48 CHAPTER 1.

ELECTROCHEMISTRY AND

I )1,()r 2

lr.'(:l,r'oscopic Techniques and

A I,plit:ations

't I lrrl,roduction
I|l r,rrpy deals with the interaction of atoms or molecules or matter with electroh
J fullntion. Molecules possess different quantum mecha^nical energy states such
Eh0trl,,, vibrational, rotational and nuclear. The transition can occur between thesd
ElBlr,p lry t,lur absorption or emission of radiation. These transitions are abided by quantum
|ler lrrrrrr,'tl selection rules.

tloscopy involves the production, measurement and interpretation of electromag-

Hlrr,r
11pl ! rrlrrr:tra arising from emission or absorption of electromagnetic radiations by atoms

ut rr,'Ltules. Detailed information regarding the structure and bonding, ds well as,various
llllr rrrrrl intramolecular processes can be obtained from the analysis of atomic and molec-
111p11 rrpr,r:tra. The instruments used for the spectroscopic studies are known as spectrom-

r,l r't rr

lllx,r,l,roscopic methods are more reliable and accurate compared to classical methods of
rurlrlysis. The following are the reasons why spectroscopic methods are widely used today

| 'fhey require very less time for analysis

',' Less sample quantity is required
il Sample materials remain unchanged during analysis and can be reused

I They give accurate results

Spectroscopic techniques have been applied virtually in all fields of science and tech-
rlrLrgy. Radio-frequency spectroscopy of nuclei in a magnetic field has been employed in
rrrrrlical imaging technique called magnetic resonance imaging (MRI) to visualize the
Irrl,crnal soft tissue of the body with unprecedented resolution. Microwave spectroscopy
trr rrsed to discover the so-called three-degree blackbody radiation, the remnant of the big
lrrr,ttg.

49
 50 CHAPTER 2. SPECTROSCOPrc TECHNIQUES AND APPLICA 51

Based on the nature of interaction, the spectra can be broadly divided

into the nrr.rrrrl, ol'ollcrgy referred to as a quantum. In 1900, the German
nl
types
l,r,rl,r)r-i(!(l t,hat the energy of a photon (E) is directly proportional
l'l,rrr k
1. Absorption spectrum:when an atom or molecule undergo a transition I ltt, l,'^ ,. hcu. The constant of proportionality h is called Planck's
from , tlr, r,rrlrr, /r : 6.63 x 10-34Js. The SI unit of frequency is reciprocal
lower energy level, Ea to the higher energy revel .Ey with a]r absorption
of a phr
of energy hu, the spectrum obtained is called a,n absorption spectrum.The 4 llr)'l'lrr,syrrrlrol v stands for { the reciprocal of the wave length, usually
i llt a;rr,, lrrrrilop], r,s wavenumber cm-I . The range of photon energies is called
tant spectral techniques such as uv- visible, IR, Microwave and NMR bek
absorption spectra (fig. 2.1). rpcctrum and is shown in Figure 1.3. Visible light occupies a very
,,; 111j, 1'lr,r'l,r'orrrtrgnetic spectrum, it is characterized by wavelengths from 380
ll'/l'rll trtrr (r'ctl).

Lrxrrrqr
Vw*qe(,ml ---*-
lo
I
r#ldIS l0ro $lx

Figure 2.1: Absorption spectrum

2. Emission spectrum:when an atom or molecule undergo a transition from I

hi1 ti isls $i.
energy level, @ to lower eneirgy level, .81 with an emission of a photon
of energj
the spectrum obtained is called an emission spectrum. For emission to
be o
higher energy states have to be more popurated than lower energy states.
H Figure 2.3: Electromagnetic spectrum
spectrum, atomic emission spectrum (AES), fluorescence spectrum etc.
belongs
this class (fig. 2.2).

,') Molecular energy levels:

;;1lk', rrL, l)()ssesses the following four types of energy.

I l,lh,r'l,ronic energy(E"l): It is associated with the electrons present in a molecule,which

lrrr ()(:(:rrpy various molecular energy levels. The molecular orbitals can be bonding
Figure 2.2: Emission spectrum ,,r rrrrl,ilrond.ing. The energy gaps between electronic energy levels falls in UV-visible
I t,P,t( )ll.

Based on the nature of the interacting species, the spectra can

be divided into two
,l Vllrrational energy(Er*)z Atoms in a molecule can vibrate by keeping the
gories 1r, rrit,ion of center of mass constant,
the energy associated is called vibrational energy.
l,',,r cxample HCI molecule can undergo bond stretching vibration. The energy gaps
1' Atomic spectra: Which arise from the transition of electrons between the lrr,lween vibrational energy levels falls in the Infrared region.
energy levels
;l tlotational If a molecule rotate in space about an axis passing
energy( E,ot)i
2' Molecular spectra: Which arise from the transition of electrons between diffe I lrrough its centre of mass, it is said to possess rotational energy. Rotational energy is
molecular energ-y levels. uv-visible, IR, Microwave and NMR spectra 1rosseSS€d only by molecules of a gas or a liquid. The energy gaps between rotational
belong to
category. r,norgy levels falls in the microwave region.

