SPECTRoscOPY TECHNIQUES AND APPLICATIONS 137

Dower Diffraction: It is used to examine small weakly interacting crystals in random

orientations.
This techniques can also be used to study polycrystalline materials such as metal and alloys.
..VRayReflectivity (XRR) techniques are used for studying the detailed surface properties of
materials for e.g. it isused to probe the electron density perpendicular to the surface and there by
ives the information about surface roughness, thinfilm thickness and density.
c Scattering SAXS and WAXS: Also called NCD (non-crystalline diffraction). It provides essential
information on the structure and dynamics of large molecular assemblies in low ordered
environment.
s3. X-Ray photo electron Spectroscopy (XPS)technique provides wide range ofinformation regarding
atomic composition, oxidation states and chemical structure.
S4. Diffraction is the phenomenon is bending of waves around small obstacles and the spreading out
of waves across small openings.
s5. Scattering is a process where waves are deviated due to certain irregularity in the space.
56. Flame photometry is a techniques based on emission techniques to determine several metal
cations qualitatively and quantitatively.

PROBLEM WITH SOLUTIONS

Problem 1. Indicate the regions of the electromagnetic spectrum in which the following photons
willlie.
(a) =600 nm (b) v=106 Hz
(c) =2000cm-! (d) v= 40 cm-1
(e) =200nm
Solution. (a) Visible (b) Radio frequency (c) IR (d) Microwave (e) UV
Problem 2. In which region of the spectrum the electronic spectra occur? What is its spectral
range?
Solution. The electronic spectra occurs in isible and ultra violet regions of the electromagnetic spectrum.
The spectral range for visible region is 12500 to 25000 cm and for UV region is 25000 to 70000 cm-!.
Problem 3. The selection rules for spectral transitions in atomic spectra are:
() An =1, 2, 3, 4, ... and (ii) Al=t1.
Using these selection rules, deternmine which of the following transitions are allowed and
which are forbidden:
(a) 1s ’ 2p (6) 2s ’ 3s (c) 2p ’ 3s
(d) 3d’ 4f (e) 4p ’ 5f ) 3p ’ 3d
Solution. For allowed transitions, both selection rules should be obeyed simultaneously. Accordingly,
allowed transitions are: (a), (c), (d) and() and forbidden transitions are: (b) and (e).
 138 ATEXTBOOKOF ENGINEERING CHEMISTRY

Problem 4. List all the electronic transitions possible for (a) CH, (b) CH,CI(c) HCHO
possible transition is
Solution.(a) In CH,,there are only sigma bonds. So the only
Þ-g*
(6) In CH,C1, there are no Tt or r* molecular orbitals. So the possible transitions are:
o ’ o* and n o*

(c) In H-C-0, all the bonding, antibonding and molecular orbitals are available,
following transitions are possible: so the
O’ o*, n’ o*, T’ T* and n ’ T*
Problem 5. The UV spectrum of acetone shows two peaks at m= 280 nm.
max
bmax and
Ami=190 nm, max = 100.
(a) Identify the electronic transitionsfor each and (b)which is more intense?
Solution. (a) The longer wavelength (280 nm) is associated with smaller energy transitionn ie.,
The transition t T* 0ccurs at 190 nm.
n’T
(b) The larger the value of .mthe greater the intensity ofthe transition. Therefore, T ’ T* is
more intense.

Problem 6. Identify the two geometric isomers of stilbene, CfH,CH =CHC H, from their )
values, 294 nm and 278 nm. mar
Solution. The two geometric form of the given formula are:
C,H, CH CH C-H
and
CHCH H CCH,
cis trans

Steric strain would be greater in the cis form as compared to trans form. The steric strain
would
prevent full coplanarity of the cis phenyl groups and the conjugative effect is attenuated. Thus the
higher energy cis-isomer has the shorter The isomer with = 278 nm is cis and other is trans.
max

