IR Spectroscopy Problem Set 3

Name SOLUTIONS Ch 1b, Problem Set Three
Section Side 1 of 16 Due Friday, J an. 27, 2012

Rec TA at 4 PM in the Drop Box

1. Vibrational Motion, Infrared (In)active Modes & Degeneracy (10 points)
In lecture you saw different types of vibrational motions for a linear triatomic molecule
and a bent molecule. (To get a better feel for these molecular motions, you may want to
look at the animated .gifs for the six different vibrational modes for the -CH
2
group at:
http://en.wikipedia.org/wiki/Infrared_spectroscopy#Theory.) When the stretching and
bending motions were presented in class, we briefly discussed which vibrational motions
were infrared active and which were infrared inactive for each molecule.

Consider the normal modes for the vibrational motions of a planar molecule, GaI
3
.

(a) In the Figure above: are there too many, too few or just enough diagrams drawn to
capture all modes of vibrational motion for this molecule? Briefly explain your
answer. (4 points)
(b) Identify which modes are infrared active and which are infrared inactive for GaI
3
.
Briefly explain your answer. (6 points)
Solution for Problem 1a
There are just enough diagrams since the molecule has six vibrational degrees of freedom
(4 points). Student does not need to show work.
Solution for Problem 1b
Only the first mode,
1
, is infrared inactive; all other modes are infrared active. The
molecule has no permanent dipole moment and the symmetric stretch in
1
does not
cause a dipole moment. All other motions,
2
-
6
, produce a dipole moment.

2. Molecular Electronic Spectroscopy (40 points)
You perform experiments and measure the following spectroscopic constants for the
ground and first excited states of carbon monoxide, CO.
Parameter (Units) Ground state (X
1
+
) First Excited State (A
1
)
r
e
() 1.1281 1.2351
e
(cm
-1
) 2170.21 1515.61
e
x
e
(cm
-1
) 13.46 17.25
D
e
(cm
-1
) 90 230 25 160
Data from: A. Ellis, M. Feher & T. Wright, Electronic and Photoelectron Spectroscopy:
Fundamentals and Case Studies. Cambridge University Press (2005), p. 30.
For this problem refer to the following potential energy figure.

You should notice that the curves for potential energy are no longer parabolic, as they
would be for an ideal harmonic oscillator. To include anharmonicity we often model the
spring (oscillator) potential using the Morse potential, which leads to this equation for
vibrational energy levels,
( ) ( )
2
2
1
2
1
,
+ + = v x h v h E
e e e v vib

,
or as a term value,
( ) ( ) ( )
2
2
1
2
1
+ + = v x v v G
e e e

,
with
e
expressed in wavenumbers. The symbols are defined as:
e
: the oscillation frequency (the same as in OGC/OGN or
e
);
x
e
: a dimensionless quantity, called the anharmonicity constant, which accounts for
deviations from an ideal harmonic oscillator;
Other symbols commonly used:
r
e
: the equilibrium internuclear distance (average bond length, same as r
eq
in figure).
D
e
: the dissociation energy measured from the bottom of the potential well. The
dissociation energy is the energy required to dissociate a molecule into atoms with zero
velocity.

2. Molecular Electronic Spectroscopy (continued)

(a) On a single plot, sketch potential energy versus internuclear distance for both the
ground and excited states. (You may use wavenumbers instead of energy for the
y-axis.) Label important features (r
e
, D
e
) with their values for CO. In addition,
you should sketch the first six vibrational energy levels for each state. (10 points)
(b) In the electronic ground state at room temperature, which vibrational state is most
likely to be occupied? J ustify your answer. (5 points)
(c) In the electronic ground state, what is the spacing between lines in rotational
spectroscopy? Express your answer in wavenumbers. (5 points)
(d) Calculate the spacing between lines in rotational spectroscopy for the first excited
state. Express your answer in wavenumbers. (5 points)
(e) Calculate the zero-point energy for the molecule in its excited state. Express you
answer in J oules. (5 points)
(f) By what percentage does the force constant increase when the molecule
fluoresces from the first excited state back to its ground state? Report your answer
with three significant figures. (5 points)
(g) When we analyzed vibrational motion in class, we assumed that the force constant
which is a measure of bond stiffness was proportional to the bond energy so
we could make approximations when we didnt have exact values available. For
this problem, use the data in the Table to estimate the value of the dissociation
energy for the first excited state. How does it compare to the measured value?
(5 points)


Solution for Problem 2a

10 points total:
1 point for general shape of curves (not just parabolas)
1 point for labeling curves with words or symbol to denote the state
2 points for minimum of excited state slightly to right of ground state minimum
2 points for labeling equilibrium radii (1 point each)
2 points for labeling energy levels in some way
1 point for vibrational energy levels about equally spaced in ground state
1 point for vibrational energy levels getting smaller in excited state

It is not important if the student uses energy or wavenumber for the y-axis. It is not
important if the student puts the zero energy mark at the bottom of the well for the
ground state or at the dissociation level.