,l 'tYanslational energy(Et on")z If the position of centre of mass changes with time
2,L.L Electromagnetic spectrum l,he molecule is said to possess the translational energy. Ttanslational energy of a
Electromagnetic radiation consists of electrical and magnetic waves rrrolecule is usually not quantised. It becomes quantised only when the molecule is
oscillating perpendic-
ular to each other. They travel with velocity of right r:onfined in a box of nano-dimension.
1c: s xtosm/s) i" "ie-r"i. trr"
frequency(z) and wave iength (,\) are related by the equation, y :
X. Electromagnetic 'l'lrr,rcfore the total energy of the molecule can be written as the sum of all these energies
radiation has the properties of both particles *d *".,r"r;-The particl".^ur" : Ea *
called photons, l')tut,rt Eua6 * Erot * Et on"
 52 CHAPTER 2. SPECTROSCOPrc TECHNIQUES AND APPLICA ,S
LAW 53
Moreover Ea >) Eoi6 )) 8,6 )) Etuon" and the transrational
energy is negrigibly
Therefore it is approximated DS Etotot : E.t*Eooo*E,otElectronic 'f,$4
transitions of a m<

rrt
g
J T
*
fi

Figure 2.5: A bearyr of light through a solution

t4 , lrl llt. irrtensity of incident radiation and / the intensity after passing through any
llrlr lrrrr.ss r of the medium, then
E

u l:"+:fo"n"a*
Figure 2.4: Molecular energy levels tnl] :1*",
are always accompanied by vibrational and rotational
transitions. Similarly vibr
z.soetool] : km
transitions are always accompanied by rotationar transitions.
as broad band.
Thus uv rp""ir,rrr, ,
r"*+:€m (2)
: k12.303 called molar extinction coefficient, value of which depends on the
2.2 Beer-Lambertrs Law ,l'the absorbing molecule and type of absorption. The equation (i) differential
lfll ntr<l equation (2) is the integrated form of Beer-Lambert's law. Logarithm of ratio-
when a parallel beam of monochromatic electromagnetic radiation
is passed through htl,r'rrsities of incident light (16 ) to the transmitted light (1) is called absorbance ,A,.

:5:*:-.::*,1:1,:l
radiation
ql= 1,once1t1fi"".
with thickness of the
(") , the iate or au"r"*" in intensity (_d.r)
rcsr]: a
solution (azj is p.oportionJ lo the intensity of (3)
radiation (1) at that point and also to the concentration (c
) of the solution. r,rluation (2) and (3)
Note: The decrease of intensity (d1) is more when intensity of light A=ecr
increases. As the number (4)
photons per unit area increases, the number of encounters
ofphJtons with absorbing molecu.
increases' The decrease of intensity (d.r) is more when rxluation (4) is the simplified form of Beer-Lambert's law. Tlansmittance (T) is
concentration-;,*#";;"."i"., o, the ratio of intensities of transmitted to incident light,
rr,,rl as
absorbing molecules per unit area increases, the number
of encounters of photons with absort
molecules increases.
T:;
-dI x Ic
-----
CI,T 'l'lrlrrrfbre the equation (2) can be written as,
-dI A: €Clc: logT
*:klc -
Where 'k' is proportionality constant. l'lotrr equation (a) , a plot of absorbance (A) versus concentration (c) should be a straight
lltrl passing through the origin for a cell of given thickness (r), whose slope is er (fig.
-dI : 'J li). Beer-Lambert's law ( equation (2)) can also be written in exponential form
kcdr
1- I : Ioe-ko (5)
 52 CHAPTER 2. SPECTROSCOPrc TECHNIQUES AND APPLICA nt,)RT"s LAW 53

Moreover 8"1 )t Ea16 )) E76 )) Et on" and the translational energ'y

is negrigibry
Therefore it is approximated ds Eutot : E.t*Ea**E,olElectronic transitions
of a mr

an
9

Figure 2.5: A bearyr of light through a solution

tl l,', llr,'irrtensity of incident radiation and l the intensity after passing through any
llrh Lrrr.ss r of the medium, then
d

H ["+ : fo' *"0'

,Ig
ln- : kcr
Figure 2.4: Molecular energy levels I
are always accompanied by vibrational and rotational transitions. z.sozlosl] : kcr
Similarly vil
transitions are always accompanied by rotational transitions. Thus ,Is
as broad band.
UV specirum to87 : €cr (2)

e : k/2.303 called molar extinction coefficient, value of which depends on the

2.2 Beer-Lambert,s Law of the absorbing molecule and type of absorption. The equation (1) differential
nttd equation (2) is the integrated form of Beer-Lambert's law. Logarithm of ratio-
When a parallel beam of monochromatic electromagnetic radiation is passed lttl,r,rrsities of incident light (16 ) to the transmitted light (1) is called absorbance 'A'.
through
absorbing solution of.6rvur
given w'us,ur@uruu
concentration (c) the of oecrease
r=ate or
urre r-in[e
\t;,, , in mtenstty
decrease
m intensity (_d.
(-d,I)
with,thickness of the solution (dr) is proportional to the intensity usr]: a (3)
Tli"llt"
radiation (1) at that point and also to the concent.*tio, (c of the solution.
Lr i.r"t
) crquation (2) and (3)

