Anal

yti
calTechni
ques 6.
1

CHAPTER-
6
ANALYTI
CALTECHNI
QUES

6.
1INTRODUCTI
ON

ToRecapi
tul
atetheWavepar ameter
s
The el
ect
romagneti
cr adi
ati
on can be des
cri
bed i
na
numberofpr
operti
esofparameter
s.

Wavelength()
Iti
st hedist
ancebet
weent hetwoadjacentcr
est
s
(
C-C)ortroughs(T-T)i
napart
icul
arwave.
Iti
sdenotedby
t
helett
er (l am da) C  C
Unit
susedforwavel engthar e:
Angstr
om(A0)=10-10m =1 0-8cms
Micr
ometer(m)=10-6m
Nanometer(nm)=1 0-9m
T  T

Frequency( )
Fr
equency may be def ined as the numberof
waveswhi chcanpas sthr
oughapoi ntinones econd(i.
e.
numberofvi br
ati
onsi nunitti
me)ofanel ect
romagneti
c
radi
ation.
Frequency(
)=Vel oci
tyofli
ght/Wavel ength
=c/ 
Veloci
tyofl
ightc=31 010cm/sec
Wavelengthi ncm
6.
2 Engi
neer
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str
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I

Theuni
tforf
requencyi
scycl
espers
econdori
n(Hz)
.
Wavenumber( )
Thenumberofwavesperuni
tlengt
hi sknownaswave
numberandi
sexpr
ess
edasthereci
procalofwavel
engt
h.

Wavenumberisex pr
ess
edast cm-1)
hewavespercm ( .
Thi
suni
tisal
socal
l
edKays er(
K).

Thewavelength,thef
requencyandt
hewavenumber
arer
elat
edasfoll
ows:

= =

6.
2ELECTROMAGNETI
CRADI
ATI
ON

Electr
omagnet i
cradi
ati
onisatypeofenergythatis
transmittedthroughspaceatenormousveloci
ti
es.I
ttakes
manyf or ms,themos teasi
lyr
ecogni
zablebeingli
ghtand
radiantheat .Lessobviousmanif
estat
ionsincl
udeX- r
ay,
Ultravi
olet,microwaveandradi
oradi
ations
.

Theel
ect
romagnet
icr
adiati
onisfoundt
ohavedual
nat
ure-thepar
ti
cl
enatur
e(photons)andwavenat
ure.

Thepr i
ncipl
esandlawst hatgover ntheabsorpti
on
ofradiati
on applyt o al
lwavel engths for
m X- r
ay to
radi
ofr
equency.The abs orpt
ion meas ur
ementsi nvol
ve
thedeter
minat i
onofthereductioninpowers uff
eredbya
beam ofr adiati
on asitpas sest hrough an absorbi
ng
medium ofknowndi mensi
ons.
Anal
yti
calTechni
ques 6.
3

Tabl
e6.
1-Ther
egi
onsofel
ect
romagnet
ics
pect
rum

Type oft r
ansi
tion r esulti
ng Fr
equency Type Wavel
engt
fr
om ads or
pti
on Hz of h
spectr
omet r
y
Change of I nner 3x 1016 – X-r
ay 10nm –
electroni
c electron 3x1018 100pm
distr
ibuti
on Out er 3x 1014 – Visi
ble 1micr
om –
electron 3x1016 -UV 10nm
Change of Mol ecular 3x 1012 – I
R 100microm
conf i
gurat- vibrations 3x1014 –1microm
on
Change of Mol ecular 3x 1010 – Micro 1cm –
orientati
ons r otations 3x1012 wave 1microm
Change of Spi n 3x08 –
1 ESR 100cm –
spin orientations 3x1 010 1cm
Spin 3x06
1 – NMR 10m –
orientations 3x1 08 Radio 100cm
waves

Whenthemonochromat i
cr adiat i
onpassest
hrough
as amplecontaini
ng an absorbing s peci
es,theradi
ant
powerofa beam i sprogress
ivel y decreas
ed asmor e
energyisabsorbedbythepar ticlesoft hatspeci
es.The
decreasei
npowerisexpressedby

1)Lamber
t’
slaw
2)Beer
’sl
aw( Or
)Beer-Lamber
t’
slaw

Lamber
t’
slaw
Lambert’
slaw s t
ates that “when a beam of
monochr omatic r adiation i s pas s
ed t hrough a
homogeneousabs or bi
ngmedi um,ther at
eofdecr ease
of intensi
ty of t
he r adiati
on ‘dI’witht hickness of
absorbingmedium ‘ dx’isproporti
onaltotheint ens
ityof
theincidentr
adiat
ion‘ I
’”.
6.
4 Engi
neer
ingChemi
str
y-I
I

i
.
e, ……… (
1)
Oni
ntegr
atingtheequat
ion(
1),
bet
weent
hel
i
mit
sI=I
0at
x=0andI =Iatx=x ,
weget

……… (
2)

wher
e,k=abs
orpt
ioncoef
fi
ci
ent

i
.
e.,

Theaboveequat
ioni
sknownasLamber
t’
slaw.

Beer
’sl
aw(
or)Beer
-Lamber
t’
s’sl
aw

Whenthemonochr omati
cr adiat i
onpas sesthrough
as amplecont aini
ng an absorbing s peci
es ,ther adi
ant
powerofa beam i sprogressi
vel y decreased asmor e
energyisabsor bedbyt heparticlesoft hats peci
es .The
decreaseinpowerdependsupont heconcent r
ati
onoft he
absorberand thel ength ofthepat ht raversed byt he
beam. Therel
ationshi
pisexpressedbyBeer ’slaw.

LetI0b et her adiantpowerofabeam i nci

dentupona
sect
ionofs olut
iont hatcontainscmolesofanabsorbing
substanceperl it
er.LetIbet hepowerofthebeam afteri
t
has t r
aver sed x cent imeters of t
he sol
uti
on.As a
consequenc eofabs orpt
ion,Iwil
lbesmall
ert
hanI0.Beer’
s
l
awr elatesthes equant i
ti
esas
Anal
yti
calTechni
ques 6.
5

I
nt hi
sequat ioni
scall
edast hemolarabsorpti
vit
y.The
l
ogarit
hm ( tobase1 0)ofther ati
obetweent heincident
andthet ransmit
tedpoweri scall
edtheabsorbanceoft he
sol
uti
on.
The abs orbance increases di
rectl
y wi th t he
concentrati
on oft he absorbi
ng speci
esand t he pat h
l
engtht r
aversedbyt hebeam.

ThusBeer-Lambert’slaw s t
atest hat,“whenabeam of
monochromat i
cradiati
oni spas sedthroughas ol
utionof
anabsorbi
ngs ubstance,ther ateofdecr eas
eofintens i
ty
ofradi
ati
on‘ dI
’withthicknes soft heabs or
bingsolution
‘
dx’is proporti
onalt ot he i ntensit
y oft he i
nci dent
radi
ati
on‘I’aswellast heconcent rati
onoft hesolution
‘
C’.

