UNIT

6 SPECTRoScOPIC
TECHNIQUES AND
APPLICATIONS
PRINCIPLE,
ELECTRONICS ISPECTROSCOPY,
NSTRUMENTATIVIBRATIONAL
ON &APPLICATIONS
&
OF
sPECTROSCOPY OF DIATOMIC MOLECULESROTATIONAL
0.l. Define spectroscopy.
Ans. The term spectroSCopy was (R.GPV., Dec. 2013)
originally applied to the branch of science
that was based upon the resolution of visible
wavelength. With the passage of time, however, radiation
the
into its component
been broadened to encompass studies meaning of the term has
spectrumandleven some techniques which involving the entire
do not at allinvolve electromagnetic
radiation e.g., mass, electron and
acaustic spectrOscopy. electromagnetic
0.2. What are the merits and
demerits of instrumnental analysis ?
(R.GPV. Jan/Feb. 2006)
Ans. The merits and demerits of
Merits -
instrumental analysis are given below -
(i) In instrumental method, small
sample can be used.
(ii) High sensitivity in results is obtained.
(iii) Measurements or results obtained by
reliable. instrumental methods are
(iv) The determination is very fast.
(v) Byinstrumental method even complex samples can be easily handled.
Demerits -
(1) An initial or continuous calibration ofthe instrument is required.
) Sensitivity and accuracy depends a lot on the instrument.
(i) The cost of equipment is very high.
) It works accurately in between aparticular concentration range.
) Specialized training to handle the instrument is needed.
(vi) Sizable space is required.
162 Engineering Chemistry
the visible
(R.GPV., B. Tech.
Q.3. Most absorption bands in
Give reason.
UV-spectra are very
Ans. Visible-UV spectra involve electron energy
level broad
of several vibrational and
electron
vibrational and rotational levels. The transition ass0ciated
may occur
rotational states of one electronic
several vibrational and rotational states of a higher level
level. Since a to ny of
number
of transitions are possible, so a large Hence
corresponding to different wavelengths.
absorptions wilargakee rIulrascibee,
of.
spectra are very
0.4. Write informative note on U.. visible
broad.,
spectroscopy.
(R.GPV., Dec.
2006,
Or June 2007)
Write short note on U. V. spectroscopy.
Ans. Principle - When electromagnetic radiations of
(R.GP.V., Dec. 2012)
(a= 200-400 nm) or visible region (). = 400-800 nm) are passed ultraviolet Tegon
compound with multiple double bonds, some part of the incident
absorbed. The quantity of absorbed radiation depends on the
through
tradiations is
a