A: €cr (4)
'l'ltr rrluation (4) is the simplified form of Beer-Lambert's law. Tlansmittance (T) is
rlullrrcrl as theratio of intensities of transmitted to incident light,

r:!- Io
-dI
, xIc 'l'lr,,rr'lbre the equation (2) can be
dr written as,

-dI (1) A: €Cfr: - logZ

*:klc
Where 'k' is proportionality constant. l"t , ,trr equation (4) , a plot of absorbance (A) versus concentration (c) should be a straight
lltrl passing through the origin for a cell of given thickness (r), whose slope is er (fig.
'.lli). Beer-Lambert's law ( equation (2)) can also be written in exponential form
-dI
-7-: kcdr
I : Ioe-kt* (5)
 54 CHAPTER 2, SPECTROSCOPrc TECHNIQUBS
AND APPLICA
I' 1,, ; I I' I, I,) S I' ECTROSCOPY
55
1.2 -
1+
0.8 +
{ 0.6I A: ecr
0.4 L
0.2 L Here, e and thickness ,fr' are constants,
therefore
oJr A1 c1
u.u
0.o ZA"O {O.O 60"0
Az c2

concrntration
0.045 0.04
(uill 0n22:
Figure 2.6: plot of Absorbance ",
cz:0.0795M
against concentration for
a given thickness
2'2'3' A 50 ppm standard solution of Fsz+ after d,eueroping red corour
In uV-visibre spectroscopy, wi,th
absorbance -4 is protted ',,!,!';*?,,1!Y",:?::::':"*itl?n:." it o.e at-oeo n* wniJ on unknown so-
spectroscopy,transmittan""-ir'pfoti"Jl*"r"r, against waverength, whereas
in '#:"ff;Tff:"tr":i;
wave number. rt ltrtrt'srn'ittance of 0.r. Find' the concentrat,ion of unknown Fes+ sorut,ion.

-logT : ectr
Here, e and thickness ,tr, are constants,
therefore
logTl c1
logT2 c2
los0.2 50
Problem 2'2't' The-percentage transmitjg,nce log0.4 c2
of a 0.01M dye solution c2:28.4ppm
']u,Zi,ffi:,':iZ;"k'7J' ;i";*;;;;;|0"'ooo e: - irii'ini,noo,o,oonce in ethanol is
(A) and mo
3.il UV-Visible spectroscopy
\'lnilrk'light absorption is known to all of us,
Ans: because this is what causes objects
r,hrttrt'd' For example, a blue dye appears to be
blue because ttre tight at the red end
e;r.r'r,rum is absorbed, reaving the of the
blue light to be trr.rr*itt"a.-Human
,n tt spectrometer analysing the light reflected eye is functioning
r.o* trr" .*face of a solid or passing
u,u Du
A:lonlo
"I
tlrr,,rrgh a liquid.

A= . 100
: f 'r'lrrciple: urtraviolet-visible spectroscopy (uv :
o'6e8e 200-400 nm, visibre : 400_g00
Fromequation(q';: trtrr) corresponds to electronic excitations d;:"
;:d llr" r.olecular orbitalq of the systems. th" ;g; revels that correspond
In particular, transitii"ns involving zr orbitals to
where & :2cnt :0.2d,m l"rr(' pairs (n : non-bonding) are and
important and so UV-visible spectroscopy
Molar absorption cofficzent,€:!- A
0.6989 r,r'' fbr identifying conjugatedi systems is of most
which tend to tarre st.onger absorptions.
cI O.tmota,rrrffiTdiG :349.4mo1-1dm2
2.3.L Classification of Electronic Tlansitions
Problem 2'2'2' o oy." solu-tion of concentration
0.01M shows absorbance \vlten a molecule absorbs energy in
of 0.0/i at ds. uv-visible region, its electrons are promoted
T#offJ""l^::::,;:y#:tL:,X{n',n;;;;:;,;;;;:""iit,0,, unde*oii bonding molecular orbital to i,n antibonding from
^
.l.ctrons are involved in electronic *otJ"ut* *uii.r. rrrr"e distinct types of
"tna),to,, transitions. These are o electrons, zr
electrons and non-
lr,nding electrons(n)' There are bonding
and antibonairg-*oi""rlar orbitals
associated
56 CHAPTER 2. SPECTROSCOPrc TECHNIQUES AND APPLICA \ I, ;I I II,I') SI'IiCTROSCOPY 57

