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0% found this document useful (0 votes)
213 views16 pagesSpectroscopy 1
Uploaded by
Rajendra GoudaCopyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF or read online on Scribd
4
oP ach
{CODE No: CH 404 S.D.M COLLEGE, UJIRE Reg No:
(AUTONOMOUS)
CREDIT BASED I SEMESTER EXAMINATION, DEC-2013
M.Sc - CHEMISTRY
PAPER - MOLECULAR SPECTROSCOPY
TIME:3 hrs MARKS: 70
Note: Answer any 10 subdivisions from Question no.1 Part A and any FIVE questions from
PartB
PART-A
Answer any TEN subdivisions 10x2=20
1. a, Calculate, Inox for a rigid diatomic molecule for which at 300K, the rotational constant is
1.566cm"
b. What are hot bands? How can their nature be confirmed?
c. Show that rotational spectrum of symmetric top molecule Is Independent of K value.
d. In vibration-rotation spectrum of CO, spectral lines in the R-branch are not equally spaced-
— Why?
. Define and explain the rule of mutual exclusion in Raman spectroscopy.
7
/f. Give reasons: the symmetric stretch of methane gives completely plane polarised Raman line.
g. Write the major IR bands (in cm’) for o-hydroxy acetophenone.
h. What is plane polarised light? How can it be distinguished from a unpolarised light?
i. Give reasons: The C=0 stretching frequency is much less in amides as compared to that in
esters. :
j. Give reasons: TMS is generally used as an internal staridard in *H NMR spectroscopy.
k. How do you distinguish between propanoic acid and 2-chloropropanoic acid from their *H
NMR spectra?
|. Give reasons: Acetylenic protons appear at low é values in the 'H NMR spectrum.
PART-B
Answer any FIVE questions 5x10=50
2. a. Explain any two factors affecting the intensity of spectral lines.
b. Discuss the effect of isotopic substitution on the rotational energy levels and the rotational
spectrum of a diatomic molecule.
.. Calculate the force constant for the bond in HCI from the fact that the fundamental
vibrational frequency is 8.667x10? s*, [34443]
3. a. Explain the factors causing the broadening of spectral lines.
b. Draw the schematic diagram of a microwave spectrometer. Explain its various components.
(5+5]
4. a. Discuss the vibration rotation spectra of diatomic molecules. Draw the energy level diagram,
sketch the possible transitions and the corresponding spectrum. li Move Bn Sep
b. Discuss the Raman activity of fundamental vibration modes of H20, using the concept of
polarisability ellipsoid [6+4] 40: CH,
»SCOPY.
5. a. Write a note on sample handling techniques in IR spectroscoPy
b.
itable examples, explain how IR and Raman spectroscopies are Useful in eluciaayic,
ith suitable examples,
molecular structure.
[4sey
; i vibrati
6. a. Explain with suitable examples, the effect of hydrogen bonding interactions on vibrational :
( : 4
frequepcies. ay
Aeon a id-catalysed muta rotation of glucose.
ae _
c, How inter and intramolecular hydrogen bonding can be distinguished by IR spectroscopy? 03
7. a, Comment on the C=C stretching frequency in unconjugated linear alkenes, conjugated linear
alkenes and cyclic alkenes.
04
b. Predict the important absorption bands in the following
fe}
> own CoH
ii) Me0,C- COM
ii) Meo,’ MMe Bs
©. Calculate the IR stretching frequencies of C-H and C-D bonds (K for C-H=5x10° dynes/cm,
for C-D 5x10° dynes/cm 03,
Be a. sage any two factors influencing the chemical shift values in
*H NMR spectroscopy.
_b-Prédict the chemical se positions for the protons in,
cxoH
cook oO
[+4]
a note on vicinal coupling.
b. What is Pascals triangle? Explain.
-£-Predict the chemical sI
[6+4]
9 aw
Positions and their multiplicities for the protons in [44343] cH/OC 404 S.D.M. COLLEGE, UJIRE foley 1
: (AUTONOMOUS) Reg Not is
CBCS I SEMESTER EXAMINATION, DEC/JAN 2015-16
M.Sc. - CHEMISTRY / ORGANIC CHEMISTRY
Paper: MOLECULAR SPECreOsCoPY
MARKS: 70
TIME: 3 hrs
‘Answer any ten subdivisions from Question No. 1 in Part A and any five questior
ns from Part
PART-A
Answer any 10 subdivisions 10x2=20
as
2
3.
a) Explain the criteria for the molecule to be microwave active.
b) Explain zero point energy.
©) Write and explain Morse Potential function.
d) Give the selection rule for vibrational rotational Raman spectra.
‘e) What is mutual exclusion principle? Explain with an example.
1) Define the terms Stokes’ and Antistokes’ lines.
4) How will you distinguish the compounds in each of the following pairs by IR?
a) Ethanal and Ethanol b) Acetonitrile and acetamide
h) C=O absorption of benzaldehyde appears at 1700cm'* and that of salicylaldehyde at
1666cm" why?
i) What are hot bands and overtones?