incident light as well on the nature of compound. Due to wavel

abbsorpt engt h of
The ion light
radiations, the bonded electrons go to higher energy levels. of
absorbed radiations can be determined by spectrometer. quantity of
The modes of electronic energy changes which occur, when radiation in
U.V. and visible region is absorbed by an organic compound are -
() Transition between Bonding Orbitals and Antibonding Orbials -
For example,
G’ o* or t ’ T*
The excited state closely resembles the polar character
C= C ct -c
(ii) Promotion of Non-bonding Electron (iLe., Unshared Pair, n)
into Antibonding Sigma or Antibonding Pi ie.,n ’ o or n
’t*-Ihest
involves transitions of non-bonding lone pair of hetero atoms (e.g., o, n) to u
empty non-bonding molecular orbital. The absorption bonds for such transtions
occur in longer wavelength with low
intensity. wavelengths and even Small
Structural units which absorb selective
structural changes bring about perceptible changes in wavelength ofradiation
absorbed is called chromophores,
C= C,-C=C,-C=N, -N=N,-C0
undergo ’ *transitions in the short wavelength regions ofU.V.Iradiations
Polar groups such as -OH, - OR, - NH,- SH and-X(halogen)having
unshared pair of electrons and may show absorption above 190 nmsuch
groupings are called auxochrome.
Shivan-2024) Spectroscopic Techniques and Applications 163
noted that energy gap between non-bonding and antibonding
It may be
MO.of ethene
is greater than that between the corresponding M.0. in 1, 3
Ntadiene. Consequently, 1, 3-butadiene has its Amax at 17l nm (of higher
energy)thanthat of ethene at 217 nm (oflower energy). Thus, in general, the
greaterthe
number of double bonds present in agiven compound the longer is
at which it absorbs U.V. radiations.
thewavelength
Compounds containing carbon-0xygen double bond also absorb light in
the U.V. region.
spectro
0.5. Explain the instrumentation and working of the U.V.
photometer.
Ans. Instrumentation of U.V. Spectrophotometer- The following are
the important components of the U.V. spectrophotometer. most common
i) Source of Radiation - The following are the
radiation sources used in U.V. spectrophotometer lamps
(a) Hydrogen discharge lamps (b) Deuteriumarcs.
(c) Xenon discharge lamps (d) Mercury
to disperse the
(ii) Monochromators- Monochromators are used component of the
radiation according to the wavelength. The essentialelement and an exist slit. The
monochromator are an entrance slit, a dispersing
silica. The dispersing element disperse
prism is generally of quartz or fused component, wavelengths where the exit
the heterochromatic radiation into its
slit allow the nominal wavelength topass through. detectors are commonly used -
(üi) Detectors- The following types of cell, light
(a) Photovoltaic or Barrier Layer Cell - In this
as selenium leads to generates the
striking surface of a semiconductor such
current generated in proportional to the
electric current. The magnitude of the
on it.
intensity of the light beam fallingPhotoemission
Photocell or Cell This cell consists of a
(b)
internally with a thin, senstive layer ofcalcium and potassium
glass bulb coated electron when light fall on it, this laver is
oxide or silver oxide. This layer limit
metal ring insert near the centre of the bulb forms the anode
cathod. A an electrode covered
(c) Photomultiplier Tube - It consists of charged plates, each
material and a series of positively
withha photo-emissive higher potential. The plate is covered with a material
chargedd at a successively
Cs-Sb, whichlimitt several electron for each electron collected
such as Be-Cu or
surface. This is extremely very sensitive and very fast in response.
on its from the detector is received by the
(iv) Recorders - This signal recorder pen.
recording system provided with a
() Sample and Reference Cells - Matched pair of cells made of
or fused silica are used.. Generally quartz cells are used in the ultraviolet
quartz
region, and also visible region. Single beam and double beam U.V.
spectrophotometers are available commercially.
164 Engineering Chemistry (R.GPV., B.
Working of Double Beam U.V.
Spectrophotometer-The tt
emitting fhom the source is allowed to pass through
a
The UV. raiatieYon Tech.,
monochromator un
of wave lengths
miror system. The radiation of narrow range system
diviCodesming beato
which
the monochromator is received by the rotator sample cell the oVt of
into two identical beams, on passing through a and other
output from the
Sample gample Cothrnogeh
on detector. The
reference cell are
sensitive
focussed
amplifier. The
detector 1s
to phase (X), Beam
signal transmited by the amplifier
recorded
are transmitted and
which is connected torecorder.
The chart device is coupled to Rotating
Prism
Optical Device g
the rotation of the prism. Thus, Light (Y) Reference Pen
the absorbance or transmittance Source
Beam
of the sample is recorded as a (X) and (Y’ Mirror
function ofwavelength. The U.V. A and B’ Photocell Spectrum
spectro photometer shown in Motor Amplifier
fig. 6.1. Fig. 6.1 U.V. Spectrophotometer
Q6. Explain briefly the applications of U. K. spectroscopy.
(R.GP V, Dec. 2003, Feb. 2005,
Or
Write short note on applications of U.Vspectroscopy.
(R.GPV., Dec. 2013)
Ans. Applications of U.V. spectroscopy are given below -
(i) Qualitative Determinations Analysis U.V. spectroscopy is
used for characterizing aromatic compounds and conjugated olefins and
identification is done by comparing the U.V. absorption spectrum ofthe sample
with the U.V. spectra of known compounds available in reference books.
(i) Quantitative Analysis - U.V. absorption spectroscopy can be
used for quantitative analysis of such compounds, which absorb ultraviolet
radiation, the determination can be done on the basis of Beer-Lambert's law,
according to which absorbent
A =log I,/ I, = log T= e/c
For the quantitative determination of an organic compound the
at which its solution has the maximum absorption is wavelengu
in mixture analysis. identified. is also sc
It
(iii) Determination of Molecular Weight - U.V.
be used for determining spectroscop
the molecular weight of compound if it canbe
converted into suitable derivatives which shows an absorption bandinspectrun
For example, many hydrocarbons and amines form picrates the absorption
spectra of picric acid is not effected by complex
(iv) Study the Tautomeric Equilibria -formation.
spectroscopy
canbe

used to determine the percentage of keto and enol U.V. in

compound,
form present
Shwan-2024) Spectroscopic Techniques and Applications 165
acetylacetate,
ethyla by measuring the strength of therespective absorption
as
GNh
hands,
Kinetics of Chemical Reactio-It can be done by
() Sady of concentration
echangein
the of reactant or product with time provided
aSuring product
product exhibit suitable absorption in the U.V. visible
of the reactants or to concentration.
As absorbanceis directly proportional
one
region.
w) Detection of Impurities - The impurities present in organic
ompounds can be easily detected by U.V. absorption spectroscopy. The main
this method are -
esons for the superiority of intense.
(a) The band due to impurities are very
(b) The organic compound can be
classified into saturated
little absorption, while the unsaturated compounds have
aompounds having
strong absorption bands.
spectrometer. Give its
0.7. What are the essential partsof U. V.-visible
(R. GPV, MarchApril 201O)
inportant applications in analytical chemistry.
Or
its applications.
Describe U.V. spectroscopic instrument and mention
(R.GPV., June 2013)
Ans. Refer to Q.5 and Q.6.
spectroscopy.
Q.8. Discuss brief introduction of electronic (R.GPV., Jan/Feb. 2007)
Or
spectroscopy. (R.GPV., May 2019)
Write brief note on electronics
Origin of Electronic Absorption Bands - In organic molecules,
Ans. excited with the absorption of
electrons of o, T or n bonding orbitals may get rst'on
electronic radiations. pes of of bonded electrons from
there is electronic exéitation
So, whenever. arise. This phenomenon is called
higher energy levels, U.V. spectra
lower to
The possible transitions in electronic energy levels is
electronictransition.
shown in fig. 6.2. o* (Antibonding)
* (Antibonding)
Energy
a (Noa-bonding)