with a and zr electrons. Electronic transitions are classified into

four types o ---+ yrq nrrrl y'trtr,re antibonding zr molecular orbitals. In the ground state the six zr
7r--+ T*, fr --) zr* and n --+ o* transitions. For example formaldehyJe molecule rtl,r (x)cupy bonding molecular orbitals. Here the transition takes place from
C-O o and zr bonds also non bonding electrons or", o*yg".,
atoms. [{t t 7,., t,o LUMO $a.\*o, is observed at 247nm
o.*
It* LUMO
Ilnlurr.,t There are three double bonds in conjugation. It has six zr molecular
otoo* o*
t,
ntofit n to
Elrlt,nlx (',1\,tltz,tbz,tht,rbs,/ra) formed by the linear combination of six atomic or-
n
1t
HOMO
rt* bltrl, 1g, orbitals). Here ry'1, tlt2 and,lts arc bounding molecularorbitals and |tt,$s
Sltl y'roru'c antibonding zr molecular orbitals. In the gtound state the six zr electrons
{,, o
Ht'lll,.y bonding molecular orbitals. Here the transition tales place from HOMO
H2C*$: to l,tJMO. The .\*o, is observed at 255nm. Herc tlt2 and rfu are degenerate orbital
(tntttrt rrnergy) ar.d rlta and tlts are also degenerate.
Figure 2.7:, Blectronic transitions in formaldehyde molecule
V6

1. o ----+ o* transitions:The saturated hydrocarbons are transparent to uv_vir

Vs V5-
light.Therefore they are colourless. The saturated hydrocarborr, V+ LUMO
give only a .. I ry4 {rs- LUMO
o* transitions of c-c o bond and c-H o bond. This type "r, occurs i.=z+zn-
150nm. The ordinary uv machines take spect* orrly from
saturated hydrocarbons cannot be detected using uv-visible
of transition
200-700nm and \r2
ur,
_+_
-r.l--l-
Ha'rr,rn

v:fr
------ I
vr{t-
I
L=25snm
HoMo

2. 7t
spectrometer.

-+ zr*transitions:The unsaturated hydrocarbons containing double or tri

rfr
-{+--
-
--
v, --ff-
bonds shows this type of transition. For example c:c (a) (b)
of ethylene molecule gi -/
an absorption maxima at 16gnm. so normal uv machin""*itt-rrot
show such t -
tions. In the case of molecule containing conjugated double
bonds, these trans
can be observed from highest occupied n'*oi"*t., l,'igure 2.9: Molecular energy level diagram of (a)1,3,5-hexatriene (b)benzene
orbital (HoMo) to lowest r
cupied zr molecular orbital (LUMO). In the case of t,a-buiadiene
these transi
are observed at 217 nm. 1,3-butadiene has four zr moiecular
orbitals(/1, ,br,rlrr,i,
formed by the linear combination of four atomic orbitals 'H;;;Ur:;;;rp
are bounding molecular orbitals ffid
lporlit.rr;. As more and more double bonds come into conjugation the absorption comes to
lrs and. $4are antiboniing n molecular orbi t'he visible region. In the case of lycopene a red coloured natural dye of tomato,
In the ground state the four n electrons occupy bonding mo-iecula. l,lrere are 11 double bonds in conjugation therefore \*o, is observed at 505nm. It
orbitals. I
the transition takes place from HOMO
{2 to LTJMO r/, wittr A*o, :ZITnm. is estimated that there is an increment of 30nm with every increment of a double
bond in conjugation.
o
n' --------1- LUMO

n -----*l.L
(, __{+_
I L=169nm
HoMo
vr-*-*{l_
ffi
(a) cH2:6s, &) Figure 2.10: Lycopene
_f
Figure 2.8: Molecular energy diagram of (a)ethene (b)1,&butadiene n ---) zr* transitions: Such transitions are observed in aldehydes and ketones,
which contains ) C : O group which has both zr electrons and non bonding elec-
trons (with oxygen atom). These transitions are generally observed with low inten-
sity when compared with o ---+ o*and fi ---+ r*tra,nsitions. (These transitions are
1,3,5-hexatriene: There are three double bonds in conjugation.
molecular orbitals (th,rbz,th,tb+4ts,/o), formed by the li.rla'.
It has six zr symmetry forbidden and hence observed with low intensity absorption. The n and zr
combination of six orbitals are at different planes whereas zr and n*are in the same plane). For example
atomic orbitals (p orbitals). Here lt1,tlt2 and ry'3 are bounding
molecularorbitals and formaldehyde molecule shows n ---+ zr* transition at 290 mn with very low intensity
 58 CHAPTER 2. SPECTROSCOPrc TECHNIQUES
AND AP. I' I 5 I I I I, I' SPECTROSCOPY 59
where as fl- ---+ zr* transition
at 1g0 mm with high intensity(not
nary uv instrument readable in It'rl lry vibrational and rotational transitions. Therefore discrete lines are not
yhich tut""-rp""ir,rr., r.o* zoo ,r,- ti'soo.r-;.
unsaturated ariphatic ketones show'n conju Itr l,lr. spectrum and thus it appears as band with an absorption maximum.
-j. ,- transitions above 290nm.
4. n ---> a* transitions: compounds
containing s,N,o etc which
electrons show these types contain nonbon
of t.rrrriiio.r", these transiri.rr'1." arso
-t-Jk",
occur in low intensity. The forbidden
ab"o.piion pru"" brow 200nm.
2.3.2 fnstrumentation
t*H$zn
IT,YTL:l:::Tff$:.":llXHIfl right source, monochromator
(prism or grating),, t
I 0.6
ment ramp .,a n - ai,"h,,s"
Most of the spectrometers u."
;;;.
h^'i"T"'i,l iJ"T:3f"xfli::[r#:ffis::l
;
0t
(
L'
,U
L{mrx)*395
aorft" u"ui ir"trr*"rrtr- ,lluum {[]
of light is split into
:$:::i":[i*:1":"11,IJHi"d;h'";;"i1tt]"
T:T ;;. ;;;ffi
(',*pre beam 1 ) and the other thrc w
rererence (rererence
J#:lt:[tilii::fiil,Tfff":,]A;T ll
.[
o'a
,Ti"":,ffT,fffli'i*:i^,"i":;T;;# cuvette. rhe pure sorvent I
in another similar cuvette.
The most ;#ffi;,t:;.,:,?il:lTorvent is taken as rJf..",
rere, * I
Ltmrx)*t55
and cyclohexane. The intensities water, ethanol, hexi
detectors and compared.
;i *il; hght beams are 6n,are
en measured by electro
compared' If tr,g
-^^ ffffi I:;iJ:;:;iffi.l:,l"iT
the sam^lo,l^^^
"*pr";""'ffi -r
1,;i:";"I.J."::#j*
is detected and recordea. ?*:r;:*#i*1ylt
*," o"or,
then 1 is ress than .re and
, this diffe
o{* ''-
";ilf:'J;J:"##;rlHI:; +:r_:T,"Tffi: 2Br 30$ 40a 5AO 60Onrf
Itnm)

