University of Chittngong

Department of Chemistry
Third Year B.
Se.(llonours) Exnmination 2019
Course Title: Electronic and Spin Resonanee
Spectroscopy
Course No: Chem 3303
Marks- 50 Time- 3 hours
IN.B.-The tigures in the right margin indicate full marks. Answer
the any FIVE of
tollowing questions including question
No.I.
1. (a) Define Marks
absorption spectroscopy.
(b) What is x10
wave function?
(c) What do you mean by atomic and molecular
Give examples. spectroscopy'?
(d) What is lLarmor
frequency in NMR?
(c) Which law is used in 90%
quantitative spectroscopic
analysis?
() What is orbital
angular momentum?
(8) Why is the structural formula of TMS used in
NMR
spectroscopy?
(h) What is spin-lattice relaxation?
) Why is derivative curve used in ESR
spectroscopy?
) How can you convert the infra-red region froin wavelength
to wave number?

Page I of 4
 and
1+1
T r a n s m i t t a n c e
between
reiationship
that
is the Absorbance
What
value
of
5. (a) is the
What
recorded and 1+2t2 A b s o r b a n c e ?
How are they in
T r a n s m i t t a n c e ?
are
atomic spectra to 35%
E
absorptivity,
(a) What corresponds
molar
atomic spectra.
Discuss the origin of of the
presented?
How ca1 we 2+3 What is the
significance
atomic emission speciroscopy? (b)
What is molecular spectroscopy?
(b) atomic emission
estimation
unknown elements by for the
quantitative
identify he describe a
procedure
Briefly
spectroscopy? (c) Becr's Law.
on the basic of has an
of a n analyte concentration
unknown
solution having 5 pp1n
An wavelength.
motion of nucleus? (d) cell at 519
nm
fa) What is precessional
of 0.217 in
3. one cm
absorbance
solution.
associated with the interaction of of that complex
(b) Describe the principle the molar absorptivity
Calculate
with the suitable beam of
electromagnetic
proton spins
radiation. condition for a 1+2
the
by i) number ii) location ii) intensity 2
What are rotational spectra? What is
(cWhat do you mean
. (a)
'H-NMR spectroscopy? give such spectra'7
and iv) splitting of signals in diatomic molecule to
and 2-chloro 2 lithium by using the cnergy
(d) Draw the possible 'H-NMR spectra of ethanol (b) Describe the atomic spectra of
propane.
level diagram.
Discuss the construction and operation of FT-NMR 3
c)
of ESR spectroscopy. What
(a) Discuss the basic theory spectrophotometer.
substances are ESR active and why? (d) What are the advantages a double beam UV/Vis-
What is hyperfine structure? Explain the origin of hyperfine
(b) spectrophotometer over single beam spectrophotometer?
splitting of ESR signal of nethyl radical.
Page 3 of 4
(c) What is g-factor? What structural information do you obtain 1+3
fromg-value measurement?
Page 2 of 4
 Explain any FIVE of the following: 25
(a) The spectrum of
hydrogen possesses a series of liries
despite having only one electron;
(b) A proton in a
magnetic field absorbs radiofrcquency
radiation;
(c)The relative intensity of lines in the rotational spectra of
diatomic molecules
(d) Selection rules and fine structure of
spectral lines of atormic
spectra,
(e) Electronic spectra of diatomic
molecules;
Frank-Condon principle for
electronic spectra;
How do unpaired electrons in presence of magnetie field
absorb microwave radiation?
Page 4 of 4
 Departmont ( hemiatr

nivereity of hitta
VLamination, 201%
Third Var B. e11onours,

nhjrt hemistry
o e Title: Klectrunie and pin Meennance pectrnny

urse ( e ; hem. 140

1 hrour
Full Murk; 50 (redit 2) Tis
7gwey tmv /IV qurfun imluling gUestinn
JNeNi " uf rn h q t i n shunlhr niiataind in ony wer r 1i

w ' s in the r1sht hrmd de inulu ant: ahe full mrk

(stions Mark

1A1&wer all l the oilvay tiini, la1ctiy

fiWhat cde yon ncan ly ittupic eflectorn atmicspectra

What i meant by wave furiction?

(c) Whal is meant by spin-spin coupiing in NMR?