K (Bonding)
a (Bonding)
Molecules
(+os)
Fig. 6.2 Transitlon in SimpleOrganie
() o o ransition -This type of electronic transition requires
amount of energy. So compounds
having single
large
covalent bond or
 166 Engineering Chemistry

o-bond cannot absorb in U.V. or viz., region in other

radiations.
(RWords
.GPV., B. Tech.,ean
are transparent for these
(ii) n ’ o Transition -
hese
atoms can have this type of electronic
atleast one lone pairs of electrons sO,
Compounds
transition having
Organic compounds
shows this type of transitions, C- OH, C- OR,
C-
0, N, S
because these or
atorns Tiai
with
Ondhasog n
This transition requires lesseraamount of energy NH,, C- X
absorption in U.V. region due to CH,OH or
this type of transition.
Co (i) n’ t Transition - This
compounds with transition CHy-C shwy
is possible in
energy. Carbonyl >C0 grouping shows lowe stl
9y
U.V. region due to this type of transition.
(iv) 7’r Transition -Two types of
bands
whose energy is in between the energies ofn ’o* arisenby this transtions,
and
nabsorpion
T*
(a) K-bandi- Those organic
system give K-band. Due to conjugation, redcompounds which have transitions
shift is
intensity of absorption. The following table shows observed with
some K-bands
conugated
increased
Table 6.1
S.No. Compounds K-band
max (mu)
Emax
() CH, -CHCH=CH, 217 21
(i) CH, CH=CHCHO 217 16
(I11) CH, =CHCH =CHCH=CH, 258 35
(iv) CH, (CH =CH), CH3 296 52
(b) B-band- Benzene has a broad
absorption peak at 254
achromophore is present in
benzene ring, we get absorption bands withnm.lag li
bathochromic shift as compared to K-bands.
The B-bands in aromatic
compound are given in following table
Table 6.2
S.No. B-band
Compounds Amax(mu) Emax
(i)
Benzene 254 204
(6) Naphthaline|(
312 250
(ii) Phenanthrene
330 250
 Spectroscopic Technques and Applcations 167
Shianh2024)
on elsctronic transitions. (R.GPV, Nov, 2022)
Write brief note
toQ.8
Ans.Refer Discuss about electronic
What is electronic spectroscopy ?
applications of U.V spectroscopy. (R.GPV, June 2022)
and
pansitions,
Refer to Q.8, Q.4 and ).6.
Ans. |R.GPV, June 2008, Nov. 2018 (0)|
Ql. Define R, value.
pure substance and the distance
ns Theratio of distance moved by the
Re value.
bythe solvent front is called
moved
The distance moved by the pure substance
Revalue = The distance moved by the solvent front

Q.12. Discuss chromophores. (R. GPV, Nov.2018 (0))

Or
(R.GPV, Dec. 2013)
Write short note on chromophores.
Or
(R.GPV., June 2014)
Define chromophore with example.
when present in a compound, make it coloured. In
Ans. Some groups groups,the absorption takes place in
other words, due to presence of such
range. These groups are known as chromophores. For example,
visible
>C=C<>C=0, - N=N-,- NO,
O = O etc. Hyper Chromic
Batho Chromic
Electronic excitation in these group Hypso Chromic
(Blue Shift) -(RedShif)
can be made easily.
The position and intensity of an Hypo
absorption band of a chromophore mayof
Chromic

be modified by the attachment

substituent group in place of hydrogen
structure.
on the basic chromophore shifted
Theabsorption maxima may be 100 200 300 400 500 600 700 800
wavelengths
to longer or shorter and its Blue Red