4) The observed chemical shift of @ proton is 300 Hz from the TMS signal and the operath
frequency of the spectrometer is 100MHz. Calculate the chemical shift in terms of 6 (PPM).
k) Indicate the number of signals and multiplicity of each signal in CCHy-CHa-CHz-Br and
Hxc—CH—CO.H
a
1) What are the criteria for selecting solvent in PMR spectroscopy? Give any two solvents.
PART-B
Answer any 5 questions 5x10=50
a) Discuss the effect of isotopic substitution on rotation spectra of diatomic molecules.
Comment on its application.
4y>-The rotational spectrum of HF has lines 41.9 cm” apart. Calculate the moment of Interia &~
band length in HF.
b) What are the factors affecting the width of spectral lines? Explain, 44343
a) Sketch the normal modes of vibration of CO, and H20 molecules and predict their IR activity.
b) Show that for a regid rotor molecule, the energy difference between adjacent lines in a
rotation spectrum of a diatomic molecule is a constant.
ron the basis of anharmonic oscillator of a diatomic molecule, give the following
i) Expression for vibrational energy 6
&
S
é
IME: 3
Time
AW election rule for allowed transition.
Potential energy diagram for various vibrational energy levels.
34344
4,_a7Explaip classical theory of Raman «..ect
'b) Discuss the origin of PQR branches in vibrational rotational spectra of a molecule.
©) Discuss the sample holding techniques in IR spectroscopy.
ws oe
bitte the different possible structures for the molecules of the type AB2. How do you
ascertain each structure based on the study of their IR & Raman spectra.
>a) With @ neat diagram explain the Instrumentation in IR spectrometer.
44343
©) Give any three advantages of Raman spectroscopy over IR spectroscopy.
& a) Explain how IR spectroscopic techniques used in the study of hydrogen bonding.
b) Write a note on i) Finger print region ii) Fermi resonance
1g the functional groups of acids, ketones &
44343,
©) Explain how IR spectral studies help in identifyin
aldehydes.
ispersion & circular dichroism, Give their differences.
44343
7. a) Define optical rotatory
i
b) Explain Cotton effect,
©) Explain octant rule with an example.
Festricted rotation and hybridisation
8. a) What is chemical shift? Explain how anisotropic effect,
44343
influence-chemical shift values.
li) NMR shift reagents
b) Write a note on
i) Karplus curve
©) Explain the importance of decoupling techniques in NMR.
HoBr which gave following PMR data
Iii) doublet 5 3.33,2H
°- 8) Explain coupling constant and factors governing coupling constant,
44343,
‘A.compound has the molecular formula Cy
fi) multiplet 6 1.95, 14
i) doublet 5 1.04, 6H
©) Write a note on the use of NMR in medical diagnostics,
3900000000000000000000000000X € NO: CH/OC S 404) S.D.M COLLEGE, UJIRE Reg No:
(AUTONOMOUS)
CBCS I SEMESTER EXAMINATION, DEC -2016
M.Sc. - CHEMISTRY /ORGANIC CHEMISTRY
Spectroscopy
TIME: 3 HRS. MARKS: 70
Answer all nine subdivisions from Question No. 1 in Part A and any four questions from Part
PART-A
Answer all subdivisions 2x9=18
1. a) Explain the criteria for a molecule to be microvrave active.
b) Write and explain Morse Potential function,
©) Intense band is shown by HCI at 2886cm" and weak band at 5668 cm’ & also 8347¢m"!.
Calculate equilibrium frequency and force constant.
d) What are overtone bands?
e) C=O of benzaldehyde is seen at 1700cm" and salicylaldehyde is seen at 1660cm why?
) What is the role of auxochrémes in UV-visible spectroscopy?
4) The observed chemical sift of a proton is 300Hz from TMS and the operative frequency of
spectrometer is 100MHz, Calculate the chemical shift in terms of 5 (ppm).
h) Write a note on NMR shift reagents.
i) Identify the number of ®CNMR frequencies in a) Chlorobenzene b) 1,3-dichlorobenzene_
PAR’
Answer any four questions 13x4=52
2. a) On the basis of Harmonic oscillator of a vibrating diatomic molecules give the following
i) Expression for vibrational energy (cm)
ii) Energy level diagram showing vibrational energy levels
ili) Expression for AEfor v=1 to v=2 transitions.
b) What is stark effect? How does it affect the pure rotation spectrum of a diatomic molecule?
¢) The microwave spectrum of HI consists of series of equidistant lines with spacing of 12.8cm",
Find the moment of inertia and internuclear distance, (at mass of H=1, I=127).
(54444)
3. a) Write notes one the following
i) Zero point eneray
ji) Selection rule in vibrational spectroscopy
Hot bands
b) Explain the effect of Isotopic substitution on the rotational spectra of a diatomic molecule.