jH"
Wtt.Qgurce w -
Figure 2.72: UY Visible spectrum of an organic compound

lrsr,tiiffi*!a*

2.:1.4 Applications of uv- visible or Electronic spectroscopy

sEtsctsr 2
ro
l. For the detection of aromatic compounds, conjugated dienes etc.

For the characterization of dyes and colorants.

q&ffi; Ur*&t*$ 1 3. Detection of impurities. For e.g. benzene is a common impurity in cyclohexane
;r;*1" I which can be detected by the absorption at 2b5nm.

Figure 2.11: Instrumentation Determination of unknown concentration. This is done by comparing the absorbance
of UV Visible spectrometer with the abborbance of the standard solution.

2.3.2 UV-VisibIe spectrum: Study of kinetics of chemical reactions. If a reaction involve shift of absorption
frequency or wavelength ,the rate of such reaction can be easily monitored.
It is a p10t of Absorbance (,4) against
absorbance is a characterisiic-rrt,r",
**r:1""q*rr, ) of light. The waverength
of rrraximum 6. Widely used in medical lab for quantitative estimation of blood sugar, cholesterol
have very different absorption
a"risi"r"g ; i;;; .-,Differ"nt eornporrncls may etc. These tests are done by measuring the absorbance after developing colour with
maxima .rralu"oruu*u.'friu"r.onic
tranritronx rr,re ,suary suitable reagents.
 60 CHAPTER 2. SPECTROSCOPrc TECHNIQUES
AND APPLICA ,\t,t,)(ifRoscoPY 61
2.4 IR Spectroscopy
--+
o==o o*c-0
Symfiritlc SirBHrlrlg Asy|trrtrlc &tr€bhlng
Ho Cilrrqg ln dfd6 ffiofi|efit Cfi'$go ifi dlpole morfi6nl
lR lri&lvs lR scllv6

\
2.4.1 Origin of IR spectra f*oilnplar$ o=c=a
\\
aonding,.oul$bnd
Bsddlng
h dpolL munent -.
chdngE h ,

The photons in the IR

changa
tFl ect i,e frTll***
region are not enerscrin 6h^r._L a

:::'J;T]ffi :1,1J:'*;#:?.; Figure 2.13: Stretching and bending vibrations of COz

"ilw*:'"',;"u"'[Jb;;;;;'F1,ff
y:*tii:":":^:ffi[i*[:#*t,,,:?;lr;*:*rx jjro.,and_,husdin
,rurur:I*;,'fi:;1i:xi!ieilXr1Hil;T'i+*iJr3;3".t"""-jl;, lrrrrics during vibration, the centre of mass should not change its position. It is to
;^ffi
tionar .pu"t.,irrr-' ^-tational transitions, ,rrJ *rJ't'#rrl"liJ* cailed
vibrationar_ rol
111,',

lrl rrol,r:d that bond length changes during a stretching vibration and bond angle remains
rr,rrrrl,t,nt. But in bending vibrations bond angle changes and bond length remains con-
#"ffiTd#ilLH:T."*.tTfi":iTi:r,.j";,x3,,ff nl rtltl..