I
tisex
pres
sedas

…… (
3)

wher
e,k=mol
arabs
orpt
ioncoef
fi
ci
ent
.

Onint
egrati
ngtheequat
ion(3)bet
weenl
i
mit
sI=I
0atx=
0andI =Iatx=x,weget ,
6.
6 Engi
neer
ingChemi
str
y-I
I

(
or)

(
or) …….
(4)
Wher
e, =mol
arabs
orpt
ivi
tycoef
fi
ci
ent

Equat
ion(
4)i
scal
l
edBeer
-Lamber
t’
slaw.

Thus,theabsorbance(A)isdir
ect
lypr
oport
ionalt
omol
ar
concentr
ati
on‘C’andthicknes
s(or
)pat
hlength(x)
.

Appl
i
cat
ionofBeer
-lamber
tsl
aw

Determinati
onofUnknownconcent rati
onofasol
uti
on
Beer–Lambert’sl
aw canbeus edtodet
ermi
nethe
unknownconcent r
ationofasolut
ion
As t
andards olut
ionofknownconcentr
ati
onCs i
s
fi
rstt
akenandi t
’sabs or
banceAsismeasur
ed.

Thenaccor
dingt
oBeer
-Lamber
t’
slaw

……….
(1)

LetCu be t
he unknown concent
rat
ion oft
he s
olut
ion
Anal
yti
calTechni
ques 6.
7

whichi
stobedeter
mined.
Theabsor
banceAuofthegi
vens
olut
ioni
smeas
ured.

Weknowt
hat

 …….
.
….(
2)

Fr
om equat
ion(
1)and(
2),
weget

 ……….
(3)

Wealreadyknow theconcent
rat
ion ofs
tandar
d
sol
uti
on Cs and t he absor
bance Au and As were
experi
mentall
y measur
ed and hence t he unknown
concentr
ati
onCucanbecalcul
atedf
rom t
heequati
on(3)
.

Li
mit
ati
onsofBeer
-Lamber
t’
slaw:

Thi
slawcanbeus edonlyfor
dil
utesolut
ion.
monochr omati
cradiat
ion.
thesys
t em maint
ainedatcons
tantt
emper
atur
e.

Sol
vedPr
obl
ems:

1)Thetr
ansmit
tanceofasolut
ionis30%.Deter
minet
he
absor
bance(
or)opti
cal
dens
ityofthesol
uti
on.

Soluti
on
Transmit
tanceT=0.
30
Abs or
banceis
6.
8 Engi
neer
ingChemi
str
y-I
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A=
=–log0.
30
= 0.
5229

Example2:Thesol
utionofconcentr
ati
onof2.
510-4M has
the per
centage absorpti
on of 25% in a 1 cm cel l
.
Deter
mine i)theabsorbance(
A)and i
i
)themol ar
absor
pti
oncoeff
ici
ent().

Solut
ion:
Given:%T=25%(or
)0.
25
-
4
C=2. 51
0 M; x=1

i
)Abs
orbance:

=–
log0.25
=0.6021

i
i
)Themol
arabs
orpt
ioncoef
fi
ci
ent

=0.
6021/2. 0-4
5x1
=2408 .

Example3:Theabs orbanceofas oluti

on1
.210-4 M.is
foundtobe0.23inapat hlengthof3.0cm.
Deter
mi nethe
molarabsor
ptionofthesol
ution.

Solut
ion:
Given:A=0.23;C=1
. 0-4;x=3.
21 0cm
Weknowt hat,
Mol
arabs
orpt
ivi
ty,
Anal
yti
calTechni
ques 6.
9

=
89dm3mol
= 638. -
1
cm-1.

Example4:As oluti
ons
howsat r
ans mit
tanceof20%when
taken i
n a cel lof 2.5 cm thickness.Cal cul
ateit’
s
concent
rati
oni fthemol
arabsor
pt i
onc oeff
ici
entis12,
000
3 -1 -1
dm molcm (AnnaUniv,Jan’2005)

Solut
ion:
Given: T = 20%( or
)0.20;x=2.5;
3 -1 -1
1
2,000dm molcm

Weknowt
hat
,

 =

= .

Example5:As ol
ut i
onofthi
cknes s2cm t ransmi
ts40%
i
ncidentli
ght
.Cal
culatet
heconcent rati
onofthesolut
ion
giventhat =6000dm3mol -
1
cm-1.
(
Annauni vJune2005)
Solut
ion
3 -
1 -
1
Given:T=40%=0. 40; =6000dm molcm .
x=2.0cm;
6.
10 Engi
neer
ingChemi
str
y-I
I

wehave,

= 3.
31 0–5mol
61 dm–3

Exampl e6:
A monochr omat i
cradiati
oni sincidentonas olut
ionof
0.06 M concent r
ati
on ofan abs orbi
ng s
ubs tance.The
i
nt ensi
tyoft heradi
ationisreducedt oone-fourthofthe
i
nitialval
ue afterpas si
ng t
hrough 8 cm l ength ofthe
soluti
on.Calcul
atethemol arextincti
onco-
ef f
ici
entofthe
subs ance.(
t AnnaUni vMay2004)

Sol
uti
on:
Gi
ven:C=0.
06M;x=8cm ,

Acc
ordi
ngt
oBeer
-Lamber
tlaw,

=1254dm3mol
. -1
cm-1
_
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__
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____

6.
3INTRODUCTI
ONTOSPECTROSCOPY

Al
l chemi
cal s
peci
es i
nter
act wi
th t
he
Anal
yti
calTechni
ques 6.
11

electr
omagnet i
cradiat
ionandi ndoingso,dimi
nis
ht he
i
nt ensi
tyort hepoweroft heradiantbeam.Absorpt
ion
spectroscopy i
sbas ed upon the measurementofthis
dec r
easei n power( orat tenuat
ion)oft he r
adiat
ion
broughtaboutbyt heanalyte.

Itis conveni entt o characterize abs orptiomet ri

c
met hods accor di
ng t o the t ype of el ectr
omagnet i
c
radiati
onempl oyed.Theyar eX- rays,Ultraviolet,Vi s
ible,
I
nfrared,mi crowaveandr adio-f
requencyr adiation.
A whi te sour ce ( el
ectromagnet icr adiation) i s
focused on t o a nar row s l
itand t hen made t o pas s
throught hes ampl e.Thel ightisabs orbedbyt hes ampl e
andt hisiss eparatedi ntoitsconstit
uentf r
equenci esbya
fi
lt
erandt hens enttot herecorder.Att hi
spoi ntitmaybe
helpfultocons iderwhathappenst otheener gyabs orbed
i
nt heabovepr oces s
.

A gi
vens amplecontinuestoabsor
bener gyand
showanabs orpt
ionspectrum asl
ongasweirradiateit
.i.
e.
af i
nit
enumberofmol ecul
esappeartobecapabl eof
absorbi
ng an infi
nit
e amount ofener gy.Pl ainl
yt he
moleculess
houldgetri
doft heabsor
bedenergy.