depending upon the substituent

chromophore
Fig. 6.3
position with respect to the maxima are given characteristic
names
some shifts in the absorption
Batho Chromic Shift(Red Shif) -It is a shift of Amax to longer
(i)
wavelength.
Hypso Chromic Shift (Blue Shif) - It is a shift of? a to shorter
(i)
wavelength. Chromie Shift- It is accompanied by increase in intensity
(iii) Hyper
of absorption. Chromic,Shift- It is accompanied by decrease in intensity
(iv) Hypo
of absorption.
 168 Engineering Chemistry
Q.13. Whie a note on Beer-Lambert's law. (R.GPV, BTech.
Sote and derive Beer-Lamberts llaw of (R.G PV,
colorimetry, Nov/De.
Write short noteon Lambert-Beer law.
Or
Write short note on Beer and Lambert 's law,
(R.GPV, June/July 2006,
Or 2006,
(R.GRV.Sep. 29,
2007, 1Dec.
2012,
Discuss Beer-Lambert's law.
Or (R.GPV, Dec. 2013)
Explain about Lambert and Beer 's law.
Or
(R.GPV, Dec. 2017)
State and explain Or
Beer-Lambert's law.
(R.GPV., Nov. 202,
Ans. Lambert's Law -
transparent medium, then theWhen a
monochromatic (R.G PV., June 2023)
of transmittedlight
is passed through a
intensity
I,h x10-k/ radiation is given by
where lo is the intensity of incident
substance. radiation and /is the thickness of transparent
Beer's Law - Beer found that the
solutions now the concentration of Lambert' s law is also applicable to the
solution is to be considered. Hence
I=lo x 10-*C
Lambert-Beer' s Law - When a beam of
passed through a homogeneous
solution, the monochromatic
decrease
radiation is
thickness of medium is proportional to the in the intensity with the
concentration of the solution. So intensity of radiation and
dI
c I.C
d/
So that dI
dI
d/ =8. L.C or =e C. dl or I =l x10-e.C/
I
or
=108C/ or = ECl= A
where e =k/2.303 is
called the molar absorptivity
log10
i0 1, =A is called the
absorbance. coefficient, anu
where C is molar A=Cl
0.14.Derive concentration, andl is the
thickness of the medium.
Beer-Lambert's law and application of U. V. spectroscop
Ans.
Beer-Lambert' s Law - Refer to 0.13. |R.GPV, Non 2018 (0)
Application of U.V. Spectroscopy - Refer to Q.6.
 Spectroscopic Techniques and Applications 169

Sianeand derive Beer-Lambert's law giving its applications and

Q1s (R.GPV, June 2009)
pmiations.
For
Beer-Lambert's law, refer to Q.13.
Ans.
Application - From this equation, we can determine the concentration
absorbingin ultraviolet or visible region. We measure the absorbance
t'ypecies,
solution of known concentration or called a standard solution.
,ofa
In this case, A =sC!
As = l ...)

where s =
solution of known concentration.
Standard
unknown concentration
NOw,we measure absorbance A, of a solution of
C solution, we have
.. sand l are constant, so for unknown
A, = sC!
Au = el ..i)
Cu
From equations (i) and (ii), we get
As Au or C= A C, ...ii)
C, C, A_
determined values, so C
Since Cs,is known,and A, A, are experimentally
can be calculated from equation (ii).
-
Limitations This law possess following limitations compared to
blue region as
(i) These cells are less sensitive in the
other regions of the visible spectrum.
depends upon the wavelengths of
(i) The current output of the cells
the incident light.
fatigue.
(iii) These cells show tendency to
The current produced photovoltaic cells cannot be readily amplified
(iv) because of the low internal resistance.
by the conventional electronic circuit
State Beer-Lambert's law. Explain how this law can be used to
0.16. solution. (R.GP., June 2013)
determine the concentration of coloured
Q.15.
Ans. Refer toQ.13 and
the basic laws ofphotochemistry. How the laws may
017. Name andstate solution ? (R. GPV, June 2012)
used to determine the concentration in
be photochemistry are as follows -
Ans. The basic laws of
Grothus-Draper law, also referred to as the first law of
(i) "only light which is absorbed can be effective in
photochemistry, states that
producingchemical change.
 170 Engineering Chemistry
(i) Stark-Einstein law or Einstecins law of
(R.GPV, B. Tech.,
states that "in the primary process, each reacting molecule isphotochemical
quantum of effective light".
() Lambert's Law - According to it "equal
radiation are absorbed by successive layers of equal| fractions
activaetueidvalebyo,
substance". of of
thickness the: incident
Refer to Q.15.
0.18. State Beer-Lambert 's law. Discuss
absoting
eperimental technique of colorimetry.
Ans. Beer-Lambert's Law - Refer to Q.13.
in(Rst.rGuP.mentV, aJunetion2010,
and
Instrumentation In a colorimeter a narrow beam of
the solution under test through filter or difraction grating. Theelight
currentpassgenerated
in the photocell is proportional to theamount of light transmitted by thes through
The current generatedinthe photocell will be the greatest whentthe
light
by the solution is the greatest i.e., the coloured solution is most dilute
solutitoen.d
transmi
Sample
Filter Photocell
Iris