(d) What do yon nmean by a blank solulion?

)Convert the range of tu: vi:ible spectrum, 390 to 780nm

Inllo- (i) kJ and (ii) cn

"
() What arc the nethods used for the production
falomic: spectra
Puy1 of1 ,:01% henuCUh nem.-3 303
 internal tandland in riing
is 1 5 chuvsen at an

Why

NM specfra"
(H,OH
Draw
ESR spectra of
backgrund of rand
spoctrin has
a

he reuonde
as
which is referred to
luctuatioi of signal:

(chonse any one ofthe tollowng),

1) oise o fne n

(ay sirnpiified ugal

11) wgral t 1ie 1at1o

t, many iacuors do aifut the intensity of

pectra sthe

).2. a What are tomic spoctra' Deeribe tne atomic sper. of 3

ithium wing the enerE level diagram

b Iesrita: t.co "Ru39e)-- Savnder (npl.ng and 515

Coupiing in abnic spectroKopy,

: ) What i: a "teim syabl"? Find out úe yound tetm

fr aluminin/Ai) aty

1,201h m",hem-}2
211
 3 3.
aDeduce
this
Beer -Ianbert'Ouestions
s Mark
law is not law. Indic
ndicate the cases where
oheyed 3

toW can
vou
O A
Substance with
determne the nknown
the helo of coneenlr:euf
a
UV-Visible spectrone ter
Asolution of const.uent, X of an
CoCentration in carbon tnknown
tetrachloride
absorbance of 0,720 at 445 nm exhibits an
Cadeulate thie conentration in 1.00 cm cell a

the constitucnt, X.
Given- 0xi0 w ' ev
.4.a) What is Lannor
frcqueney"2
(biow dors NMR
Clear
spectronseopy relale lhe tenn
ti1agictie re onnce
c) What knds ot
spinning varticies are
responsve io
Spn resonance speclroscopy

(d Discuss, with
examples, shiclding and de-shieldung
phenomena observei ian NMR speciroscopy.
(aWhat substances are ESR active and why?'Explain the 21
reasons f»r
using derivative curve to draw ESR spectra.
What do you mean by hypertine interaction? Explain the 1+2
origin of ihyperfine splitting of ESR signals.

i
i isviu. DiloW lildi ror a Iree eiectro, , and
g
discuss the roBe of g-factor in
getting structural
the
infornation of the sample under
investigation.
Puge. 3 f
 uestio Aav.

following 3.5+3.5
Q.6. Explain any THREEof the
3
etfect and anomalous
Zeeman effcct,
(a) Zeeman

oftUV-Visible transitions
(h) Diflerent types
(with examples and figures);
)Relavation proccsses in NMR;

Selection rules and fine structures of pectral ines of

atomie spectra;

Ditferentiation betwecn Cti-C1- il; and

CH CHCH, by analyzing their ESR- spectra
drawing of spectra must be shown).

.7. fa) Wha: is meant by emission spcctra Describe thc method i 43

for the idcntification of
elentents by atomic emission
spectroscopy,

h) What is Frank-Condon
principle? Discuss, with suitable 2+4
diagram, how the principle can be used to
explain tie
iritensity of vibrational electronic
spectra?