Apos s
ibl
emechani
smf ort
hisi
sbyther
malcol
lis
ion.
An energized mol
ecul
e col
l
ideswi t
hit
sneighborsand
graduall
yl osesit
sexcessenergy tothem aski neti
c
energy.Thes ampl
easwholebecomeswarm.

Anothermechani s
mi sthattheenergygainedf rom
radiati
onislostasradiat
iononcemor e.Amoleculeint he
grounds t
ateabs orbsenergyatfrequencyandi tsener gy
i
sr ais
edanamount E=hvabovet hegroundstate.Itis
thusi nanex ci
ted,unstabl
econdi t
ion,butbyemi tti
ng
radiati
onoff r
equencyvagai n,i
tcanr ever
ttothegr ound
state.
6.
12 Engi
neer
ingChemi
str
y-I
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Thespectr
um obt
ainedcoul
dbeeitherduetot
he
excessradi
ati
on whi
ch i
snotabs or
bed ordue t
othe
emitt
edradi
ati
on.

Thestudyofs
pect
ros
copycanbecar
ri
edoutunder
t
hef
oll
owingtwoheads:

At
omi
cSpect
ros
copy
Interacti
on ofel ectromagneticr adiati
on wi t
h at oms
whi char emos tcommonl yint heirlowes tener gys tate
(grounds t
ate)r esul
tinginelectronictransiti
onsi scalled
atomi cs pectroscopy.The s pectrum obt ained isa l ine
spectrum.
Mol ecularspectroscopy
I
nteracti
on of el ectr
omagnet i
c r adiati
on wi th
mol ecules iscal l
ed Mol ecul
ars pect
roscopy.Thi smay
resultintransi
t i
onsbet weenr ot
ational,vi
brationalener gy
l
evel sandel ectronictransi
ti
ons.Thes pectrum obt ai
nedi s
acompl i
cateds pectrum.

Di
ff
er encesbet weenAt omi candMol eculars pectr
a
At omi cspectra Mol eculars pect r
a
1 Iti spr oduced due Iti s obt ained f rom t he
to i nteraction of int eracti
on of mol ecul
es
atoms wit
h wi th electromagnet i
c
electromagnet i
c radiation.
radiation
2 At omics pect r
aare Mol ecular s pect r
a ar e
Lines pectra. compl icateds pectra.
3 Iti sobt ained due It i s pr oduced due t o
to electr
onic vibrational,r otationaland
trans i
ti
on i n an el ectronict ransiti
on i n a
element mol ecule.
Anal
yti
calTechni
ques 6.
13

Abs
orpt
ions
pect
ros
copy
Ifelect
romagnet icr
adiati
onsofcertainwavelengt h
rangearepas s
edt hroughthes ubs
tanceunderanal ysis
,
radi
ati
onsofcer tainwavelengthsar eabs or
bed byt he
subst
ance.The s tudy ofthisiscal l
ed the abs
or ption
spect
roscopy.The wavel ength abs or
bed characterizes
somes pecifi
cf uncti
onalgroupoft hecompoundort he
compoundi tsel
f.
Hi
gherener
gy
l
evel

h

Gr
ounds
tat
e
Abs
orpt
ion

Hi
gherener
gy

h

Gr
ound

Emi
ssi
on

Emi ss
ionspect roscopy
Ifelectromagnet i
cr adiation ispas sed through a
substanceort hermalener gyi sgivent ot hes ubst
ance
underanal ysis,theenergyi sabs or
bedbyt heat om.The
electr
onsint hegr ounds t
ategetex ci
tedtohi gherenergy
met astabl
es tates.Theseex cit
edel ectronsar eshortl
ived.
Sot heyemi tener gyt oret urnt ot hes tablestate.The
study oft hisi scalled t
he emi ssi
on s pectros
copy.The
6.
14 Engi
neer
ingChemi
str
y-I
I

s
pect
rum obt
ainedi
scal
l
edt
heemi
ssi
ons
pect
rum.

Fl
uor escence
The electr
on i
nt he exci
ted levelretur
nt oi t’
s
grounds tateeit
herdir
ectl
yorins t
epswi t
ht heemi s
sion
ofcertainamountofenergy.Whent hi
semi s
sionofli
ghtis
i
ns t
antaneoust hephenomenonisknownasf l
uores
cence

Phosphorescence
Whent heelect
ronintheex ci
tedlevelret
urnt
oit’
s
grounds tat
ewi t
ht heemissi
onofl ightaftersometime
l
ag, i
tisknownasphos phorescence

Photochemicalreacti
on
Whent heabsorbedenergyi
sstoredbytheat om or
moleculeandus edinpr oduci
ngsomechemi calreact
ion,
theresult
ingchemi calreacti
oniscall
edphot ochemical
react
ion.

6.
4CALORI
METRY

I
ntr
oduction
Color
imetr
yi sconcerned wit
ht he vi
si
bler egi
on
(
400-750nm)oft hes pect
rum.Thei nst
rument,usedf or
measuri
ng absorpt
ion ofradiantenergy i
nt he visi
ble
r
egionfr
om thesubstancesi
scolor
imeter.

Preparati
onofthecolouredsolut
ion:
Alt
hough s ome des i
red const
it
uents are self
coloured,i
tisus
uallyneces
sarytodevel
opacolourbythe
additi
onofoneormor ecol
ourfor
mingreagents
.Chemical
met hodsus edt
opr eparesui
tabl
ecolouredsol
uti
onsare
usuallycal
ledchromogenicreact
ions
.Thecolourfor
ming
Anal
yti
calTechni
ques 6.
15

r
eagent
sar
eknownaschr
omogeni
creagent
s.

Exampl
e:Thecomplexi
ngagentammonium hydr
oxi
deis
addedto getbl
uecol
oureds
olut
ionandtoesti
matethe
cupr
ousi
ons

I
nst
rument
ati
onf
orcol
ori
met
ry

Pri
nciple
Colori
met r
yi sconcernedwi tht
hedet erminat i
onof
theconcent rat
ionofas ubstancebymeas urementoft he
rel
ati
ve abs orpti
on ofl i
ghti nthe visi
bler egion wi t
h
res
pectt o a known concent rat
ion ofs ubstance.The
i
ntensit
yoft hecolourcanbeeas i
lymeas uredbyus inga
photoelectr
iccolori
met er
,from whichtheconcent rati
onof
col
oureds oluti
oncanbeobt ai
nedbyBeer– Lamber t
slaw.