Galvanometer

Fig. 6.4 Single Beam Filter Photometer

ExperimentalTechnique -
Block Diagram of Colorimeter - It is shown in fig. 6.5.
Narrow Filter or Grating to Select Test
Beam of Appropriate Wavelength Solution Photocell Meter
Light of Light (Coloured)
Fig. 6.5 Block Diagram of Colorimeter
Working - In a colorimeter, a narrow beam of light (of prope
wavelength) passes through the solution under test towards asensitive photove
diftraction
Generally, colorimeters are provided with arrangement of filter orwavelength
grating. Consequently, it is possible to selectthe most appropriate generated
(or frequency) by choosing a particular/filter grating. The current
in the photocell is, of course, proportional to the amount of light ttraansmitted
by the solution. This-in-turn depends upon the depth of colour ofsubstance
light
under test. Thus, the current from the photocell will be greatestwhenthe
sollution
transmitted by the solution is greatest.
This whenthe coloured
occurs
 Spectroscople Techniques and Applcatlons 171
SNann2024)
peneralImeter is calibrated to show not the fraction
dihute, However, the fraction of light absorbed. This will be proportional
ost ransmitted,butthe
concentration of the coloured substance in the test solution,
the
w are the main parts of an infrared spectrometer ?
Explain
019. What
inbrief
chpart instrument usedfor recording infra and spectra is called infrared
Ans. The spectra photometer. Most of the instrument have a
spectrometer orinfrared
(5000 to 667 cm'),
range off 2u to 15u
which is used in infrared spectroscopy consists of following
Theinstrument
parts
() Source of Radiation-The main sources of mid infrared
radiation are
(a) Nichrome wirewound on a ceramic support.
(b) Nernst-glower is a filament which containing oxide of
iconjum, thorium, yittrium and cerium held together with a binder.
(c) Globar, which is bonded silicon carbide rod, when heated
electricity at 1200 to 2000°C, they glow and produce mid-LR. radiation.
(ii) Monochromator - Prism and Grating are commonly used for
this purpose. The prism materials used commonly are Sodium-chloride,
potassium bromide, lithium fluoride etc., the most commonly used prism
materials NaClor KBr are hygroscopic.
Advanced infrared spectrophotometers produce the I.R. spectra by a
procedure based upon interferometry. This is known as Fourier transform
infrared spectroscopy.
(iii) Detectors The I.R. detector generally convert thermal radiant
energy into electrical energy. Two types of L.R. detectors are in use, (a) selective
(b) non-selective. In selective detectors, the response
depends upon the
wavelength of incidentradiation. Example-Photocells, photoconductive cells,
L.R. phosphorus.
(iv) Sample HolderGaseous samples are collected in a gas cells
equipped with mirrors. The simplest gas cells consists of a glass or metal
cylinder 10cm long and closed with appropriate windows.
Liquidsamples are collected in a variety of absorption cells like cavity
cell, demountable cell, sandwich cell ete. Cavity cell is made by matching a
parallel sides holes in a salt black. The demountable cell consists of a pair of
salt plates separated by a gasket mode of metal or teflon.
Solidsamples are analysed by incorporating them into a pressed plate of
alkali halide usuallypotassium bromide.
Q.20. How a sample can be analyze by infrared spectrometer 2
Ans. In infrared spectrometer a source of infrared light emitting radiation
s present, which gives radiation to the whole frequency range of the instrument
 172 Engineering Chemistry
(R.GPV., B.Tech.,
One beamn of such light is passed through the sample to be
molecules fells within
frequency of vibration of the sample of the he
examined. Ifthe frequency of vibrationenergy sample
from this moleculesrangS of to be
absorb
the range of instrument it will
scanned by comparingthe intensities
of the light.
beams before The Sel s itin,
over which the
through the sample, the wavelength range grating.
and
aftseprecrurn
in
can be sprayed out by using a prism or
corresponding to
The
spectrumcomparison pas ing
18 TOade
chart showing
wavelength or
downwards
frequency.
peaks
These spectrums are absorption Consistsagains
obtained ploted fa

corresponding wavelength thrrough detectors, which detectafter the pasSing of

the
substances in the sample.
Compounds can be examinedliin the
presence
vapour phase, as pure liquid, in
and in solid state. solution
(i) In the Vapour Phase In vapour phase analysis,
analysis is done
after removing water vapours from the sample. The vapour is
infrared beams. The end walls of the cells generally made offsodium
introduced'na
special cell of about 10cm length. This cell is placed directly in the path of
chloride
which is transparent to infrared radiation.
(i) As aLiq uid The liquid drop is measured after squeezing betyeem
the two flat plates of salts separated by a gasket made of metal or telon. A
variety of absorption cell for liquid are available, they are cavity cel.
demountable cell, sandwich cell etc.
(iti) In the Solution - The compound is dissolved to give 1to 5%
solution in CCl, or alcohol free CHCl3. The solution is taken into aspecial el
with 0.1 to lmm thick cell wall, made up of sodium chloride. Asecond cel
with equal wall thickness, containing pure solvent is placed in the path of
other beam in the spectrometer to balance solvent absorption. In dilute solution
spectrum, are desirable because intermolecular forces, which are strong in
crystalline state becomes minimum.
(iv) In Solid State-When the sample is in solid state it can be examined
by following two methods
(a) In it 1mg of a solid is finally grounded with a drop of liquio
butadiene
hydrocarbon or is C-H vibrations are to be examined with hexachloro chlonide
The mould thus obtained is pressed between two flat plates ofsodium with
(b) In i't the solid is grounded with 10-100 times in quandiy
hydraulic
pure KBr, the mixture is pressed into a special mould by means ofa
press. These KBr pallets containing sample gives better spectra.
ingerprins
.21. "IR spectra is often characterised as molecular
Justify this statement. recognisabl
Ans. This is because different functional groups pproducepeakscanbe
peaks at nearly definite positions in IR spectra. Most of the
Sivan-2024) Spectroscopic Techniques and Applications 173
assignedduetothe presence of specific groups in the molecule. So IR spectra
alsobeused establishing the identity of the compounds.
Q22.Eyplainin brief I.R. spectroscopy% (R.GPV, June 2005, 2007)
Or
White short note LR. spectroscopy. (R. GPV, Dec. 2017, May 2018)
Ans. Infrared spectroscopy is also known as vibrational spectroscopy.
7heinfrared spectrum yields the most informations concerning the structure
ofonganic molecules. Amolecule is constantly vibrating, its bond each, contract
and bend w.r.t. each otherFurthermore, given bond may undergo several
dhterenttype ofvvibratory motions. Each mode ofvibration, adifferent amount
ofenergy and accordingly
absorb radiation of different wavelengths. Hence,
bands.
each bondgive riseto several
Therefore, infrared spectroscopy is based on the absorption of infrared
Rdiations by the molecules, Jnfrared spectroscopy is employed for qualitative
and quantitative analysis of chemicalcompounds, and are most widely used
for the identification of organic compounds.
The infrared radiation lies between the visible and microwave regions
of the electromagnetic spectrum. This region may be divided into following
types
(i) Near Infrared Region-It is the region which extends from 0.8
to 2.5 um (12500 to 4000 cm'). It is also known as vibration-rotation region.
(ii) Far nfrared Region It is the region which extends from 15
to 200 um (667 to 50 cm). It is also known as rotation region.
(ii) Ordinary Infrared RegionIt is the region which extends from
2.5 to 15 m (4000to 667 cm).
Working of I.R. Spectrophotometer - The instruments are of two
ypes single beam and double beamThe single beam instruments measures
directly the amount of energy transmitted by the sample and the spectrometer
optics, It yields most accurate transmittance measurements and is particularly
Useful for quantitative analysis, The layout of the single beam infrared
spectrophotometer is shown in fig. 6.6.
Prism Attenuator Reference Beam
Littaw
Mirror -
Detector |Exit Slit Sample
Source
Beam