Problem 7. Predict the kind of electronic transitions in (a) C, and (b) carbonyl
their intensity. group. Also give
Solution. (a) The transition in Cl, are: (i) o’ o* (allowed transitions), which is strong in
(ii) n ’ * (forbidden transition) which is weak in intensity. intensit.
(b) In C =0group, o ’ o* and t ’T*, both are allowed
transitions and strong in intensite
whereas n’T* and n ’ o*, both are forbidden and of weak
intensity.
Problem 8. How willyou distinguish between benzene and
anthracene by UV spectroscop)
Solution. The structures for benzene and anthracene are given
below:
and

Benzene
Anthracene conjugated
Anthracene will have higher than benzene. This is because anthracene is more
than benzene.
 SPECTROSCoPy TECHNIQUESs AND APPICATIONS 139

Problem9,. Arrange the following compounds in the increasing order of the their UV absorption
maxima.
(a) Ethylene (b) Naphthalene
(c) Anthracene
(d) 1,3-Butadiene
Solution. The structures of the given compounds are:
(a) H,C=CH,
Ethylene (b)|
Napthalene

(c) (d) H,C=CH CH=CH,

Anthracene 13-Butadiene

The absorption maxima (ma) is directly proportional to the extent of conjugation. Therefore,
the increasing order of absorption maxima of the given compounds would be:
(a) < (d) < (6) < (c)
Problem 10. Which anmong CH,=CH,, CH,=CH-CH=CH,, and trans CH,=CH CH=CH
CH=CH, can give may absorption at about 274 nm? Give reason.
Solution. Trans CH,=CH CH-CHCH=CH,, since it is an conjugated triene.
Problem 11. Most of absorption bands in the UV-visible spectra are very broad. Give reasons.
Solution. UV-visible spectra involve transitions between electronic energy level which are associated
with vibrational and rotational energy levels. The electronic transition may occur from any of the several
vibrational and rotational states of one electronic level to any of the various corresponding states of
higher level. Since a large number of transitions are possible, so a large number of absorptions will
take place corresponding to diferent wavelengths. Hence, specira are very broad.
Problem 12. Why does 1, 3-butadiene possess higher max m Value than that of ethene?
Solution. In 1,3-butadiene , ’1,* excitation takes place, which requires lesser energy (of higher
wavelength) than Tt ’ * excitation in ethane.
Problem 13. Which of CH,COCH, and CH,=CHCOCH, exhibit higher value of max in the
UV-visible spectra?
Solution. CH,=CHCOCH,, since it has two conjugated chromophores (double bond and C-0 group).
whereas H,CCOCH, has only one chromophore (C=0 group).
Problem 14. What kind of molecules show IR spectra?
Solution. Molecules must possess permanent dipole moment e.g., CO, NO, CN ete. For a diatomic
molecule if they don't have a permanent dipole moment then these molecules during vibration must
Show a change in the dipole moment. For example, O,, N, H, are IR inactive because they are not
satisfying either of the above conditions.
Problem 15. Calculate the normal modes of vibration of the following molecules
() CH, (ü) C,H, (i) HS
(iv) HCI (v) C,H, (vi) S0,
 140 A TEXTBooK OF ENGINEERING CHEMISTRY

Solution. Molecule Vibrational degrees of freedom of atom

-6=3 x 5-6= 15 -6=9 where n = number
() CH, 3n
12-5=7
(ii) CH, 3n -5=3 x 4-5
3n-6=3 x3-6=9-6=3
(ii) H,S 2-5=6-5 =1
(iv) HCI 3n-5=3x 36-6= 30
3n -6=3x 12 -6 =
(v) CH, 3n -6=3x3-6=9-6=3
(vi) SO,
chracterized as molecular finger prints." Justify statement,
often
Problem 16. "IR spectra is at nearly definite positions in
functional groups produce recognizable peaks specific groups in the molecule. IR
Solution. Diferent the presence of So IR
spectra. Most ofthe peaks can be assigned due to compounds e.g., it can be characterised as
spectra can be usedin
establishing the identity of the finger
prints of the molecule. vibration only; while CO, moleon).
can undergo stretching
Problem 17. Molecule like HCl bending vibrations. Why?
undergo stretching as well as vihrat:
may be regarded as a spring, whose atom can undergo back and forth
Solution. HCl molecule molecules can undergo symmetric as
well as
(i.e., stretching). On the other hand, CO,
undergo in-plane and out of plane bending. asymmetric
stretching with respect is C-atom. Also it can
Ö=C=0
Stretching Bending in CO, molecule
HCl molecule

Problem 18. What do youunderstand by an isobestic point?