the product or
i.s.
;;;':;#;::, "13]? #31:*:,*"stretchinsvi
nugtgar distance (dipore-,?.o,,
.::^.1.:'
11.1{;r
aruto-i" ,i;iliJ,H:"
"r,u,g"
change in dipolemoment
;i,ool)it'"1?
with stretching
,a ."i*,.,
fi:"::.'":'trationallv
where homo .,,"
active .r",,ir"r'J"".",
4,\r
HH
,r*"\
H
,/\
HH
2.4.2 QmrcricSrctufirg Aefrntfiicsfetfirg Badi'glnpbre
Number of vibrational
modes in a molecule:
lecuIe:
the position of an atom Figure 2.14: Stretching and bending vibrations of HzO
*:O_""*tP:ng
correspondi'g to ti."" in
cartesian three degrees of freedom
;ffifx.Tf
number l:?*Ji;",:"""Hff
of degrees "o-orai.,r1l"1"""^:l"r::^t:quires:#:T"*:f
r*"ar*';'ru:t;*i:::i:l:,1i:"':'ffi T;.lTi.#
"r ";ili";l Wlren a'group like -NHz is substituted in a heavy substrate like benzene as in aniline,
rrrore number of bending motions are observed for the -NHz group, they are rocking,
Linear molecule: For a linear molecule sr:issoring, wagging and twisting.
tional degrees of freedom, there are three translational
3n - s. For a diatomic
th";;;; tot"ut ,r,r-u";;ii,I#ffiar and two rota-
mode, i.e. stretching
motecili" : modes possibre is equar
,i.rrr", th;;; ;;",r;;" (s.x _< _ to 2.4.3 Mechanism of Interaction
vibration ir ib,"T
,;;;;r-# Ii."r"r,i.,g2 vibration.
1) vibrational
During the vibration of a molecule if there occurs a change of dipole moment, it will lead
to the generation of an oscillating electric field and act as a source of electromagnetic
utar pranes. out of tire ii}*:_,;;;,:,mme,ric
rr-ir"ai"I#*"0"., .;,;;;;;TJ:mf+llimf:*
=1*"1}:,.;:'.'.;;**:i1".*#}ffi:.r*iffi
rour radiation. Similarly when a photon of frequency come in resonance with the frequency
of vibration of a molecule, the absorption of photon takes place and the molecule starts
:F.:[":"{::::Jlil:*:"tti:B:f :# j;?r+j*:L1-i.,,;;iil."',,.].,iu",*. oscillating with the frequency of radiation.Consider the asymmetric vibration of CO2, a
ilT.'j"Tffi i,T. jH,:H:r,r'"4':i::r"#;uihf;[1tr,T,,#liii:r.l:,ff; fluctuating electric field produced is as shown.

Non Linear molecule:

F.or & non lin^. molecule
2.4.4 Vibrational energy states of a diatomic molecule
freedom.For u""-or" rrr" ther. it,r..llrr (i vilrrrrrirrrrrl ,lr,r,,rrrrs
" ",i'i',,i,1,1,,,,r, A simple harmonic oscillator can be considered as a model for vibrating diatomic molecule.
freedoms. ,;r;;;il:,:Hr[i,ln'::
Ti,*
u"m." co,' ;"# H'ffi
"r"r""*;';.""t atoms..l,.rr.r' (Jr r ,, ;r of
Consider two atoms of masses rn1 artd ?r)2 conn€cted by means of chemical bond of force
ff ;[::"1T, ffrffi;i;: ;l;
;
lii I. ;:l i,, l;i; li:llii,l;:;
constant 'k'. The system is analogous to the system of two masses connected by means of
:, an ideal spring. According to classical mechanics the fundamental frequency of vibration
 62 (',,,',,t,titt 2. S.ECTROSCO,T
TECHNIQUES AND A,,LICA
III SI'I'CTROSCOPY 63
6
lr n In to quantum mechanics, for the transition of vibration energy levels, the selec-
ll
+ I fltn rrrl,,rs given by Av:t1 i.e., vl-v: -F1, therefore equation (4) becomes

hus - lL,
uo: u (5)

r nrlrration (5) impliesthat frequency of absorbed infrared radiation (z) is equal to

lnrrurrrtal vibrational frequency of the molecule (26 ).Thus there should be only a
, lirrc in the vibrational spectra of a diatomic molecule. In fact a band is observed
,nrl of a single line which is due to unharmonicity at higher quantum levels, In the
Figure 2'15: Mechanisam Eo,,,, phase the vibrational transitions axe accompanied by rotational transitions and
of interaction of osc,rating IR spectrum will be having sharp
dipore ofco2in asymetric
st
& npectra will be complex, but in the solid phase
(r, )i. given by llrar rr pt,ion peaks, therefore IR spectrum is usually taken for solids and seldom for liquids
ittr I l,,tLses.