Rotating
Sample Entrance Mirror
Entrance Slit of
Monochromator
Slit
Fig. 6.6 Layout of aSingle Fig. 6.7 Optical Null Double Beam
Beam
Infrared Spectrophotometer Spectrometer
 174 Engineeing Chemistry
(R.GPV,B. Tech. te
Double beam instruments are particularly useful in qualitative
Two designs of double beaminstruments, which are
null system and electric beam rotating system. The widely
used
double
shown in fig. 6.7.
0.23. Write brief note on vibrational modes in IR

Ans. Theinteraction of infrared radiations with

s pectrom et
(Rsp.GecPV,troscopy.Nov, 202)%
matter can be
molecular dipoles associatedI
in terms of changesin with
underston
can involve either changes in bond length
(stretching) or bond angle (bending).
Some bonds can stretch in-plane
(symmetric stretching) or out-of-plane
(asymmetric stretching).
vibrations.Nibratin,
Bending vibrations can be either in
plane (as; scissoring, rocking) or out-of Symmetric
plane (as; wagging, twisting) bending Asymmetrie
vibrations. (a) Stretching Vibrations

Out-of-plane Wagging Out-of-plane Twisting In-plane Rocking In-plane Scissoring

(b) Bending Vibrations
Fig. 6.8
Q.24. Write note on applications of I.R. (R.GPV., March/April 2010)
Or
State the applications of I.R. spectroscopy. (R.GPV., Dec. 2011)
Ans. The important applications of I.R. spectroscopy are as follows -
() Qualitative Analysis L.R. spectroscopy is particularly usetul
in the qualitative determination of compound or component in a mixture. IK
spectroscopy was successfully used in jdentification of various organk
compounds such as alkynes, aromatic, inorganic ions.
(i) Ouantitative Analysis-The quantitative determination offgiven
offunctional
compound is based on the determination of cconcentration of one hexane
group of compound
and hexanol being estimated.
andthen concentration Supposecanthere
ofhexanol is a mixture
be determined
of
by measuring
absorption of OH bond. The following formula is used for caleulatingthe
concentration.
A=- log l, =abe
Shivani-2024) Spectroscoplc Techniques and Applications 175
where, A-Absorbance
IIntensityof radiation after leaving the sample
Intensity of radiation before entering the sample
a-Absorptivity of cell
hInitial path length of same cell and
solution,
e- Concentration of
Ifa and b are constant then,
A cc
Hence, c can be measured by knowing
A.
i) In ldentifying the Compounds - The LR. spectrum of the
compound is compared with that of known compound and from the
emblance of the two spectra, the nature of the compound can be established e
eiothe particular group of atoms give to characteristics absorption band in
wavelength in
he L.R.spectrum i.e., Aparticular group absorb light of certain
belongs.
IR. spectrum no matter to which compound it
(iv) In Detecting Impurities in aSample- ILR. spectroscopy is
very useful to detect impurities of the sample, I.R. spectra of impure sample
WIl show some extra absorption bands, by comparison with I.R. spectra of
Dure compound. Hence these extra bands if impure sample indicates the impurity
of given sample.
() To Distinguish between Intra and Inter Molecular Hydrogen
Bonding We know that generally, it is not possible to distinguish between
intra and inter molecular hydrogen bonding. This can be done by taking a
series of I.R. spectra of the compound at different concentration as the
concentration is increased, the absorption of bond, due to hydrogen bonding
increases. While that due to H-bonding remains unchanged.
C22031
(vi) Elucidation of Structure - Elucidation of structure is possible
by l.R. spectroscopybecause it gives valuable information regarding molecular
symmetry, dipole moments, bond lengths, bond strength etc.
(vi) In the Study of Reaction Kinetics- We know that any reaction,
thereis always bond breaking and making in the reactants. 1.R. spectra arises
from thedifferent modes of vibrations in bonds, so if we withdraw the sample
Tom reaction mixture in aregular interval of time, and study its L.R. spectra,
He Can draw some inference regarding the kinetics of reaction.
(vii) Study of Polymers-Infrared techniques have been used in the