Curr
ent Li
ghtt
rans
mit
ted  (
1/Concent
rat
ion of
sol
uti
on)

Wor
king
I
nac olor
imet er,abeam ofl i
ghtisdirectedt hr
ough
at r
ans parentcellcont ai
ningas olut
ionoft hecompound
being anal ysed.The compound abs orbs l ight at a
parti
cular wavel engt h. The unabs orbed r adi
ation
(tr
ansmi t
tedlight)ispas sedt hrought hedet ectorwher e
thelights i
gnalsar econver tedint otheelect ri
cals i
gnals
whichar erecorded. Theout putgr aphobtainedi sapl otof
theabs orbanceoft hel i
ghtversusconcent ration.

A=l
og(
I0/
I)

Theamountofli
ghttr
ansmit
teddependsont
hedept
hof
col
ouroft
hetes
tsolut
ion.
6.
16 Engi
neer
ingChemi
str
y-I
I

Components
Radiat
ionsources
Tungsten–fil
amentlamp
Functi
on:
Provi
desthewavelengthr
angeoft
hevi
si
bler
egi
on
(400-
750nm) .

Samplechamber
Cuvetmadeoffus
edgl
ass
Funct
ion:
At r
anspar
entcel
lmadeoff
usedgl
asshol
dst
he
tes
tsample

Sl
i
ts-Funct
ion:

Ent
rances
li
ts:I
tpr
ovi
deanar
rows
our
ceoft
hel
i
ght
.

Exi
tsl
i
t: I
ts el
ect
s a narr
ow band of dis
per
sed
s
pectr
um ands
endsitt
othedet
ect
or.

Fi
l
ter
Monochromator
Funct
ion:
All
owstheli
ghtoftherequi
redwavel
engthtopass
thr
ough,butabsor
bstheli
ghtofot
herwavel
engths
.

Detect or
Photosensi
ti
ve devices are used t o detectthe
radiati
ons .
Funct i
on:
Convertsther adiat
ion si
gnalsreceived fr
om the
sampleintotheelectr
icals
ignals
.
Thes edet ectorsarecapableofpr oducingcurrent,whi
ch
i
sdi rect l
ypr oport
ionaltot heintensi
tyoft her adi
ati
on
received. Thustheradiantenergytransmit
tedthroughthe
Anal
yti
calTechni
ques 6.
17

s
ampl
eismeas
ured.

Recor
der
Digi
tal
dis
play
Funct
ion:
Itdi
spl
aystheamountofr
adi
ati
onabs
orbedbyt
he
sample

COLORI
METRY-I
nst
rument
ati
onBl
ockdi
agr
am

LI
GHT FI
LTER SAMPLE
SOURCE DETECTOR
CELL

AMPLI
FIER

RECORDER

MATERI
ALSUSEDI
NCOLORI
METRY

LI
GHTSOURCE FI
LTER SAMPLECELL
Tungst
en Monochr
omat
o Cuvetmadeof
fi
l
ament r fusedgl
ass
lamp

DETECTOR
Photomult
ipl
i
er
t
ube

AMPLI
FIER

RECORDER
Digi
tal
dis
play
6.
18 Engi
neer
ingChemi
str
y-I
I

FUNCTI
ONSOFTHEPARTSUSEDI
NCOLORI
METRY

LIGHTSOURCE FILTER SAMPLECELL

Providest
he Selectst
he Samplei
skept
sourceof requir
ed i
nthi
s
radi
at i
on wavelength

DETECTOR
Conver t
st hel
i
ght
si
gnal
si nto
el
ectr
icalsignal
s

AMPLI
FIER

RECORDER
Dis
playst
her
esul
t

Es
timat
ionofConcent
rat
ionofas
olut
ion
Col
ori
metrytechni
quemaybeus edt
odet ermi
ne
t
he concent
rat
ion ofa s ubs
tance f
rom t
he colour
ed
s
olut
ion.

Es
timat
ionofcoppers
ulphat
e
A s eri
es of known concent rati
on of s t
andar d
coppersulphates ol
uti
onsareprepared.Tothes edefinit
e
vol
umeofNH4OH i sadded.Thesear ethebluecol oured
sol
uti
ons.Thecol ori
meteri
ssetatzer oabsorbanceus i
ng
ablanks olut
ion,withaproperfil
ter
.Now abs orbanceof
eachstandards olut
ionismeasuredus i
ngthes amef il
ter.
Anal
yti
calTechni
ques 6.
19

Agraphisplott
edbetweenabsorbancevsconcent
rati
on.
Thi
splotiscal
l
edcali
brat
ioncur
veandwi l
lbethestr
aight
l
ine pass
ing t
hrough or
igi
n.Thi
si saccor
ding t
o Beer-
Lambert’
slaw.

Abs
orbance,A =Cx

Since,t hepat hlengt h(x)isfixed fora givencell

,the
abs orbance( A)isdirectl
ypr oporti
onalt oconcentr
ati
on
(C).Similar
ly,tothetes ts
olut
ions ameamountofNH4OH
i
s added and t he absorbance of t he tests ol
uti
on
(unknowncoppers ulphate)i
smeas uredusingthes ame
colori
met er.From thecali
brati
oncur ve,t
heconcent r
ati
on
of t he unknown copper s ulphate s ol
uti
on can be
evaluated.

Absor
banceof
Unknownsol
uti
on


Absor
ban 
 Concent
rat
ionof
ce
unknown

Concent
rat
ion

Cal
i
brat
ioncur
ve
Es
timat
ionofFe3+(
fer
ri
c)i
ron

Fe3+i
sacol
ourl
esssol
uti
on.Sot
otheferr
ics
oluti
on,
KCNS(or
)NH4CNSisaddedtogiveabloodredcolour
ed
compl
ex.

Fe3+ +6NH4CNS [ Fe(

CNS) 3-
6] +6NH4+
(
Bloodr
edcolour
edcomplex)
6.
20 Engi
neer
ingChemi
str
y-I
I

A s er
ies ofs tandards olution oft hi
o cyanat e
3+
compl exofFe ( ferricammoni um sul phat e)areprepar ed.
Thecol ori
met eri ss etatzer oabs orbanceus i
ngabl ank
solution,wi t
h a pr operf i
lt
er.Now abs or banceofeach
standar ds oluti
on i smeas ured using t hes amef i
l
ter.A
straightl i
ne cal ibration curve is obt ained by plotting
bet weenabs orbancevsconcent rat i
on.Thi sisaccording
toBeer -
Lamber t’
slaw.

Abs orbance,A =Cx

Since,thepat hlength(x)i sfi
xedf oragi vencell
,
the abs orbance ( A) i s di rect
ly pr oporti
onal to
concentration(C) .Simil
arl
y,tot heFe3+ t
es tsoluti
on,t
he
same amount of t hi
o cyanat e is added and t he
absorbanceoft het estsoluti
on ismeas ur ed usi
ng t
he
same col ori
meter . From t he cal i
brat
ion cur ve, t
he
3+
concentration of t he unknown Fe s ol uti
on can be
evaluated.