,": *Tf
where p is the reduced mass of
: (1)
the system given by
rfltrftZ I
t

Consider the bond stretch

rnr * mz ll
ts
by a length ,x, from the
(V) is given by mean position, then potential
energy
la
'rt
3

V : -!p*z d
2 (2)
Substituting this in the
r Sch"^.li
;he Schrodinger
her_^-r^ *",il
of harmonic equatron on sorving, the eigen
or ^^^:r, ;;";; ffi#:T1;iH,|:H:l
a
values of energies faeflrodGlhh|rfir#

E:(v+)lnn Figure 2.16: Potential energy diagram of a vibrating molecule

(3)
(r,l

[iri;
"=
tf Hi,".i T?'ff :H:ul* 11 ]?':", 0, 7,2,3 rn the ground
Xj:ilt
itl:f ;31,fl ;!?..,+,,*#"*rru#:LT"T:1m;,*T,3#'i;;,Ji,lH,fl
;:ff :,'#*:?Jffi Tv;Jff';:::ff Ht Problem 2.4.L. The CO molecule absorbs i,nfrared, frequency of 21.40crn-r Calculate
#":i:Ifj-ffi :**v"};::ffiff
::]J:rl=il:"i:,ffi'xf;[]****:*rxili'"i+lri.4I{fi $t the force constant of the chem'ical bond,
: 16 amu.
giuen that atomic nxasses of C :12 amu and O
iiil!:n'r-':ff
energy of a molecule can h"". .?J;'JT,Tfffi
'evcr oe vrbrationally at rest, bu :;gr
r&#:?'Jt;::nr:;-;.t'[*tx"iTix*tT]",;.'Jffi
; ".;^-w i","i
* "; level vl, ,n". "nil:",,H
;;;;"*"r:ffi ;: ";.:::,:::: j::,iii:lif
"iJ"i,p i.1,nTiII;,;;*,". Ans: From equation (1)
hli,fi HF:i,t1;a:,:JJffi:rd1i.Hy:r
vibrationat ""t,o,"opf
from lower vibrational
irr".ir"f;;il:J,f**rron
u'rure'ce rn energy lev,lt u r,. rrpper
is equal to electromagn.l,i<:
energy [z absorbej
absorbed. rrr,rlirr,r,ion of 1
uo:2n
AE:1,
squaring and rearranging force constant (k) can be wri'tten as
*)n,o- (, + ))n,o : r,,
(u' +
k: Atr2uilt
(vl _ v)huo _ lu,
g) (v) is equal to fundamental aibrational frequency
Frequency of absbrbed i,nfrared, radiation
 64 CHAPTER 2. SPECTROSCOPrc TECHNIQUES
AND APP, 65
,\'I'I'CTROSCOPY
of the molecule (us). Therefore

k : 4tr2u2 lt
but u: cD Therefore
k:4n2(cr)2Lt
ITIyTTIZ

mt*mz
lt : t2xt6 x 1,66 x 70-27 Kg:
DT t6 1.13g x 10-26Kg
(3 x 108rns-1 x 274000m-1)2
I:i;:;:.x
k:13491y*-r x 1.138 x t0-26Ks

*rdlr-r

Figure 2.17: lR spectrum of 2-hexanone

ications of Infrared spectroscopy

I{ere:zlced, mass (1.r) is giuen by
rThfitz
rnr * rnz
l. Determination of force constant of a diatomic molecule.
1x19
lr: 1]10 x 1.66 xt0-2zKg:t.5TT x10_2zKg Identification of functional groups in organic molecules. The presence of functional
r (3 x groups can be readily detected from the stretching vibrations of the bonds present
10srns-1 x 413800rn- t)2 x t.,zz x to-2zKs in the functional group. For example absorption range of )C:O group in saturated
=;;?;:;x ketones is 1700-1725 crn-r, -OH group in alcohol is at 3300-3500 c'm,-r , NHz
When deuteriurn is substituted
for hydrogen, force constant group is at 3200-3300 crn-l , c:c in alkenes is 1620-1650 cm-r and c-H in organic
t*mains same therefore'
compounds is at 2900-3000 crn-l
-2 7
u-q-
p
u12
__: _
Fz Identification of unknown compounds. This is generally done by comparison of
uz' l.tr IR spectrum of an unknown compound with that of a known compound. The
41.992 2x1e comfarison is especially mad.e at the fingerprint region 700-1500 crn-l which involves
_ 2+19
complex bending and fluextional modes of vibration.
un2 ii+8
v2 - 29g8cm-r
4. Determination of purity
2.4.5 Recording of fR spectra
Earlier IR spectrometers 5. To distinguish between intra molecular and intermolecular hydrogen bonding. The
operate in a coltin;rou,s-sweep
emplov purse Fourier-traasform
lriinj't""1r9l"cv.
mode, whereas modern
machines -OH stretching frequency(3300-3500 cm-L ) does not change on dilution in the case
a sample'regardless of its
physi;-#;'", il;;J'ro*r"
can be recorded on of intramolecular H-bonding. Eg. ortho-hydroxy phenol, and para-hydroxy phenol.
is mixed with potassi"*
b;;;;";[*o"" *ria, riqriJ""I?*. ,* a soltd, the sample
i" p*rr"ijnto a thrn wafor, which
In p-hydroxy phenol there exists inter molecular hydrogen bonding. The molecules
placed in the path
of the infrarJ;; 1*rr" T:,r riquids, ,.ir"*iriourd is get separated on dilution and intermolecular hydrogen bonding weakens and there
thc rr pracocr between is shift of absorption frequency with dilution. In o-hydroxy phenol the hydrogen
;:.""::,#r,:Tffi f;.[T;$T:i5xg"jj1,#ir;;:H11a,carr.-ii,u,#,u,,"" bonding type is intramolecular which is not affected by dilution'
 2.