On ofend groups and chain branching found in polymers, Useof polarise
infrared radiation has been made inthe study of certain properties of polymers.
Exampl0.e2,5. stretching of rubber.
Write short note on significance of IR spectroscop.
(R.GPV, Dec. 2013)
Ans. Refer to Q.24.
 176 Engineering Chemistry
Discuss instrumentation and
(R.GPV., B.Tech.
applications of TR
0.26.
Ans. Refer to Q.19 and
Q.24.
instrumentation and
(R.GPV,spectrosJcuonepy.
0.27 Discuss principle, applications2018,of
7 (R. GPV,,Nov.
spectroscop.
Ans. Refer to Q.22, Q.19 and
Q.28. What is spectroscopy ?
Q.24.
Discuss IR
spectroscopy ;
,Jv
uibr
neat ion2a0l
2 4 ,
instrumentationand applications.
Or (R.GP.Vgiv
.,ing Ma pyri nc
2 i
0p1 le9,
What is spectroscopy ? Describe IR spectroscopy
?
instrumentation and applications.
Ans. Refer to Q.1, Q.22, Q.19 and Q.24.
(R. GP.giVvi.n, gNov.prin2019,
ciple,
.29. Discuss in brief the type of molecular vibrations.
(R.GPV, Jan/Feb. 2006,
DDec.
Ans. Various observations indicate that the atoms in a molecules aare 2013)
in motion, which may be of different types. Considerraa simple diatomic always
A-B. The only vibrations which can occur in such a molecule are k molecule
compression or extension, along the A-B bond.
Molecular vibrations are mainly two types -
() Stretching vibration
(i) Bending vibration.
(i) Stretching Vibrations - In this type of vibration the distance
between two atoms increases or decreases, but the atoms remain in the same
bond axis.
Stretching vibrations are of two types -
(a) Symmetric Stretching Vibrations When stretching and
compression occurs in a symmetrical form, we call it symmetric stretching
vibration.
(b)Asymmetric Stretching Vibrations - When one bond s
compressing, while the other bond is stretching, then we call it
stretching vibration. asymmere
Both symmetric and asymmetric
stretching vibrations are shown in fig. 6.9.
(ii) Bending
these types of vibrations,Vibrations In
and out of the bond atoms move in
these vibrations involveaxis plane. Hence, (Symmetric) (Asymmetrie)
angle. change in bond Fig. 6.9 Kinds of Stretching
The bending Vibrations
vibrations mostly are of four types -
Shivani-2024) Spectroscopic Techniques and Applications 177
(a) Seissoring-In this vibration, two atoms joined to acentral
and I move towards away from each other, is called scissoring vibration.
atom,
vibration bond angle changes.
this (b) Rocking - In this vibration, two atoms joined a central
and both atoms move back and forth in the plane of the molecule is
atom vibration. In this vibration bond angle does not change.
calledrocking(e) Twisting - In this vibration, the structural unit rotates about
the bond
which joins it to the of molecule is called twisting vibration.
Bond angle does not change.
(d) Wagging In this vibration the structural unit moves back
the plane of molecule is called wagging vibration.
and forth, out of the plane
All of four bending vibrations are shown in fig. 6.10.

(a) Scissoring (b) Rocking (c) Twisting (a) Wagging

Fig. 6.1O
0.30. Write short note on stretching and bending vibrations.
(R.GPV., Dec. 2013)
Ans. Refer to Q.29.
0.31. Differentiate between IR and UV spectroscopy.
(R.GPV, Dec. 2010)
Ans. The diference between U.V. and I.R. spectroscopies are given below
S.No. U.V Spectroscopy IR. Spectroscopy
) The region of U.V. spectroscopy The region of I.R. spectroscopy
extends from 10-800 nm. extends from 800-20000 nm.
(1)As U.V. radiations passes more IR. radiations are weak and so
energy they are strong and so cannot produced electronic
can cause electronic transition. excitation. They cause bending
and stretching vibrations of
organic bonds.
)Unsaturated and especially con All organic bondsand groups
Jugated group only absorb in thisabsorb in this region.
region.
(iv)UV. absorption spectrum
|broad absorption bands.
exhibitsIR. spectrum exhibits sharp
peaks.
 178 Engineering Chemistry
(v) This spectroscopy gives an idea
about the presence of carbonyl |This (R.GPV., B.Tech
spectra
give an
the nature of the
thhe molecudeale. abet
group and no conjugate system. identifying