Abs
orbanceof
Unknownsol
uti
on


Absor
ban 
 Concent
rat
ionof
ce
unknown

Concent
rat
ion

Cal
i
brat
ioncur
ve
Appl
i
cationsofcolori
metr
y
 Todet erminethemolarcomposit
ionsofcomplexes.
 Tomeas urethedissoci
ati
oncons t
antsofanaci d-
baseindi
cator.
 Tomeas ur
et hemolecul
arweightofacompound.
 Todet erminethei
nstabi
li
tyconst
ant sofcompl
exes.
Anal
yti
calTechni
ques 6.
21

 Todeter
minethes
truct
ureofi
nor
gani
ccompounds
andcomplex
es.

6.
5ULTRAVI
OLETSPECTROSCOPY

I
ntroduct i
on
UVcons ist
sofbr oadabs orpt i
onbandswhi chhave
greater ut i
li
ty f or quant i
tat i
ve anal ys i
s. When
polychromati
cUVandVi si
bleradi ati
oni spas sedthrough
a medi um cont ai
ning par t
icl
es ,t hey int
eractwi t
ht he
speciesandel ectr
oni ctransi
ti
onsoccurbyt heex ci
tati
on
ofelectronsf
rom thegr ounds tatet ot heexcitedstate.UV
and visibleradiati
on have s ufficientener gy to ensure
tr
ans i
ti
onsoft heout ermostorbondi ngelectronsonly.

Si
ngl
etset
: Onexci
tat
iont
hes pi
nsoftheelect
ronsinthe
mol
ecul
arorbi
tal
sarepair
ed.
Tr
ipl
ets
et: Onexci
tati
onthes pi
nsofel ectr
onsint he
mol
ecul
arorbi
tal
isunpai
redorant ipar
all
el

Accordingt omol ecularorbit

altheor
y,theinter
actionof
atomicor bit
alsleadst othef ormat
ion ofbonding and
anti
bondi ngmolecul arorbi
tal
s.Theymaybeclassif
iedas
Sigma( ): Theel ectr
ondens it
yisconcentrat
edal ong
theinternucl
earax i
s.

Pi
()t
ype: Theelect
rondensi
tyi
sconcentr
atedabove
andbelowthei
nter
nucl
earaxi
s.

Chr
omophor
es: Thepartofthemolecul
ehavi
ngnor
el
ectr
ons whi ch is ess
ent
ial
l
y f
or
absor
pti
on,.
Ex
ampl
e C=C,C=O,N=N
6.
22 Engi
neer
ingChemi
str
y-I
I

Auxochr
omes: Pol
ar gr
oups havi
ng l
one pai
r of
el
ectr
ons.
Exampl
e –
OH,
OR,
-NH2,
-SHet
c

I
nst
rument
ati
onf
orUVandVi
si
bles
pect
ros
copy

Principl
e
When UV- Vi
sibl
er adiati
ons( wavelengthr ange–
200- 800nm)ar e abs or
bed by at om /mol ecul
es ,the
transiti
on ofval ence electrons from lowerel ectroni
c
ener gyleveltohigherelectr
oni cenergyleveloccurs.The
amountofener gyr equi
redf ort hetrans
iti
ondependson
thedi ff
erenceinenergylevelsofgr oundstateandex cit
ed
state.

E1–E0=h.

Whenex ci
tati
onoccurs,anelect
ronfrom oneofthefil
led
*
,ornmol ecularor
bit
alsgetexci
tedtothevacant or
*
 (anti
bonding)mol ecul
ar orbi
tal
s.Cor r
esponding to
poss
ibl
eexc i
tat
ions,t
herearevari
ousabsorpti
ons.

 *  * n *
 *  * n *

elect
ronsrequi
rehigherenergyforexcit
ati
onto*or*
thanthe exci
tat
ionofelectr
onswhi chinturni
sgreat
er
thannelect
rons.
Theorderofdecreas
ingenergyforthetransi
ti
oni
s

* >* =* >n* =* >n *

Worki
ng

I
naUV-
Vis
ibl
espect
romet
er,abeam ofl
i
ghti
sspl
i
t
Anal
yti
calTechni
ques 6.
23

i
ntot wohalves.Onehal fofthebeam ( thes amplebeam)
i
sdi r
ectedthr
oughat rans par
entcel lcontaini
ngas olution
oft he compound bei ng anal ys ed and one- half( the
refer
encebeam)i sdi r
ect edthroughani denti
calcellt
hat
containsthesolventorbl anks oluti
on.Thei nt
ensit
iesof
the two beamsateach wavel ength oft he region is
compar ed.I
fthecompoundabs orbslightatapar ti
cular
wavelength,t
heni nt
ens ityofthes amplebeam wi ll
bel ess
thanthatofthereferencebeam.

Themot orlightatt
enuat ordrivesanopt icaledge
i
ntot herefer
encebeam unt ilt
hedet ec t
orr ecei
vesli
ghtof
equali nt
ensit
yf rom sampl e and reference beam.The
detectorconvertsUVr adi
ationi ntoelectri
calsignalsand
sendsittorecorder.Theoutputgr aphobt ainedisapl otof
the wavel ength of t he ent i
re r egion ver sus t he
absorbanceoft heli
ghtateachwavel engt h.

A=

Thegr
aphobt
ainedi
scal
l
edasabs
orpt
ions
pect
rum

Components:
The moder n ult
ravi
olet-
visi
ble spect
romet
ers
consi
stofl i
ghts our
ce,sampl e chamber
,Mot orli
ght
att
enuator
,fil
ter
,detect
or,ampl i
fi
erand the r
ecor
ding
devi
ces.

Sourceofl
ight:
 >375nm : TungstenFil
amentlamp
 <375nm : Hydrogendischargel
amp
Deuteri
um dischar
gelamp
Xenondischargelamp
Mercuryarc
6.
24 Engi
neer
ingChemi
str
y-I
I

Funct
ion
Providesthewavelengt
hr egi
oncorrespondi
ngto
UVr adiat
ion.
Tungs t
enf i
lamentl
ampi sparti
cul
arl
yr i
chinred
radi
at i
ons,

Samplechamber(sampl ecel
landrefer
encecell
)
 Si
li
cacel
lofpathlength1cm
Funct
ion
Usedtoholdt hes ampleandr efer
ences oluti
ons
.
Si
li
cacel
l
saret ranspar
entthroughoutt
her egion

Chopper
 Cir
culardiscwi t
halternatequadrantsremoved.
Funct
ion
Rotatesandt ransmitssampleandr eferencebeam
al
ternativel
yt ograti
ng
Fi
lt
ers:
 Monochr omat ors-Itconsist
sofanent rancesli
t,a
di
sper s
ingelement( pri
sm orgrati
ng)andanex it
sl
it
.
 Grati
ngmadeofquar tz(OR)fuseds i
l
ica,
Funct
ion
Sendsindividualrequir
edf r
equenciestodetector

Det
ect
ors:
 Barr
ierlayercel
l
 Photomultipl
i
ertube
 Photocell

Funct
ion
The detect
orconver
tst he radi
ati
on si
gnal
sinto
curr
ent.Thecurr
entisdirect
lypropor
ti
onaltothe
concent
rati
onofthesol
ution.
Anal
yti
calTechni
ques 6.
25

Motorli
ghtattenuator
Funct
ion
Dri
vesanopt i
caledgei nt
ot heref
erencebeam
unti
lthedet ect
orreceivesl
ightofequalint
ensi
ty
from s
ampl eandrefer
encebeam.