) Considering the diatomic molecule as a rigid rotator.
i) Give an expression for rotational energy in cm*
J+1 transitions. (54444)
li) Expression for AE for =] to 4, a) Write short notes on
i) Combination bards
ii) Fermi resonance
t region
pos for the followin
pp ehleulate the
CH
°
IR spectra.
(54+4+4)
at
e & benzaldehyde using
solvent in IR spectroscopy?
th suitable
g using Woodward Fieser rule.
lity Finger prin
6) |) Differentiate between anil
speWhy Water cannot be used 25 2
ffecting the intensity of IR absorotion band. Illustrate wi
5, a) List any three factors al
examples.
by I) How does hydrogen bonding affect IR spectra?
¢ following O-H stretching frequency will be higher?
(54444)
_Aapamhich of the
i) Pure ethanol it) Ethanol in CS2
jons in UV spectroscopy.
plain different types of electronic transit
lain the factors affecting the magnitude o}
ethyl formamide varies with temperature.
(54444)
F chemical shift
) Ex
6. a) What is chemical shift and expl
in NMR.
Justify that 'H NMR of N,N
ii) Explain Nuclear overhauser effect.
©) Discuss the importance of decoupling technique in NMR.
ye in NMR spectra.
1) Explain the effect of chemical exchang
1 behaviour of molecules could be studied
7a)
ji) Write a note on Karplus curve.
b) What are fluxional molecules? How fluxional
has the following spectral data
using NMR technique?
mpound with molecular formula CeHeO2
Keo
IR : 2984cm™, 1741cm" and 1243cm e
PMR: 6 4.1(2H,q),2-0(3H,S),1-3(3H,t)PPM
(54444)
ScnmR: 514, 20, 60, 170 ppm
Suggest a suitable structure.
HKXKAXA AAA K AKAN me corinne imantianeNtin lsc ty
ENO: CH/OC S 404
Reg No:
S.D.M COLLEGE (AUTONOMOUS), UJIRE
CBCS I SEMESTER EXAMINATION, DEC-2018
M.Sc. - CHEMISTRY / ORGANIC CHEMISTRY
Paper: Spectroscopy
TIME: 3 hours MAX MARKS: 70
‘Answer any NINE sub-divisions form question No. 1 in Part A & any FOUR questions form
Part B selecting minimum of ONE question from each unit.
PART-A
1, Answer any NINE subdivisions. 2x9=:
2) Mention the selection rules for the vibration-rotation spectra of diatomic molecules.
bb) What is Stark effect in microwave spectroscopy?
©) How many bending modes are present in HO and CO; molecules?
4d) What do you mean by anharmonic oscillator?
€) Differentiate between chromophores and auxochromes with suitable examples.
f) What is meant by the finger print region in IR spectra? Explain
9) When does a molecule absorb IR light? Explain its significance.
hh) Acetone absorbs at 279nm in hexane whereas the value of 2, in water is 264.Snim. Why?
|) Draw the Karplus curve and mention its importance,
3) How NMR spectroscopy can be used to differentiate between Cis-and trans-stilbene
(stilbene:CHs-CH=CH-CoHs),
k)_ Why TMS is the general reference in H NMR measurements?
|) Sketch the PMR spectrum of vinylchloride(CH)=CH-Cl),
PART.
Answer any FOUR questions selecting minimum of 1 question from each unit. 13x4=52
UNIT-1
2. a) Discuss the rotation spectrum of OCS molecule. How are the CO and CS bond distances
determined?
) Describe the Morse Potential Energy Curve for an anharmonic diatomic oscillator and explain
the vibrational spectra based on the curve.
©) Discuss PQR branches in the vibration rotation spectra of symmetric top molecules. 544.44
3. a) Discuss the spectra of vibrating rotator.
b) Elaborate on the rotation spectrum of a non-tigid diatomic molecule.
) Explain the effect of isotopic substitution on the rotation spectrum of a diatomic molecule and
discuss its applications. ao
UNIT-1I
4. proutline Woodward-Fieser rules in determining 2,,,, of conjugated dienes,
b) Discuss the factors which affect the position of UV bands.
istinguish using IR spectroscopy: n-hexane, 1-hexene and 1-hexyne. 54444 their C=0 stretching frequen, 5
Jing molecules in the increasing order of n
Oe oe eto your answer: methylvinyl ketone, formaldehyde, acetophenay,
ensities of signals in IR spectra,
54444
5. py Rrrana
PG bop
b) Discuss the factors which affect the band positions and int
c) Predict the 2,,,, for the following molecules;
¥ ") ai wv)
6. a) What ts anisotropic effect? Explain with suitable example.
b) Write @ note on spin-spin coupling of NMR signals.
<) How can you distinguish the three isomers of dichlorobenzene with °C NMR spectral data.
S+ae4
7. 2) What are NMR shift reagents? Mention their significance in simplification of NMR. spectrum
with suitable example.
) State and explain double resonance technique.
Lop tatdate the structure of the following compound and justify your assignment.
Molecular formula : CoHs