(v)The spectra are usually expressed The complete

of the compound.
spectra usually estructre
terms of wavelength. in terms of are
number (v) funits.
requency exprewasveed in
0.32. Write short note on
rotational (or
microwave)
Ans. Rotational or microwave spectra is due
between the rotational levels ofa gaseous molecule
to
spectroscopy.
the result of
containing transtions
moments i.e., HC1, HBr, NH,, CO, NO, H,0 vapour etc. on
radiations falling in the microwave region. Homonuclear the permanent dipolofe
i.e., H,, Cl, O, Nz etc. and non-polar polyatomic molecules
show microwave spectra. tomiacbsCO,omolrptieodoculn notes
diasi.e.,
0.33. Discuss rotational spectra of diatomic molecules.
Ans. Assuming a diatomic molecule(AB) behaves as a
internuclear bond distance does not change during rotation.rigid rotor, it means
Consider m, and m, are the masses of two atoms Aand B
let r and rR be the distances of the atoms from the centre of
molecule.
respectively
gravity the
of
and
Evidently r = I t Ig and m A MBB
Moment of inertia (I) of the molecule is Cg
I=
Fig. 6.1I
= (mgrg)rA + (mATA )rB
= I TBm + mB)
Also
mA mp>g = mg(r- I )
From equations () and (ii), we get
m r ..()
IA (mA +mg)' "B (m +mB)
Substituting these values ofr, and rpR in equation (), we get
I=
m mÙr? mËmgr?
(m + mg) (m + mp)
m m¡r
(mA +mp) ..(V)
..(v)
where u= m mB
m + mp mA mB
 redced mess of(oe
thediatne mecle
e
anplr momentumofof rting moeee
e
E
asting molecule,
e eAngalarvelocity
momentum is quantized, and given by
angular

Rotational quantum number.

here/

Now 21 21
From
cquations (ix) and (x), we get
h2
J(0+) Joule
joules, so
is customary to report the energy (E) in cm, instead of
modified form obtained by dividing E, by hc is
qustion(xi) in
h
-.J(J + 1) cm
8n'le
-BJ(J+1)
where B -Rotational constant.
Now the rotational transitions for a rigid diatomic molecule are govened
by the selection rule (i.e., only those transitions are permitted in which the
national quantum number changes by unity), iLe., AJ=tl. The microwave
pectra are, usually, observed as absorption spectra (i.e., AJ =+ )and not in
cmission of radiation(i.e., AJ =-). Thus for atransition from Jto J+ 1, the
Otational frequency,
VU-J+) = BÊU +)(0 +2) -J(J +D)
- 2BJ+l) cm-!
Evidenly. Vo-+l) 2B
Va-»2) = 4B
V2-3)- 6B ete.
Hence the
eties of lines
rotational spectra of arigid diatomic molecule consists of a
equally spaced by 2B.
 180 Engineering Chemistry
0.34. Writethe applications of rotational spectra. (R.GPV., B.Tech., L
Ans. Applications of rrotational spectra are given below.
(i) Determination of symmetry in a molecule.
() Determination of bond length of apolar
() Determination of dipole moments of gaseous molecule,
moleculses isalso
possible by recording the spectra in the presence of electric field.
It is found that in the presence of external electric field (E),
the
rotational energy levels of the molecule occurs.
If Av = Shift of rotational frequency spliting of
u=Dipole moment of the molecule
and E= External electric field.
Then Av oc (uE)?
Thus, by knowing Eand measuring Av, u can be determined.
Q.35., Discuss principle, instrumentation and applications of
and rotational spectroscopy. vibrat2023)
(R. GPV., June ional
Ans. Rotational-vibrational spectroscopy is a branch of molecular
spectroscopy concerned with infrared and Raman spectra of molecules inthe
gas phase. Transitions involving changes in both vibrational and rotational
states can be abbreviated as ro-vibrational transitions. When such transitions
emit or absorb photons (electromagnetic radiation), the frequency is
proportional to the difference in energy levels and can be detected by certain
kinds of spectroscopy. Since changes in rotational energy levels are typically
much smaller than changes in vibrational energy levels, changes in rotational
state are said to give fine structure to the vibrational spectrum. For a given
vibrational transition, the same theoretical treatment as for pure rotational
spectroscopy gives the rotational quantum numbers, energy levels, and selection
rules. In linear and spherical top molecules, rotational lines are found as simple
progressions at both higher and lower frequencies relative to the pure vibration
frequency. Insymmetric top molecules the transitions are classified as parallel
rotation, and
when the dipole moment change is parallel to the principal axis ofro-vibrational
perpendicular when the change is perpendicular to that: axis. The the presence
spectrum of the asymmetric rotor water isimportant because of
of water vapour in the atmosphere.
Also refer to Q.34.
innstrumentation
0.36) What is spectroscopy ? Describe the principle, Non2022
process vibrational and rotational spectroscopy.
of (R. GPV,
Ans. Refer to Q.1 and Q.35.