Unit-2

KASHO2
Specro scopy
Specho scopy is -he analuaes ot eleekromagnehic
radiation scatteued absobed or emitted b moleeules
Le us tHust discuss origin ot speeum.
tranation trom G1S to
Ee Chighey -Ee ES absorption
h devel b specumn
ESto
6S Eission
Specum
E Clouen
eneg level)
classfied in to two Cakegories
Spechra Can be roady
Atomic Spechra Moleaula Spechra
which auses rom h e
Arises trom h e rantions e
of an e blw atomic ene trautionu df an
blw mole culan ene
Uevels
evels, ae
only elechonic tranaitions
L atomic spechostopy,
invol ved
molecule Can charge net ondy
The eney bt also tecuwJe
as a Hesult ot eleconic tranitions
Can due to TotaHona! Vibraiona! eneg
Uevels.
EMR Spec um
lwavelength A°)

Since E-he
wave no Ccm)
 lotal ener ot molecules Centou otf
E F e t Evib tErot" +E rans
Yavity
Charge
Cexten ot qraily
elechonicc
ie ranaition ot does rut change Totation about
h e axis
e from GGS >Es by duing to tro
absorpthion of motlon o
moleule
Pho ton of sutable S o l r a n s - n e g B e c t

Feu EvihErot tronM

E=
FetEvib t Evot

ES
T122
4 VeHY
vety Shap
intensl speehal ikea
ane desied bu
broadening. ocC
GS

J-o
Summa Candition
YCnaihioo Rangt must have peHma
y Rotakionc blw rote Loocm nent di Pole moment
Or ucrowave uevels
Hu,nN HLO not
H,,0
IRspecho- vibeleveb 5o0-Mooo Pipole moment
2) Vib or
Cm
must Change dunur
Sco py
vibrouio
ConyugaHon or
33 Elechonic or eleehovc S, 000
UV - vis spechosoPy ene To,000Cm chrOmophore
Leve in moleCules

) Kaman ibrot "ene tax 2nea Pexiodic change

Uevels N IR, visile in olaisabilty
 UV-Vis Specho scopy
nboduchion i s also knouon a s elecho nic. specc
roScopy since tinvolves Jhe promotion of és from
round state to excted staBte
i c vey sthul to predickhe no. of
Cougated.
N double bonds and also in aomatic
Contoation
Kange in texma of A in teums of -
Hooo 8oooA°- vis So00- 1, Soo Cm Vis
oo o- 4000- uv S0,000-2S0oo cm-UVN
bebw 20oo - fau Uv
above Soooo fax UV
The fan OV-rtgion is not muoh studied due
to absorption by oxgen 2 rurogen.hat's w tor
his rCgion Vaceum indrumens ae TRuinld
Absorption La
Lambexts-Beer's lar
Lambext's La When a beam ot monochro matic ligkt
Passes rough a homogenous mediumhe atio ot
deertase in intensity wthhickneas is
Proportiona to direcH
interuity ot* incident radiation
det uick neas = L Cm
Tnitial Intensity ot Jugkt - lo
-X
a t absorption interuity at dJight= T
An
-dLdT Numeual
k Conatan
d
dL kdz dn - -ki
Lo

| I - Io e-kx| Q-k
303
Beeslaw when a beam at monochwomatide digt
IS
is PoLssed hough a homogenous medium Yate of
decease of intcaty wih cknes is directly propor-
tional to intensity ot incident radiation aa wl au
Concenalion ot Solution

-dL dIC C= Conc" ot solu

dac - acr
ateu olving I - I lo

tinally Lambext -Beers La i

I =o loEcx hen&- extigction
-£cx Capilan) Ceeff.

absorptivity
If cisingld E- absonptivity
Cisin mol|£ = molax
Uog Lo is Called Absorbance ahsorptivity