Solution. An isobestic point for different absorption spectra is that point where the wavelengh
corresponding to these spectra is equal and the corresponding wavelength at this point is called isobestic
wavelength. The absorbance ([)and , Values of different species are, therefore, equal at this
point. Although max is the characteristic property of acompounds, yet different compounds may possess
same value of , by changing solvent or pH values of the solutions.
Problem 19.What property of certain atomic nuclei is involved in NMR phenomenon?
Solution. Anucleus having an odd atomic number or an odd mass number has a nuclear spin which can
be observed by the NMR spectrometer. Alarge number of spin active nuclei such as 'H, 1BC, N, "P
and 'P, have permanent magnetic moments (nuclear spin = 1/2) and can be studied by NMR spectroscopy.
Problem 20.13C is NMR active while 2C is not. Explain.
Solution. PC does not have a nuclear spin and cannot be used in an NMR experiment. In contrast; iS
isotope l3C, whose natural abundance is only 1.1%, has a nuclear spin of 1/2.
Problem 21. Predict the NMR spectrum of CH,CH-CHCI,.
a b
Solution. CH,CI-CHCI, has two sets of equivalent protons. So number of signals =2
For proton'a',n=1 soitgives adoublet as only one hydrogen atom is attached to neighbourm:
carbon.
For proton 'b', n= so it gives at triplet as two hydrogen atoms attached neighbouring cart
 SPECTROScOPY TECHNIQUES AND APPLICATIONS 141

hlem22. Predict the NMR spectrum of CH,CH,0H.

C b a

Solution. CH,CH,OH has three kinds of protons viz., CH, CH, OH, a singlet is observed for OH
proton.
For protons a, n = 2 so triplet is observed due to coupling with CH,-group at downfield.
For protons b, n = 3 and n' = 1, so (3 + 1) (1 + 1) =8 lines multiplet is observed at in between.
For protons c, n=2 so triplet is observed due to coupling with CH,- group at up-field.
Problem 23. How many NMR signals do you expect from each of the following compounds, Indicate
also the splitting pattern of the various signals.
(a) CH,0CH, (6)CH,0CH,CH, (e) CH,CH,OH
Solution. (a) One signal (singlet); (b) Three signals (singlet, quarlet, triplet); and (c) Three signals
(singlet, quartet, triplet).
Problem 24. How would you distinguish between the following pairs of compounds by NMR
spectroscopy?

(a) CH C CH, and CH,CH,C-H

(6) CH, C CH, and CH,-C-OCH,

Solution. (a) CH,COCH, will give only one signal, while CH,CH,CHOill give three signals; and (b)
CH,COCH, willgive only one signal, while CH,COOCH, will give two signals.
Problem 25. How willyou distinguish between the three dibromobenzenes by their NMR spectra?
Solution. o-Dibromobenzene will show two peaks, m-dibromobenzene will show three peaks; and
p-dibromobenzene will show only on peak.
Br Br

-Br -Br Br -Br

0 C b

0-Dibromobenzene m-Dibromobenzene p-Dibromobenzene

(two peaks) (three peaks) (one peak)
1:1 1:2:1

Problem 26. Which member of each of the following pairs of the structural isomers would be
expected to exhibit a single peak in its NMR spectrum?
CI
(0) CH, CC, or CICH, CHCI, (b) or -CI
CI

H,C H,C CH,

(c) C=CH, or () CICH,CH,CI or CHCHCI,
H,C H,CCH,
(e) H,C=C=CH, or CH C=CH
 CHEMISTRY
142 A TEXTBOOK OF ENGINEERING

Solution.