Ampli
fierandRecor di
ngsystem
 Pen/digit
alrecor
der
Funct
ion
Theout putgraphwhichisaplotofthewavelength
oftheent i
reregi
onversustheabsorbanceofthe
li
ghtateachwavel engthisobt
ained.

ULTRAVI
OLETSPECTROSCOPY:

I
nst
rument
ati
onBl
ockdi
agr
am

LI
GHT CHOPPER
SOURCE

REFERENCE
FI
LTER

DETECTOR

MOTORLIGHT AMPLI
FIER
ATTENUATOR

RECORDER
6.
26 Engi
neer
ingChemi
str
y-I
I

Appl
i
cat
ionsofUVSpect
ros
copy
Ultr
aviol
etspectroscopyhasbeenmai nl
yappl i
ed
forthedet ecti
onoffunct i
onalgroups(chr
omophore)
,the
extent of conj ugat i
on, det ecti
on of pol ynucl
ear
compounds by compar i
son et c. Some impor t
ant
applicat
ionsofUVs pectroscopyareasfoll
ows:

1
. Detecti
onoffunct
ionalgroups:
Thi
st echni
queisappli
edt odetectt
hepres
enceor
absenceoft hechromophore.Theopt i
onsofabandata
part
icularwavel engt
hmayber egar
dedasanevi dence
fort
heabs enceofapar t
icul
argroupinthecompound.

2. Extentofconj
ugat
ion:
The extentofconjugat
ion i
n pol
yenes can be
es
timated.

3. Di st
inction in conj
ugated and non-conj
ugated
compounds:
I
talsodi st
inguishesbet
weenaconjugatedandanon-
conjugated compound.The f ol
l
owing is
omers can be
readil
y disti
nguished si
nce one i
sconjugat
ed and the
otherisnot.

Theforbi
ddenn* bandf ort
hecarbonylgroupin
the conj
ugated compound wi
l
lappearatlongerwave
l
engt h compared to that f
or t
he non conjugated
compound.

The alkyls ubst

it
ution in an alkene caus
es a
bathochromics hi
ft
.Thet echniqueisnotmuchus ef
ulf
or
theidenti
fi
cati
onofi ndi
vidualalkenes
.

4. I
dent
if
icat
ionofanunknowncompound
An unknown compound can be i
dent
if
ied by
Anal
yti
calTechni
ques 6.
27

compar i
ngit’
ss pectr
um withtheknowns pect
ra.I
fthe
two s pect
ra coinci
de,the two compounds must be
i
dentical.I
fthe two spectr
a do notcoi
nci
de,then t
he
expectedstr
uctureisdi
ff
erentf
rom t
heknowncompound.

5. Exami nationofPolynuclearhydr ocarbons

Benzene and pol ynuclear hydr ocarbons have
characteri
sti
cs pectraintheul t
ra-violetandvi si
bleregi
on.
Thust hei dentif
icati
onoft hepol ynuclearhydr ocarbons
canbemadebycompar isonwi tht hes pectraofknown
polynuclearcompounds .Thepr esenceofs ubs t
it
uentson
the ri
ng,gener all
y,s hi
ft
st he abs orpti
on max imum t o
l
ongerwavel ength.

6. Det ectionofi mpuriti

es:
UV absorpt i
on s pect
roscopy is us
ed fordet ecti
ng
i
mpuri
ti
esinor ganiccompounds ,because
i
) Bandsduet oimpur i
ti
esareveryintens
e.
i
i) Saturated compounds have l i
ttl
e absorpti
on
bandanduns aturat
edcompoundshaves t
rong
absor pt
ionband.

7. El
uci
dat
ionoft
hes
truct
ureofVi
tami
nsAandK.

8. Identif
icationofacompoundi ndifferents olvents:
Somet i
mes ,thest
r uct
ureoft hecompoundchanges
wit
ht hechangei nt hesolventwhi chcoul
dbei dentifi
ed
9. Quant i
tativeanal ysis
Determinat ionofs ubstances:
UV abs orpt i
on s pectroscopy is us ed f or t he
quantitati
vedet ermi nat
ionofcompounds ,whi chabs orbs
UV.
Fir
st,absor bance( opti
caldensit
ies)oft hedif f
erent
sol
uti
onsofknownconcent r
at i
onaremeas ur ed. Beer ’
s
l
awi sus edforthisdet er
mi nation.
6.
28 Engi
neer
ingChemi
str
y-I
I

where,
=molarextinct
ioncoeffi
cient
C=c oncent
ration
x=lengthofthecell
Then the graph i s plott
ed between absorbance vs
concentr
ati
on.Thuswegett hecali
brat
ioncurveinthe
for
m ofas tr
aightli
ne.From t hegr
aph,theconcent
rat
ion
ofunknowns ubstanceisfoundout.

1
0. Det
ermi
nat
ionofmol
ecul
arwei
ght

1
1. Determinati
onofcal cium i
nbloodser
um
Calci
um i n the bl ood can be det er
mined by
converti
ngt he‘Ca’pr esenti n1mloft hes erum asi
t’
s
oxalateandr edissol
vingitinH2SO4 andt r
eatingitwi
th
dil
ute cerics ul
phates olution.The absorpti
on ofthe
sol
ut i
onismeas uredat31 5nm.Thust heamountofCai n
thebloods er
um canbedet ermined.

12. Det ermi nati

on ofconf i
gurati
ons ofGeometrical
I
s omers:
The resul
tsofabs orpti
on show thatci
s-al
kenes
absorb atdi f
fer
entwave- l
engthsascompar ed totheir
corres
pondingt r
ans-i
somers.

6.
6INFRAREDSPECTROSCOPY

I
ntroduct
ion
Theat omsi namol eculedonotr emaininfixed
rel
ati
vepos i
ti
onsbutvi br
ateabouts omemeanpos i
ti
on.
Thisfactisus ed inthe IRs pect
roscopy.The inf
rared
regi
onint heelect
romagneticspectr
um ex tendsf
rom the
Anal
yti
calTechni
ques 6.
29

redendofthevisi
blespectrum tothemicrowaveregi
on.
Theregi
onincl
udesradiat
ionatwavelengthsbetween0.7
and500—m or ,i
nwavenumber s
,bet
ween1 4000and20
cm-1.
Thespect
ralr
egionisspli
tint
othreer
egions

NearIR( 12,500-4000cm-1)
The abs or
pt i
on bands r esulti
ng f rom har moni c
overt
onesoff undament albandsandcombi nationbands
arepres ent.Thisr
egi onisusedf orquant itat
ivewor k.
-
1
MidIR( 4000- 650cm )
Manyus ef
ulcor r
elat
ionscoul dbeobt ainedf rom
thi
sregi on.Thi sregioni sdividedi ntotwor egions-t he
-1
groupf requencyr egion4000- 1
300cm andf ingerpr int
regi
oni n1 300-650cm-1.
I
n t he group f requency r egi
on t he pr i
ncipal
absorption bandsmay be as si
gned t o vi bration uni t
s
consi
stingofonl yt woat omsofamol eculei .e.touni t
s
whichar emor eorlessdependentont hef unct i
onal group.