(A)
Lambexts Beers Laus
A £C
ie Absor bance reman Constant it Concen tration
and hickneas of absorption dayua ote changed in
Yvesee aio
i s called lranmuttance
A Ecx
A AbsorbanCe
Conc a t solution
TCTranamittane) =-
Cisin l d e is called
Pahlergth
=
absor ption coett ov,
absovpttvity molan extnction Co et
iFCisin molld EH is caled mola absorptivity.
 what happensif pah lengh is corutant
A path lengh is Conat A (Absor bance) shaas
Rneaxelatonship widh Con ot solution.
A EC

A compound hawina Conc l6sqld TCAuttd

absor bance value 20 a Amax 5lo nm uing ro Cm
CeLu Cal absorptivity and mela absosptivity value
C Nol wt ot CopoUnd -
Yoo)
Conc? of Comp lo
A = 20
1 oCmn
A =Ec E =
_A = Roo L9 Cm
CL
GUven Nol wt ot compovnd - 4ooo

Hola con" Ccin mallu)

4oo
EN= 20
8 xio'dmo Cm
(lo )I
when Uv ught is passed hrough a solu
Hadiand powe is duced to sol. Cal Absorbance
CA 201o
what ae he imitattons of Lambet Bev's lau
Honochwomattc utght should be wed
i) Solution should be di lute.
ii )lemperaHlane vauiaHon shauld not be
too lage
Absorption Naxima The value of uhen
absorption is maxi mum called max

Amax
4pes of eleconic lranaitions

. n- n-

4- C 0
4
C-C-c=C
C-C CC

Highe eneg states aue designatd as higheu enegy

meleulau
oy Bitals and also called anti bon dinq
orbtals The highly probable hanuitton due to
of
of guartided enexgyinvolves h e pronoion
absorption orbitals
from kigky ocupiedHalecula
to avai lable uNlled moleculau orbitala
tanaition He
Hig enegy PToceas bonds
since
ae Vey gong Suw tvanaition requires radiaion
veushert wave length Chigh eneg4) so
Veu
Ules in
in fa bvV region.
o Ccus % in satwated hydrocasbon
e mehane Propane ett.
ii
n-
having one
T occw in satuated Copound
heteuo aBom wh unshaed
of e. e pai
heteua-akomqt exeited in to *
aadibonding esbit
CH-0-H -NH
)T- OcCu in unsatattd Comp, aomatHc
Compoonds.
iv) - In i s unahaued pais of és ot
heteuoatom qets excited in to r* anibon ding
OYbitals
enegy Ovde
-*n-* 7 -* -*

e CH0-H Possible tranaitiona ane

Single bond unahaued
- *
Paà es
CH-- - Possible trauitions ane
Single bond
m-
-*
undaned paiu ot es
deuble bond x)
Find tanations in Ro, RCN RNO2RNH2
Conyugated diene
 ChYomaphovc Auxochrome
Chwomophores 0Le molecules or tunc' gröp
having T orditals h a show chaacteistic dbsorp-
Hon in UV vis rglon ie hey ane Colov develapinq
They axe of too typed:
which qroup Containa T es ahey undexgo7-*
transi fions eg eylene etc.
i)which contaln boh 7 n elecons 2 he
undege - 7* 2n-7* transition eg.

C=0 EN ele

Auxochrome An 9Toup wch does not itself acas

Cvomophove bu whese prtacnceittshe absorption
band h e ae Color enhaneing group e9-on,
NH ekc.
HpechrOmic
Absorption Intenaity Shifts Hupsochronic Bahechvomc
T t leads
i)Baahochromic shit:
Shift ot absorptt oo maximna
touwauds longey wave lengh Hpochromic
due to prtsence ot Conugakion
auxochrome. T is caled
Red shf+ A max VIBG yOR
i t Hypsochromit shift SWft of absorption maxinna
to wdds Shorte wave lengh due to elhe
Teova ot Conugakion Change in polaiJty
etc
) Hupex-chromic shift Intonuity of absorption
makima mcrtases ie Emax inortases

iv Hypo chromic Shitt nttnsity decreases.