(a) CH, CCI,

H,C-CH, (d) CICH,CH,CI
(c)1 |
H,C-CH,
(e) H,C=C=CH, show only
woould be expected to single peak in itg
Which of the following compounds
Problem 27.
NMR spectrum? (i) Dimethyl ether
() Acetone (iv) Methyl iodide
(ii) Methyl acetate (v) Chlorobromomethane
(v) Dibromomethane (vii) 1-chloro-2-bromoethane
(vin) 1, 2-dibromomoethane
NMR spectra
following compounds will exhibit a singlet in their
Solution.The (ii) Dimethyl ether
(i) Acetone
(ii) Methyl iodide
(v) Chlorobromomethane
(v) Dibromomethane
(vii) 1,2-dibromomoethane
present in the following compounds?
Problem 28. How many different kinds of hydrogens are
(a) CH,CH, (6) CH,CH,CH,
(e) (CH),CHCH,CH, () H,C=CH,
(e) CH,-CH-CH, )C,H,NO,
(e)C,H,CH,
Solution. (a) One (all equivalent) (b)Two (CH,CH,-CH,)
d

c) Four (CH),CHCH, CH, (d) One (all equivalent)

H,C H
(e) Four () Three (2 ortho, 2 meta and one para)
H
(g) Two ring protons are little affected by alkyl group are equivalent.
Problem 29. How will you distinguish between p-xylene and mesitylene on the basis of NNIK
spectroscopy?
Solution. Both the compounds exhibits two singlets; one for the ring proton and the other for metiy
methyl
protons. The relative intensities of the peaks are, however, different. In p-xylene, the ratioof
protons to ring protons is 6:4 or 3:2, while for mesitylene, it is 9:3 or3: 1.
 SPECTRoScOPY TECHNIQUES AND APPLICATIONS 143

Problem30. How many kinds of protons are there in

() CH,CH, (i)CH,CH,CH,
(i) (CH,),CHCH,CH, (v) C,H,CH,
() C,H,NO, (v) CH, = CH,
(vi)CH,CH= CH,
Solution.()COne kind (all equivalent): CHCHÊ
(i) 2kinds: CHCH, CH, (i) 4kinds: (CH;), CH" CH; CH;
(iv) 2kinds: C,H{ CH
Theoretically, there are three kinds of aromatic protons, viz, ortho, meta and para. However, the
Ging Drotons are little affected by alkyl groups and are thus nearly equivalent. (v) 3 kinds: 2 ortho,
meta and one para, the ring protons are affected byNO, group as it is very strong electron withdrawing
group.

NO,
H,

H, H
H,
H, H,
(v) One kind (all equivalent).
H, H,
CH H°
(vii) 4 kinds:
H
Problem 31. Determine which of the following molecules willshow spin-spin coupling in their
NMR spectra. If the coupling or splitting is observed, give the multiplicity of each kind of proton,
i.e. give the number of lines arising from each proton:
H H
(a) CICH,CH,CI (6) CICH,CH)I (c)
H H

H CI H
(d) (e) H,C C H
Br H H

(g) CH (h) CH,-C(C,)-CH,

CH,
Solution. Spin-spin splitting is not observed in (a), (c), (g) and (h) which have only equivalent protons.
into a 1 :2: 1triplet.
e protons of the CH, groups in (b) are non-equivalent each being split
144 A TEXTB0OK OF ENGINEERING CHEMISTRY

protonsoneareis not
the two since equivalent and each is split into a doublet. The vinyl
not(d),
(e) are In equivalent cis to Cl and the other is cis to Iso that each is split into
Notice that in this case the protons undergoing spin-spin interaction are on the same carbon, protons
of the CH=0 group arel:3:3 not equivalent; the CH,
In () the protons of CH, and the proton
CH=0resonance is split into a :1
resonance is split into a doublet and the quartet.
distinguish between the isomers p-xylene
Problem 32. How can the NMR spectrum and ethy
benzene?
Solution. The isomers are:

HC-CH, -CH,CH,
p-CH,C,H,CH, C,H,CH,CH,
b NMR spectrum consists of two o ,
CH. CH.CH. has two kinds of protons and its
He
C,HCH}CH has three kinds of protons and its NMR spectrum consists of a singlet of quartet
for Hand a triplet for H.
Problem 33. Predict the proton NMR spectra of H,, CH, C,H, and CH,.
Solution. All he four molecules contain equivalent protons which do not show spin-spin interaction
Hence, their proton NMR spectra will consist of one signal only, i.e., asinglet.
Problem 34. Predict the NMR spectrum of CH,CI -CHCI,.
b
Solution. CH, C]-CHCI, has two sets of equivalent protons. So number of signals =2
For proton 'a, n=1 soit gives a doublet as only one hydrogen atom is attached to neighbouring
carbon.
For proton b', n=2 so it gives atriplet as two hydrogen atoms attached to neighbouring carbon.
Problem 35. Predict the NMR spectrum of CH,CH,OH.
Solution. CH,CH,0H has three kinds of protons viz., CH. CH, OH, a singlet is
C a

proton. observed for OH

For protons a, n= 2 so triplet is observed due to coupling
For protons b, n =3 and n' = 1, so (3 + 1) (1+ 1)=8 lineswithCH,- group at downtielo.
For protons c, n =2so triplet is multiplet is observed at in betwee.
observed due to coupling with CH,-group at upneu
Problem 36. Name any five important surface
Solution. The important surface characterisation characterisation techniques.
() Macromolecular techniques are:
Crystallography (MX)
(ii)X-Ray Reflectively (XRR)
(iii) Scattering - SAXS and WAXS
(iv) X-Ray Photoelectron
Spectroscopy (XPS) in Surface Chemical Analysis
(v) Dynamic Secondary lon Mass
Spectrometry (DSIMS)
(vi) 3D Profilometry using White Light
Interferometry (3DP)
 SPECTROscOPY TECHNIQUES AND APPLICATIONS 145

Problem 37. Define Diffraction and Scattering.

Solution. Diffraction is defined as bending of waves around small objects and spreading out of waves
acrosssmall openings.
Scattering is a process by which waves are deviated due to certain irregularities on the surface of
anyobject.
Problem38. Distinguish between diffraction and scattering.
Solution.() Differaction is a process observed only in waves, whereas scattering takes place in waves
particles.
as well as
() Differaction is a coherent process i.e., it requires that the surface must be regular so far as
distances are concerned in comparison to the wavelength of the diffracted wave. But scattering
is an uncoherent process i.e., it willtake place when the surface is rough in terms of distances
as compared to wavelength of light.
Problem 39. Why the colour of sky is blue?
Solution. The Rayleigh scattering causes the blue light from the sun to be scattered more than other
wavelengths of light.
Problem 40. What do youmean by Synchroton Technique? Point out its main advantages.
Solution. The technique by which measurements are made using asuitable strong beam from radiations.
It is employed in the following cases:
(i) Diffraction/ Scattering surface characterisation
(ii) Spectroscopy
(ii) Polarimetry
(iv) Imaging
Problem 41. What do you mean by MRI? What for it is used?
Solution. MRI menas Magnetic Resonance Imaging Spectroscopy. It is mainly used for the diagnosis
of soft tissues of human body.
Problem 42. What do you mean by GIXD? Give its two applications.
Solution. By GIDX, we mean Grazing Incidence X-ray Diffraction. Its applications are:
(i) It is used for measurement of strain at the interfaces, which will tell whether the equipment
can work under the prevailing conditions or not.
(ü))System such as alloys and semiconductors, oxides, surfaces polymers and biological films
can be investigated.
Problem 43. What do you mean by ToFSIME? Mension its important applications.
Solution. By ToFSIMS, we means Time-of Flight Secondary Ion Mass Spectroscopy. ToFSIMS is
mainly used to investigate organic materials at surfaces and interfaces.
Froblem 44. What do you know about 3DP? What for it is used?
Solution. 3DP means Three Dimensional Profilometry technique. It is used for measuring surface
topography quantitatively by using white light interferometry.
 146 ATEXTBOOK OF ENGINEERING CHEMISTRY
REVISION QUESTIONS