Solution for Problem 2b
The student can either perform the complete calculation or use the approximations we
discussed in class. Ill only present the approximation here.

The Boltzmann distribution is,
(
T k
E
g
g
n
n
B
exp . (2 points)
We know that k
B
T200 cm
-1
at room temperature (1 point; from lecture notes) and that a
typical vibrational frequency is on the order of 1000 cm
-1
. (1 point) Since the ratio of
E/ k
B
T is large, the Boltzmann distribution predicts that the population ratio between the
excited state and the ground state is very small; so mostly just the ground state is
populated at room temperatures. (1 point for final answer)

Give full credit to a student who refers to page 8 of Lecture #2 (or other reliable source
not wikipedia) and quotes the text Vibrational energy levels: mostly just the ground state
is populated at room T.

Give no credit if the student just writes the statement/answer without justification/source.


Solution for Problem 2c
The lines in rotational spectroscopy are separated by 2B,
I
h
B
2
4
2
= ,
and the moment of inertia is
2
R I = and ) /(
2 1 2 1
m m m m + =

(2 points using the three equations above in some way)

2
2 1
2 1
2
1
4
2
R m m
m m h
B
+
=

Since 2B is a frequency and we want to express this result in wavenumbers, divide both
sides by the speed of light,
2
2 1
2 1
2
1
4
~
2
R m m
m m
c
h
B
+
=
.
(1 point for dividing by speed of light somewhere in problem to convert to wavenumbers)

( ) ( )( ) J
s m kg
cm
m
m
A
kg x
u
A u u
u
s m x
s J x
B
2 2
2 2
2 20
27 2 8 2
34
/
10
10
10 6605387 . 1 ) 1281 . 1 (
1
9949 . 15 0000 . 12
9949 . 27
/ 10 9979925 . 2 4
10 6260688 . 6 ~
2

=

8640 . 3
~
2 = B cm
-1
(2 points total: 1.5 point answer; 0.5 point sig figs)
(intermolecular distance had five sig figs and all constants should have more than that in
the above calculation)

Solution for Problem 2d
The internuclear distance changes but the reduced mass does not, which means you only
have to take a ratio of the internuclear distances to find the new value.
(3 points for taking a ratio OR for substituting the new value into the equation from the
previous part OR any other logical way of getting an answer)

2235 . 3
~
2 = B cm
-1
(2 points total: 1.5 point answer; 0.5 point sig figs)

Side note: Why are there so many sig figs for an equilibrium internuclear distance? If
you remember, we usually estimate the internuclear distance from the rotational constants
(not the other way around as we did in this problem). If you look at tables of rotational
constants for molecules, youll even see numbers with more sig figs sometimes even
nine or ten. No measurement can be made as precisely as frequency, so when utmost
accuracy is important, one should strive to measure the phenomenon of interest in terms
of a frequency. (H.A. McGee, J r., Molecular Engineering)


Solution for Problem 2e
Starting with the equation for the anharmonic oscillator,
( ) ( )
2
2
1
2
1
,
+ + = v x h v h E
e e e v vib

.
The zero-point energy can be found from the v=0 state and the equation for vibrational
energy levels,
e e e zeropo
x h h E
2
int
2
1
2
1
|
.
|
\
|
=
. (2 points)

In the Table the frequency is in wavenumbers; so we must multiply by the speed of light,
( )
e e e e e e zeropo
x hc x hc hc E
2
1
2
int
2
1
2
1
2
1
=
|
.
|
\
|
=

(1 point for realizing that you have to multiply by the speed of light)

Solving for the zero-point energy,
( )( )
m
cm
s m x s J x E
100
cm 25 . 17
2
1
1515.61cm / 10 9979925 . 2 10 6260688 . 6
2
1
1 - 1 - 8 34
|
.
|
\
|
=

20
10 497 . 1

= x E J
(2 points total: 1.5 points answer; 0.5 points sig figs)
NOTE: the value for
e
x
e
only has four sig figs.