."#{t-O=
CHAPTER SPECTROSCOPrc TECHNIQUES
AND APPLICA ,, NA4IT SPECTROSCOPY 67

(rr) lf number of protons odd and number of neutrons even . Net neutrons spin is
: L,*, |"'; such nuclei
Irrsrnot€fld$r*.tff&rg hp.hy&oxyptcrol
li-..
\)
zcro but, proton pairing leaves odd half integral spins I
rrre NMR active eg.lH; I : :
*,1+Cl;I f;
(lr) tf number of protons even and number of neutrons odd. Net proton-spin is
: |. One
fnffiS9e*'** zero but, neutrons pairing leaves odd half integral spins eg.|3C;1
neutrons spin lefb out in pairing in |3C; such nuclei are also NMR active
Figure 2.18: Intermolecular
and Intramolecular H_bonding
'I' will have (2I*1) possible orientations.
mechanics tells us that a nucleus of spin
Table 2.1:
.1: Infrared rrrs with spin I will have 2 possible orientations. lff and 13C are the examples for
F\rnctional functional rruclei. In the'absence of an external magnetic field, these orientations are of equal
IR f.equen"y strength of band lJond
group (tm-') . If a magnetic field is applied, the energy levels split. Each level is given a spin
()-H energy(lcJmol-r tic quantum number, I. For ?n; t -- 1, There ate 2 x 1 + 1 : 3 orientations are
N-H J Strong, broad I 465
3100-3500 lMedium I

C-H 2700-3700 | 3e0 .Aaolied

weak
C:C 2000-2200 weak
470 Nt field *agrraic netd
C:C 1600-1680
840
l=da
weak ,
C:O 1630-1800
610
tltg"s 745 :Fi
,
i

2.5 IH-NMR Spectroscopy bo

t3)
6 t -
IU
\ !

Principle Nucrear magnetic resonance.spectroscopy -{ lr+tr&

depends on the absorption
of r
fiyJ*"i,1[:::::Hr".ln*:::-"::t'ia-r..*itli.yff
the nexr higher one.rhe ;",gynucrearspinstate
";;;-;;;'ffiil"#"'E:H""J.Tffl#fil:Tlj:?r;,
The energv required for transitions-falts Figure 2.19: Energy levels of a nucleus with spin quantum number I
ffi-ir"Jr;teld' i., ,"aio frequency region (60
;,,rssible in a magnetic field, the spin orientations are *1,0, -1
in a magn"r
.|:?iffi
l,1
.;L!ix,' T:;T":,1"ffi f" H:* " T:lo
s ybatemi_c partic
When the nucleus is in a magnetic field, the initial populations of the energy levels
th" atoms
the atom"'(5u"i
(such * ;br ,r,"*
as
"clthese sni.o
""^ -^,:T:8-,"u.d T spinning on their
^, axis. In most rr,re determined by thermodynamics, as described by the Boltzmann distribution.
The
'oli'";;"#:T-d;,:.T"xilrrril",l["liffl';",;r]fi: krwer energy level will contain slightly more nuclei than the higher level. It is possible to
ll:."ffi1f#;J"ffiiJj: Hf::1::",1j1*: ,pTs (such as rr1 and 13c) the nucre
.fi1l""fr#:J11Jff,'ff .xcite these nuclei into the highei level with electromagnetic radiation. The frequency of
,1",,""'*::**sanovera,E;;-il;ffi 11]?IiH,T:l radiation needed is determined by the difierence in energy between the energy levels'

1' If mass number is even (mass

number is the sum of protons
(a) If both number
of protons and number of neutrons
and neutrons)
2.5.L The precession of nucleus in a magnetic field
neutrons separately pair-up are even. protons and consider the spinning of a top in gravitational field, the spinning axis get tilted by an
inside nucreus, then the nucreus
:0) such nuctei are not Nnan l"ti"" has no net spin (I angle 'g' and starts piecessing with a frequency. The potential energy of top decreases as
(b) If both number of protons "s. ii;j;
C,i;b prJcer"ing angle 'g' increases. In this discussion, we will be taking a "classical" view of the
and number of neutrons are odcl Lehavior of tn" nucleus i.e. the behavior of a nuclear magnet in a magnetic field. Imagine
will be even)' Protons ,r"rri.ors separatery pair-up insickr
(rrrruss number
a half integral spin in "'d r,r<:r.rrs Ieaving a hydrogen nucleus of spin +j in a magnetic field. This nucleus is in the lower energy
each kind
"1gitr."i", in*'".-,rirr. lrrr*rrr.r.d giving
ii-:t'i'e"')'
tevetli.e. its magneti" *o*"rrf a[gn with the applied fietd). When a nucleus is spinning
the
#ffl ;'iT :il};l)":T ""r'-"u"r,,i ar" NM,,,.'ti,i' "g on its axis in the presence of a magnetic field B, this axis of spin will precess around
magnetic field,jusi like the precisional motion of a spinning top in gravitational field' The
2. If mass number is odd f.equ"rrcy of precession is termed as Larmor frequency. When this frequency becomes
identical to the radio frequency) resonance occurs and flipping of proton takes place with