l. What is molecular spectroscopy? How does it differ from atomic spectroscopy?

2. Show vibrational, rotational and electronic energy levels on an energy levelspectra li In
diagram.
region of electromagneticspectrum do rotational, vibrational and electronic which
3. What is spectroscopy? Explainthe principle and working of spectrometer, giving its neat diagram,
type ofelectronic
4. Why molecules absorb in UV-visible region? What are the transitions that can
occur in a molecule? Discuss giving examples.
5. (a) Define the following terms:
(ii) Hypochromic shift
(i) Bathochromic shift
(iv) Hyperchromic effect
(iii)Chromophore
(b)On what factoros do (i) and (ii) depend?
and why?
6. (a) Which solvent is generally used in ultraviolet spectroscopy
(b)Explain any two of the following in respect of UV -visible spectroscopy:
() Bathochromic shift (i) Blue shift (iii) Hyperchromic effect
7. (a) What do you understand by nuclear spin? When will a nuclei show nuclear maongt
resonance?
(b) Which of the following nuclei do not show NMR ?
'H, H, 12C, 1C, l4N, 15N, l60, 19F, 3P, 32s.
8. (a) Draw the low and high resulution spectra of C,H,OH.
(b) What type of molucules gives pure rotational spectra? Derive expressions for frequency of
rotational lines.
9. How can one establish whether a carbonyl group is part of an aldehyde, ester or ketone from
uv-spectroscopy?
10. (a) What is the principle behind nuclear magnetic resonance spectrum?
(b) Define the terms bathochromic shift and hypsochromic shift. What structural feature may
produce bathochromic or a hypsochromic shift in an organic compound.
(c) What is the importance of IR spectroscopy in finger print region
11. (a) Why is methanol a good solvent for UV but not for IR
spectroscopy?
(b) Differentiate between bathochromic and hypsochromic shifts.
(c) How do you distinguish between different types of transitions involved in
UV-visible
spectrophotometry?
12. (a) lndicate the number and type of H-NMR signals
expected in CH, CH=CH,
(b) Explain chemical shift in NMR.
3. (a) What type of molecules exhibit
vibrational-rotational spectra and why?
(b) What do you understand by termspin-spin coupling? Is the coupling constant independent of
the applied field or depend on it.
 SPECTRoscOPY TECHNIOUES AND APPLICATIONS 147

is cause of chemical shift in NMR?

14. (a) What
(b)) Give the high resolution 'H-NMR of methyl ethyl ether.
15. (a) What are different kinds of electronic transitions? Explain chromophores and auxophores.
(b) Discuss the principle of uy-visible spectroscopy.
16. (a) Draw and explain'H NMR spectrum of Ci,CHCHCICHCI,
(h What is meant by shielding and deshielding of proton of a nucleus?
(c) Hydrogen chloride can undergo stretching vibration only while carbon dioxide can undergo
stretching bending vibrations?
17. (a) What is the range of peak identification region in IR spectrum ?
(6)Discuss the factors contributing tothe broadening of spectral line.
(c) Discuss IR spectroscopy and its applications.
() Give the possible electron excitations for () CH, CH=CH, (i) CH,CHO.
(e) What is the difference between allowed and forbidden transistions?
18, (a) The absorption bands in uv-visible spectra are broad. Explain.
(6) Explain spin-spin splitting in NMR.
19. (a) Arrange the following in increasing order of absorption maxima.

(b) Discuss the principle of IR spectroscopy.