Puge.4 of4
31,2018/0Chem/CUIChem.-330)3
 onsider he
tolluwing systems anul tlien
calk tul.t eieri
theelectron and the ball for n 2 ( onment on the results ,
support the quantization of energies for tlheso cases
IGiven, h-6 626 10 J«.|
An clectron (m, = 9 1 ] *10 " kg) is moving in a one
)
dimensional box of lengtlh 10x10 m
(i) A metal ball (m 0.001 kg) is moving in a on
dimensional box of length 0.1 m.
Draw ihe plots of and along the length x in a one
dmensional box lor n =2and 3.
mbolize the spin momontum and orbital angular mainenluie
of an electron in an atom.
What do you understand by 2D3/2? Calculate the orbital angula
momomtum and total angular momentum of this term.
With an appropriate energy level diagram, explain the atomi
spectra of Li.
Discuss the effect 'of magnetic field on atomic spectra with
special emphasis on space quantization, normal Zeeman ettec
and anomalous Zeeman effect.
What uo you mean by harmonic and anharmmonic vibrations
4(a)
Why does a molecule exhibit harrnonicily and anharmonicity a
different energy levels?
vibrating diatomi
(b) Deduce the euation 277 for a
molecule.
 C
HC-CH
HC-
CHs
( H,--CH; (HC-C-CH
CH
7What tpes of substances are ESR acive and whv?
)Some ionic crystals have verr ditferent g factors ranging tro
0.2to8-explain.
()What is Franck-Condon priniple? Explain how his pr
can be applied to explain the intensitry of spectral lines and th
continuum.
)How are P, Q and R-branches of linas produced in ih-
vibrational band of a molecule? Differentiate between th-
Farallel and perpendicular bands.
S. Write short notes
on any FOUR of the follow ing:
a)Isctope effect on the atomic spectra;
(b) Born-Oppenheimer approximation:
Construction and Working principle of NME
specirometer
d Spin-spin coupling in NMR spectroscop
fe) Hpertine structure of ESR lines
Fage-4of
 1+3+1
molecule
diatomic
rotating
does a
diatomic
How
spectta? h o m o n u c l e a r
rotational the
What
arc radiation?
Why
do
microwave
absorb
spcctra. ot, 5
rotational
rotational
spectra
exhibit
molecules
not
of lines
in the
intensities
relative
Describe the
b)
diatomic molecules. diatomic
molecule 5+2
for a rigid,
cquation
is equal
=7
rotational energy
the spectrum
e) Deduce lines in the
separation of two
and show that the energy
constant.
rotational 3
to 28, where B is the rotational spectrum
two lines in the
first
separation ofthe
c The frequency
molecule.
the
the moment of inertia of
Calculate
0.714 cm
ofBrF is
7 9 90 m E = 8 . 9 nnr|4+
transition n
and
spin, Larmor
rotation,
resonance
5
Deline nuclear the changes i
4.) changed with
Larmor frequency
How is the
spectroscopy.
of magnetic field strength? 3+3
Discuss thee
and denoted? =6
chemical shift? How
is it measured
What is
chemical shift.
effect of magnetic anisotropy on
control the width
of 5
How do they
relaxation processes?
What are the
the nmr band-shape?
4
spectra of the
following compounds:
d) Predict the
nmr
i) CH,CHOCH,CH,P5
i) CH CH,SH,
iii) CH=CHOCOCH;,
iv) CH SCILSCH;.
 122
are esr
betwecn esr and nmr spectroscopy. What 8
S. a) Give a compnison
derivative curves?
active substances' Why :re the esr spectra drawn as
3+2
spectra
bWhat is hypcrlinc splitting of esrspectra? Show the hyperfinc -5
ofethyl radical.
2
between the n-propyl aid is0-propy
c How can you dilferentiate
radicals by their esr spectra?
obtain from the| 1+4
What is g-factor? What structural information do you
d =5
g-factor mcasurcment?
the Morsc curve for a
the following, draw and explain
6. a) Marking
vibraing dintomic molecule.
harmonic and anharmonic
vibralional regions
i)
ii) zero-point energy
iii) dissociation energy
fundamental transition
iv)
overtone transitions
v) 5+2
v = wherc the
vibrational frequency,
b) Show that the classical
the vibrational frequency of
have their usual significance.
Why is
terms
HI?
HCI greatçr than that of first overtone and
Carculate the energy of fundamental absorption,
0.0179.
2990 cm and X,
=
=
hgfband for HCI having
w,
Page3 of4
7. a What arc atomic spectra? How they recorded and
are presentcd?
Discuss the origin of atomic spcctra.
Deseribe the Russell-Saunders What is term symbol? 2tl1+3
coupling, a
Calculate the tem symbols of a electron
6
onc- system.
) Deseribe, with energy level diagram, the production of four series of 2 6
Iines n the atomic spectra of sodium.
How are the normal and
compound doublets produced?
What are space quantization and magnetic quantum numbers? 3
8. Write short notes
on any five of the following: 4x5
Black-body radiation 20
) ileisenberg's uncertainty principle:
iii) Born-Oppenheimer approximation,
ix) Normal & anomalous Zeeman effects;
v)Frank-Condon principle;
y) Spin-spin coupling in nmr and
vii) Fluorescence & phosphorescence.
-
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