aHe
(Q Adentity 9eomerical jsomexs Values otAmax
294 nm 214 nm

214 nm
294nm
max mov
(6 a) CH=*10H=CH-1-UH CHC-CH-CH=H-CH3

b) CHCoCH CHCHLeCHa
c) -Coouta
Ana CH=UH-CH=CM-CH-CH

Effeek ot Polay A
Non Pola Solvent on n-* tranaitions
Hemains Sqme
Maxima tor non- polax compounds
a) Absorption el as non pola solvents
in polaH as
is sited with
6) Absorptiom maxia tor Polax compoonda
in Polanity of solvents.
Change
i) n-*-Absorption band moves
increaainghe polauy
to shartex w avelength by longe Lwave lengh by
Absovption band moves to
i) TT* af soventhe dipole
incasing e polauty dowehe
exct
enegy ot exctt
eneg1
wh solvent
Intenactio
han h a of qround stat
qround state.
State moHe
 - not for IR uhy?
9Mehanol is g0od solveat tor Uv

absovbs n UV below 200 nm which is

A Mehanol
below iks range so it dbes not intutene.
YCspeahve is
s ome
Yspechive
s hue (A &B) to the
Assign heA
On h e
On
basic lollouwing
ot
Ov-data

shows peak at 222

nm
isome
a 216 nm
Somes shews peak

CAJ CB
lbehax
Hint
Fünt Geatt extent ot conugation, higheu
of M
9 In absorptton celu, Ihe hnsmittanie
an
& hat ot oiN Solution
Solukion of Subs tance X is 8o/
ot anothen Substance Y is 6o a givcn avelength .

at soluhiön havinq|Min
what is he trand tHtance
XLol in y .
Hin A- Ax tAy C48)
Applicatlon of. UVVis Speehroscopy

a DeteHon ot extent of Conugation.

b)
6) Dishnctlon in ConjuaaBed and "Non Conugaa
CopoUnds
cc) Tdenification atunknoan Compounds.
d Dettainakion unknown Concenkation & mol ut
ot Copounds.
e) ualitaive 4 uatitative analyais.
e.)
 OV-visible Spectvo scoPY
P1oblem
Willhe value of absosption change if pah lengh
ofbeam, of lght hroughh sanple is
doubled and
and Contentation is made hal.

A ec
A C E

C C
A
Az
A A

( Guye labeled ray diagram ot calonmetey

Wave Remainin
white ength
Tans
igAt mited

Sowtce Prism Single sple

Cuvett
ligk DetectoY
lave lengh
MonochyOmator
 Eechonic absorption band ane broad
A
Fe
having
Eq Totalton
Cs well as ubrahion
his eleebronic transitions le oLsociatea
wh yotational and vibraiona tranisitiOns
So broad peak in Uv- vis is qenenated.

( Effect of pola& non polan solvent on

T-R*K tranisitionn
Polan Solvent in R* hanution
due,to
Pola colvent intuatien
Ee ofexCittd stale
deerease3
T L
E as
E A
i s is Known as
okhochronic
Shft
Efee of of Polan Solven on n *
tromation (C=0)
e
Polan solvent interaeks
n
with non-bonding
e Qnd deertaile
E A ts
Oveal
ene
eNengy
incotates

ypsochondc S o
 Acetone absorb at 219 nm in hexane
CUF 264.S nm in Wato
A
CH non bonding es

due to hy drogen
bonding i n w a e

e s etengaged

Hypsochomic hift+
E
Artttne-absorb-at219HmiA-hexane

Lhee-es
230om
neutral medium a 3 0nm
in
Anline
In aeudic medium A max 03 nm
NH NH
A H

0 3 nm
8onm Nodone Not
PadH o e available PaiuofVailable
es ane avalable
toY ConugaHon
FuPsoCromic svft
'Cblue shift Amax
deereases