(c) Match the following:
C=0 NH O-H C=C
Functional group
3400 2050 1700 3350
v(cm)
20. (a) What is the purpose of using TMS in explain 'H NMR spectrum?
signal. What could be its structure?
(b) The H NMR spectrum ofC,H,Br, has only one
(c) What is a chromophore and auxochrome?
21. (a) Explain the principle of NMR spectroscopy?
UV-Vis spectrum.
(b) What information can be obtained from the
spectroscopy.
22. (a) Explain the selection rules for UV-vis
fluorescence and phosphorescence?
(b) What is the difference between
the following willabsorb at higher wave number for C==0 stretching:
(c) Which of

statement.
is often characterized as molecular finger prints." Justify this
L3. (a) "IR spectra
number of vibrational degree of freedom in following compounds:
(6)Calculate the (ii)CH,
() CO, (i) sO,
molecules will show IR spectra and why?
(c) Which of the following
H, HCI, CH,, CO, H,0
 148 A TEXTBOOK OF ENGINEERING CHEMISTRY

24. (a) Discuss the pcinciple of NMR?

(b) Explain the'H NMR patternsand intensitities of isopropyl group in isopropyl alcohol,
25. (a) What is chemical shift in NMR?
(b)What is Frank-Condon principle?
(c) Which of the following will absorb at higher wave number forC=0stretching:

NH, CI

(d) Discuss the applications of NMR with respect to Magnetic Resonance Imaging.
26. (a) What is ultaviolet and visible spectroscopy known as?
(b)What is NMR and MRI?
(c) Give number of signals in Benzene and Nitrobenzene.
(d) Explain the number of signals and hyperfine structure with suitable examples.
27. (a) What do you understand by spectroscopy?
(b) What do you understand by natural linewidth of a spectral line.
(c) Amn Or two isomer (cis-and trans-) of stibene
Whichisomer will have .
(CH,CH=CHCH) are 274 and 294 nm
of 294 nm. Explain.
(d) What is the usefulness of TMS as an internal
standard?
28. (a) Methanol is a good solvent for UV but not for IR
studies. Why?
(b) Explain phosphorescence.
(c) What are the different kinds of
electronic transitions? Explain eachtype with suitable
29. (a) What are overtones? Discuss examples.
Frank-Condon principle on detail.
(b) Give the number of lines in ESR
and spin lattice spectrum of p-benzoquinone radical anion. Discuss
relaxation in NMR. NOE
30. (a) What do you mean by
spin- 1attice relaxation of NMI?
(b) What do you mean by
resolving power of a spectrometer? Explain
prism as dispersing element. Also explain how the taking the example ot 1
(c) How does
absorption signal originate in NMR resolution depends upon slit width?
NMR spectroscopy?
31. (a)How the
spectroscopy? What is meant by resonance u
intensity of the rotational spectral lines
(b) Are the lines of
Rotational varies and why?
32. (a) In IR Raman Spectra usually spaced?
(b)On thespectroscopy
why the region below 1500 cm is
Elaborate your answer.
basis of IR called as fingerprint region.
spectroscopy,
(1) Alkane, alkene and how can you distinguish
(ii) Aldehyde andbetween following.
alkyne the
33. (a) Discuss
spin-spin
relaxation in NMR spectroscopy.
(6) Draw and explain the
ketone
splitting pattern observed in the 'H NMR of
CHCI, CH,Cl.
 SPECTROScOPY TECHNIQUES AND ApPUCATIONS 149

34. (a)Discussin brief various transitions shown by organic molecules in UV-Vis spectroscopY
with examples.
(b) Why a UV spectrum consists of band and not of peaks?
(O How willyou distinguish between cyclohexarone and 3-methylcyclopentanone on the basis
of IR spectroscopy?
(d) Discuss about anharmonicity in IR spectroscopy.
35. Draw a well labelled Jablonski diagram and explain:
(a) Intersystem crossing (b) Phosphorescence