Inthe fingerprintregi
on arethe singl
e bond
str
et ching frequencies and bending vibrati
ons of
polyat omicsys tems which i
nvol
ve moti
ons ofbands
l
inking a s ubstituentgroup t
ot he r
emainderoft he
mol ecule.

FarIR(667-0cm-1)
1
Cor
rel
atesthebendi
ngvibrati
onsofC,N,OandF
with atoms ofheaviermas s
.Thi sis wel
ls ui
ted f
or
st
udyingorganometal
li
candinorgani
ccompoundswhos e
atomsar eheavyand whos ebondsar eincl
ined t
obe
weak.

NumberofFundamentalvibrati
ons
Consi
der a molecule contai
ning N- at
oms .The
posi
ti
onofeachat om i
sr ef
erredtobys pecif
yingthr
ee
coor
dinat
es(thex,y,andz- coordi
nates
).Thust het
otal
6.
30 Engi
neer
ingChemi
str
y-I
I

numberofcoor dinat evaluesis3N.Thust hemol ecul

ehas
3Ndegr eesoff reedom.
Themol eculeisf reetomovei nt hreedimens i
onal
space wi thout change of s hape.i .
e.t here can be
tr
anslati
onalmovementwhi ch uses t hree degrees of
fr
eedom.
Als
ot he mol ecule can pos sesst he rotati
onal
movement .The r otat
ionalmovement of non l i
near
molecule usest hree degr eesoff reedom wher east he
l
inearmol eculeus esonlyt wodegr eesoff reedom asthere
i
snor otationint hebondax is.
Thusthenumberoff undament al
vibrationsfor
Nonl inearmol eculeis3N- 6
Linearmol eculeis3N- 5
I
nst
rument
ati
onf
orI
nfr
areds
pect
ros
copy

Principle
The IRs pectra are given bydi atomi cmol ecules
with per manent di pole moment s,i.e. het er
onuclear
atomi cmol ecul
esand pol yat omicmol ecul es. WhenI R
radiations ( wavelength range – 14000 – 20cm-1) ar e
abs orbed by at om /mol ecul es
,t he atoms /mol ecules
vibrateandunder got r
ans i
ti
onbet weenvi brati
onallevels.
Thet ransit
ionsint hevi br
ationalener gyl evelsareal so
accompani edbyt ransi
tionsint herotati
onal energylevels.
(SoI Ri salsocalledasRot ational–Vi brationalspectra).
Thes er esul
tsintheabs orpti
onbandst hati scharact
eristi
c
tot heat oms/mol ecules.

Thedi
ff
erentvi
brat
ionsar
e

Str
etchi
ngvi
brati
on
Thedi
stancebetweent
woat
omschanges
,butt
he
bondanglei
snotalt
ered.

Symmet
ri
cst
ret
chi
ng
Anal
yti
calTechni
ques 6.
31

Eit
her t he movement of atoms occur
s
towards one anotheroraway from one
another
Asymmet r
icstret
chi
ng
One at om approaches t
he cent
ralatom
whil
e
theotherdepart
sfrom i
t.

Bendingvibr
ati
ons
Thebondangl
echangesandt
hebonddi
stancedo
notchange.

Sci
ssor
ing(
in–pl
anebendi
ng) -
Movementofat
omsist
owar
dseachot
her

Rocki
ng(i
n–planebendi
ng) -
Movementofat
omsisins
amedi
rect
ion

Waggi
ng( outofplanebendi
ng)
+ +
Atomsmoveupanddownt hepl
anewi
th
respecttothecentr
alatom

Twi
sti
ng(outofpl
anebendi
ng)
.
- +
Oneoftheatomsmoveupandothermoves
downthepl
anewithr
espectt
ocent
ral
atom

Wor ki
ng
InaI
Rspectrometer,abeam ofli
ghtisspli
tintotwo
halves.One hal
foft he beam ( the sample beam)i s
dir
ec t
ed thr
ough a t ransparent cell contai
ning the
compound being anal
ys ed and one-
half( t
her efer
ence
6.
32 Engi
neer
ingChemi
str
y-I
I

beam)i sdirectedt hroughani denticalcel lthatcont ains

thes olventorbl ank.Thei ntens i
ti
esoft het wobeamsat
each wavel engt h oft he r egion is compar ed.As t he
compoundabs orbslightatapar t
icularwavel ength,then
i
nt ensi
tyoft hes ampl ebeam wi l
lbel esst hanthatoft he
reference beam.The mot orl i
ghtat tenuat ordrivesan
opt i
caledgei ntot her eferencebeam unt i
lthedet ector
receives light of equal i ntensit
y f rom s ample and
referencebeam.Thedet ectorconver tsIRr adi
ationi nto
electri
cals i
gnal sand s endsi tt or ecor der.The out put
graphobt ainedi sapl otoft hewavel engthoft heent i
re
region ver sus t he abs orbance of t he l i
ght at each
wavel ength.
A=l og( I
0/I
)
Thegr aphobt ainediscal l
edasabs or pt i
ons pectr
um

Components:
Themoder
nIRspectr
ometersconsi
stofl
ights
ource,
sampl
echamber,Motorli
ghtattenuator
,fi
lt
er,detect
or,
ampli
fi
erandt
herecor
dingdevi
ces.
Anal
yti
calTechni
ques 6.
33
6.
34 Engi
neer
ingChemi
str
y-I
I

Sourceofl
i
ght:
 NearIR -Tungst
enf i
l
ament
 MidIR -Nernstfi
l
ament
–madeofrareearthoxi
des
-Globarfi
l
ament
–madeofcarborundum
 FarI
R -Highpres
suremer
curyarclamp

Functi
on
Provi
dest
hewavel
engt
hregi
oncor
res
pondi
ngt
oIR
radi
ati
on.

Opti
calsys
tems
 Itis made of mi ner
al s al
ts(NaCl and KBr)
tr
ansparentt
oIRradi
ati
ons
Funct
ion
Thebeam isgui
dedandf ocusedbymir
rorss
il
ver
ed
onthei
rsurf
aces.

Sampl
echamber( samplecell
andr efer
encecell
)
 ForLiquids ample
-Rocks altcel
l(NaClcell
,KBrcell
)
 ForGass ampl e
-Cellwithlargerpat
hl ength(NaClorKBrcel
l)
 ForSolidsampl e-
Pel
lettechnique-KBr+Sampl e,
madei ntopast
e
Mulltechnique- Nuj ol+Sampl e,madei nt
o
paste.