Solution for Problem 2f
Start with the relationship between the frequency and the force constant,

k
2
1
= . (2 points)
Solving for the force constant,
2 2
4 = k .

We want to find the percent increase in the force constant after flourescence and use the
fact that the reduced mass does not change during this transition,
100 100
4
4 4
100
2
*
2
*
2
2
*
2
2
*
2 2 2
*
*
x x x
k
k k
ground ground ground

(1 point: definition of percent increase)
(1 point: recognizing reduced mass doesnt change)

( )
( )
100
61 . 1515
61 . 1515 ) 21 . 2170 (
100
2
1
2
1 2 1
*
*
x
cm
cm cm
x
k
k k
ground

% 105 100
*
*
=
x
k
k k
ground

The force constant increases by about 105%. (1 point: answer)


Solution for Problem 2g
Well assume that the dissociation energy, D
e
, is proportional to the force constant,
k D
e
~ .

Start again with the relationship between the frequency and the force constant,

k
2
1
= .
Again, well solve for the force constant,
2 2
4 = k .

We want to solve for the dissociation energy of the first excited state in terms of the
dissociation energy for the ground state and the two frequencies. Again, the reduced
mass does not change during the transition.
2 2
2
*
2
,
,*
4
4
ground ground e
e
D
D

= ,
2
*
,
2
2
*
, ,*
|
|
.
|
\
|
= =
ground
ground e
ground
ground e e
D D D
,
(2 points for getting to this equation or following similar steps)

( )
2
1
1
1
,*
21 . 2170
61 . 1515
90230 |
.
|
\
|
=

cm
cm
cm D
e

1
,*
44007

= cm D
e

(2 points answer: order of magnitude and first two sig figs are important)
Turns out that were not even close. In class you saw that we were able to make
estimates of properties to within 10% in many cases, following similar solution schemes.
This process tends to breakdown when the two atoms get very close (like in carbon
monoxide). The bond length for CO is about 1.13 , which is significantly smaller than
the bond length for a C-C triple bond (1.20 ).
(1 point: any comparison that demonstrates the student realizes the estimate isnt even
close)

3.
1
H NMR: Number of Peak Groupings and Relative Areas (18 points)

Use different letters of the Greek alphabet (, , , , ) to clearly mark groups of
chemically equivalent hydrogen atoms. From your analysis of hydrogen equivalence,
estimate the relative peak areas for NMR spectra. Use the two molecules in the top row
as examples. (3 points each)

Molecule Relative Areas Molecule Relative Areas
() ()
CH3OH
:
3:1

() () () ()
CH
3
CH
2
OCH
2
CH
3

:
6:4
CH
3
CH
2
CH
2
Br
CH
3
a
a
CH
3
CHCH
2
Cl

CH
3
CH
2
CH
2
CH
2
CH
3


(Graders: Give full credit if students reduce the ratios. For instance, if they report 1:2
instead of 2:4 then dont subtract anything.)

4.
1
H NMR: Interpreting Chemical Shifts (4 points)
Assume the reference (=0.00 ppm) is comprised of hydrogen atoms on the methyl
groups in the reference compound, tetramethylsilane (TMS). Explain why the chemical
shift increases ( values become larger) for this series of molecules.

Molecule (ppm)
CH
3
I 2.10
CH
3
Br 2.70
CH
3
Cl 3.05
CH
3
F 4.30
Solution
Hydrogen atoms on carbon atoms with electronegative elements (e.g, oxygen, halogens)
have less electron density around them and deshield the nucleus. As the degree of
shielding decreases (i.e., as the element has a greater deshielding effect), the chemical
shift increases.

The Table shows CH
3
X, where X is a series of halogens. Electronegativity increases as
you go up the column of halogens in the periodic table. (Remember that flourine has the
highest electronegativity, 4.0.) The more electronegative an atom is, the stronger its
affinity for electrons and the stronger its deshielding effect on the hydrogen nucleus.

In summary, as the electronegativity of X increases in the CH
3
X series, X causes greater
deshielding and a larger chemical shift.

