 → 9 2(1.91)(9) 34.4 cm-1
9 → 10 2(1.91)(10) 38.2 cm-1
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Example:
The first rotational line in the rotational spectrum of CO
is observed at 3.84235 cm-1. Calculate the rotational
constant (B) and bond length of CO. The relative
atomic weight C =12.00 and O = 15.9994, the
absolute mass of H= 1.67343x10-27 kg.
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1
10
92118.1
28425.3
cmB
B
247
102
34
2
.105695.14
1099793.28
10626.6
8
mkg
BI
cBhI
CO
o
CO
CO
AnmrSo
mI
r
kg
131.1113.0,
102799.1
38365.111048303.46
1056136.2692168.19
2202
27
54
m
m
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Intensity of rotational spectral lines
(Population of energy levels)
Boltzmann
distribution
Number of degenerated
energy levels
Population of energy levels is affected by;
1- Boltzmann distribution
2- Number of degenerated energy levels (levels
which have the same energies)
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1-Boltzmann distribution
oNstatefirsttheinmoleculesofnumberThe
jNstatehigheranyinmoleculesofnumberThe
)1(
JJB
eeeN
N
j
TkchTkhTkE
o
j J
kThcJBJkTJBhcJ
o
jee
N
N)1(/)1(
So,
The population of the state decreases as the J –value increases.
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Example; For HCl, 2B = 21.2 B = 10.6, T=300 K,
h=6.626x10-34 J.s, k=1.38x10-23 J/K, c = 3x 1010 cm/s
1,0 0 eN
NJ
o
o
903.0
,1
)(0509.0
1(3001038.1
1031063.66.10
1 23
1034
JJ
JJ
o
e
eN
NJ
7367.0,2 )(0509.02 JJ
o
eN
NJ
2- Make another calculations with B = 5
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Bhigherwithand
JgincreawithdecreasesN
N
o
J sin
The Boltzmann distribution alone does not fit the shape
of the spectra so, degeneracy of the states is required.
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Kinetic energy (K.E) in rotational motion =½ I.ω2
and since, angular momentum (P) = I.ω then;
I
P
I
I
I
IIE
2
2
2
22
2
2
IEP 2
I
JJhE
22
4
)1(2
22
4
)1(2
2 PJJh
IE
unit. momentum angular lfundamenta theish
unitJJh
JJP
2
.)1(2
)1(
2-Degeneracy The existence of more than two energy states having the
same energy.
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For J =1
P is quantized, so
it takes a
directions such
that the value of P
along the reference
direction are
(-1, 0, +1).
Number of
degeneracy is
2J + 1 = 3
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For J = 2
(-2, -1, 0, 1, 2)
degeneracy.
Number of
degeneracy is
2J + 1 = 2x2 +1= 5
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Effect of isotopic substitution On changing from 12C16O 13C16O, atomic mass
increases, B decreases ( 1/I), so energy of levels
becomes lower.
2B 4B 8B 12B
cm-1 spectrum
J = 6
5
4
3 2 1 0
12CO 13CO
Energy
levels
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From comparison of rotational energy levels of 12CO and 13CO
We can determine:
(i) isotopic masses accurately, to within 0.02% of other
methods for atoms in gaseous molecules;
(ii) isotopic abundances from the absorption relative intensities.
Example:
for 12CO the transition J=0 J=1 appears at 3.84235 cm-1
for 13CO the transition J=0 J=1 appears at 3.67337 cm-1
Given : 12C = 12.0000 ; O = 15.9994 amu
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What is isotopic mass of 13C ?
B(12CO) = 1.921175 cm-1
B(13CO) = 1.836685 cm-1
Now
(13C) = 13.0006 amu
μ
1
I
1B
1.046001.836685
1.921175
CO)μ(
CO)μ(12
13
15.999412
15.999412
15.9994C)(
15.9994C)(1.046
13
13
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We can obtain; atomic masses, bond length or relative
abundance of isotopes
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Applications of microwave spectroscopy
Microwave spectroscopy has been used in monitoring
and control of industrial processes. It is an ideal
process analyzer as it is:
1. non-invasive: the measurement can be made
outside of the reaction chamber, eliminates the
need for sampling or physical removal of sample.
2. non-destructive.
3. can be used for solids, liquids, gases and
suspensions .
4. can be used for dark coloured samples.
5. analyses large sample volumes, as microwaves
diffuse out from the transmitter though the entire
sample becomes lower.
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Microwave spectroscopy has been used in monitoring
and control of industrial processes, such as;
1. materials with low dielectric constants, such as
plastics, glass, ceramics and composite materials.
2. determination of moisture in various tobacco types.
3. Monitoring of a batch esterification reaction as in
the esterification of butanol by acetic acid.
4. Monitoring of the drying process in industry as it is
one that is hard to monitor. For example, huge
cakes of wet material when dried in big vessels.
5. Astrophysical applications, radioastronomy: probe
of the molecular universe (molecular clouds) using
Telescope.
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