1 point for recognizing halogen series (or that all atoms are in a single column of the
periodic table)
1 point for recognizing effect of electronegativity on deshielding
2 points for discussing deshielding and effect on chemical shift

5.
1
H NMR: Interpreting Spectra (16 points)
a. You are told that the proton NMR spectrum of an unknown material shows two groups
of peaks. The first group (a doublet) has six times the area of the second group (a septet).
You are told that the molecular formula for the unknown material is C
6
H
14
O. Draw your
proposed structure of the unknown material. Briefly explain your answer. (7 points)

b. You do elemental analysis and find that the molecular formula of your unknown
material is C
4
H
8
O. The proton NMR spectrum is shown below. Draw your proposed
structure and briefly explain your answer. (9 points)


spectrum source: Aldrich chemical.
TMS is tetramethylsilane.
Red line is the total integrated area.
Solution for 5a
Since there are two groups of peaks, there are only two types of hydrogen atoms. (1
point) Ill call them types and .
Since the peak area is 6:1 and there are 14 total hydrogen atoms in the molecule, there
must be 12 hydrogen atoms of type and two hydrogen atoms of type . (2 points)

The first group (type ) is a doublet, which means that there is only one hydrogen atom
attached to adjacent atom(s) that exhibit spin-spin coupling. The second group (type ) is
a septet, which means that six hydrogen atoms are attached to the adjacent molecule(s)
that exhibit spin-spin coupling. (2 points; NOTE: students dont need to use the term
spin-spin coupling they may use splitting or discuss neighboring atoms.)

Diisopropyl ether satisfies these three criteria. (2 points for structure)


Solution for 5b
Since there are three groups of peaks, there are three types of hydrogen atoms. Ill call
them types , , . (1 point)

From the red line you deduce that the relative peak areas are 2:3:3 for ::, moving left
to right along the chemical shift axis (x-axis). (2 points)

Since there are a total of eight hydrogen atoms in the molecule, you can deduce from the
peak areas that there are two hydrogen atoms of type , three hydrogen atoms of type ,
and three hydrogen atoms of type . (2 points)

The first group (type ) is a quartet, which means that three hydrogen atoms are attached
to adjacent molecule(s) that exhibit spin-spin coupling. The second group (type ) is a
singlet, which means that no hydrogen atoms are attached to the adjacent molecule(s) that
exhibit spin-spin coupling. The third group (type ) is a triplet, which means that two
hydrogen atoms are attached to adjacent molecule(s) that exhibit spin-spin coupling. (2
points; NOTE: students dont need to use the term spin-spin coupling they may use
splitting or discuss neighboring atoms.)

Methyl ethyl ketone (aka, MEK, 2-butanone) satisifies these criteria.

(2 points for structure)


6. IR/NMR Combination Analysis (12 points)
This is a suite of combined IR/NMR spectroscopy problems. From the spectra and
information below, derive the molecular structure. Explain your reasoning.
a. The chemical formula of this molecule is C
6
H
12
O
2
, and in the NMR spectrum below
the peaks near $\delta$=3.9 and 0.8 are triplets, that near 1.9 is a singlet. The relative
integrated areas from high to low chemical shift are 2, 3, 2, 2, 3. (6 points)

Solution to 6a: Butyl Acetate
H
3
C
O
O CH
3

From the IR we can confirm CH3, C=O, and C-O stretches. The NMR shows a singlet at
1.9 ppm from the carbonyl methyl group, a triplet at (ppm):3.9 due to the CH2 next to
the ester oxygen atom, and multiplets at decreasing values depending on the distance
from the ester oxygen.

(3 points for structure and 3 for explanation)


b. The two NMR peaks below are the only ones seen in this molecule with chemical
formula C
5
H
8
O. The integrated areas of the two NMR features are equal. (6 points)

Solution to 6b: Cyclopentanone
O

From the IR we can identify the CH and C=O stretches as well as CH2 bends. Most
notably, the IR shows only 2 mutiplets, indicating that there are only 2 sets of chemically
equivalent protons. Given the formula, it should be easy to come up with the above
structure.

(3 points for structure and 3 for explanation)

This is the end of Problem Set Three. Remember this set is due in the Ch1
homework box near the mailboxes by Lloyd Hovse. If you are unsure where this
is located, ask an upperclassman to show you.

These sets will be collected five minutes after the due date and time. Be
prompt in turning in your set! As with all sets, PS3 is due at 4PM on
Friday.

IR Spectroscopy Problem Set 3

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

IR Spectroscopy Problem Set 3

Uploaded by

Copyright:

Available Formats

Name SOLUTIONS Ch 1b, Problem Set Three

Section Side 1 of 16 Due Friday, J an. 27, 2012

You might also like