Funct
ion
Usedt
ohol
dthes
ampl
eandr
efer
encemat
eri
als
.

Chopper
 Ci
rcul
ardi
scwit
halt
ernat
equadr
antsremoved.
Funct
ion
Rotat
esandt
ransmi
tssampl
eandrefer
encebeam
Anal
yti
calTechni
ques 6.
35

al
ternativel
ytograti
ng
Fi
lt
ers:
Monochr omators-Itconsis
tsofanent rancesl
i
t,a
di
spersingelement(pri
sm orgrati
ng)andanex i
tsl
it.
 IRr egi
on – NaCl pri
sm
 FarI Rregi
on– KBrpr i
sm
 Gr ati
ngmadeofquar t
zorf usedsil
i
ca.
Functi
on
Sendsindi
vidualr
equiredfrequenci
estodetector

Det
ect
ors:
 Thermocouple(EMF)
 Bolometer(
ohms )
 Golaypneumaticcel
l
 Photoconducti
vit
ycel
l

Functi
on
The det
ect
orconver t
st he r
adiat
ion si
gnal
sinto
curr
ent .The current i
s dir
ectl
y proport
ionalto the
concentrat
ionoft
hes ol
uti
on.

Motorli
ghtat t
enuat or
Functi
on
Drivesan opt i
caledge i
ntotheref
erencebeam
unti
lthedet ectorr ecei
vesl
ightofequali
ntensi
tyf
rom
sampleandr eferencebeam.

Amplif
ierandRecor di
ngs ystem
 Pen/digit
alrecor
der
Funct
ion
Theout putgraphwhi chisapl
otofthewavel
ength
oftheentir
eregionver s
ust heabsor
banceoftheli
ghtat
eachwavelengthisobtained.
6.
36 Engi
neer
ingChemi
str
y-I
I

6.
7ATOMI
CSPECTROSCOPY

Phot omet er
Itisani nstrumentt hatfurnishest her atioors ome
function oft he r at
io,oft he r adiant poweroft wo
electromagnet icbeams .
Spect romet er
Ani ns t
rumentwi t
hanent ranc es l
it,adi spersing
device and one mor e ex i
t s l
i
t wi t
h whi ch t he
meas urement sar emadeats el
ect edwavel engt hswi thin
thes pectralrangeorbys canningovert her ange.The
quant itydetect edisaf uncti
onoft her adiantpower .
Spect rophot omet er
Itisas pect rometerwithas sociatedequi pment ,so
thatitf urnis
hest her atio,orafunct i
onoft her atio,oft he
radiantpoweroft hetwobeamsasaf unctionofs pect ral
wavel ength.Thes et wo beamsar es epar ated i nt ime,
spaceorbot h.

Thist echniqueinvol vest hestudyoft heabsor pti

on
andr adiat i
onbyneut ralat omsi nthegas eouss tate.Thus
i
nt heAASt hes amplei sf ir
stconver t
edi ntoanat omic
vaporand t hen theabs or ption oft heat omi cvapori s
meas ured at a s elect ed wavel ength whi ch i s
characteristi
cofeachi ndividualel ement .Thet echniqueis
als
ocal l
edasabs orptionf lamephot omet r
y,becaus eall
the anal yte appl i
cati
onsofat omic abs orpti
on involve
sprayingt hes oluti
onoft hes ampl eintoaf lame.Whena
sol
ut i
onhavi ngami xt
ur eofmet al
li
cs peciesisintr
oduced
i
ntot hef lame,t hes olventevapor atesand vapour sof
met al
lics peciesar eobt ained.Someoft hemet alat oms
can ber aised to ener gyl evels uff
icient
lyhi gh to emi t
characteristi
cr adiati
onofmet al–aphenomenont hatis
used inf lame emi ssion s pect rometry.Buti n AAS t he
Anal
yti
calTechni
ques 6.
37

unex
cit
edatomsser
veast
hebas
isf
orat
omi
cabs
orpt
ion
measur
ements.

6.
8FLAMEPHOTOMETRY

Pri
nciple
When a s olution havi ng a mix
ture ofmet al
li
c
species is int
roduced i nto the fl
ame, t he solvent
evapor at
esandvapour sofmet al
li
cspeciesareobtained
fol
lowedbyt heat omi zation.Someoft hemet alatoms
are excited s uf
fi
cient l
y hi gh to emit charact
er i
sti
c
radiati
on ofmet ali.e –a phenomenon us ed inflame
emi ss
ionspectr
omet ry.

COMPONENTS
NEBULI SATION
 Pneumat i
cnebul i
sers.
Funct i
on
Filament sofl i
qui
dar edr awnoutf rom thebul kof
thes ol
ut i
on.Liquids ampleisdr awnt hrought hecapillary
byt hepr essur
edi ffer
enti
algener at edbyt hehi ghvelocity
gass t
ream whi ch passesovert hes ampl eor i
fi
ce.Thi s
l
iquidiss etint
oos ci
ll
ati
on.Thef i
lament scol l
apsetof orm
droplets.Thecloudofdr opletss t
rikesanobs tr
ucti
oni nt he
spraychambert ermed a splinterori mpactbead.Thi s
breakst helargerdr opl
etsint
os mal l
erones. Theaerosol (a
veryf i
nef og)ismi xedwi t
htheox i
dant-f uelmi xt
ureand
carri
ed i nt
ot he bur ner.Dropletsl ar
gert han about20
microm ar et rappedi nt hes praychamberandf low t o
was te.

FLAME
BURNER
 Tur
bul
entf
lowort
otal
cons
umpt
ionbur
ner
,
6.
38 Engi
neer
ingChemi
str
y-I
I

 Lami narPr
emixbur ner
 Non- fl
ameatomizer.
Tur
bulentfl
owortotalconsumptionburner:
Herethenebuliserandthebur nerar ecombined
i
ntoas ingl
eunit
.Thes amplei
sdr awnupt hecapil
l
ary
andthef uelandox i
dantar ecarri
edt hr
oughs epar
ate
pas
sagest omeetandmi xwiththeanalyteatthebaseof
afl
ame.

Lami narPremixbur ner

The sampl ei s as
pirated by the st
ream oft he
oxidant.Theresult
ingaeros olisthenmixedwi t
hfueland
thens enti
ntotheflame.
Non- fl
ameat omizer:
Inst
ead off l
ame,el ectri
call
yheating devi
cesare
used.

Functi
on
Assoonastheaerosolproducedbynebul i
sat
ionint
he
spraychamberistr
ansportedint
othef l
amet hefol
lowi
ng
sequenceofevent
soccursinrapidsuccess
ion.

1
. The s olvent is evapor ated,leaving mi nute
particlesofdr ysal t
.
2. Thedr ys ol
i
dsar econver tedintot hegas eous
state.
3. A par tofal loft he gas eous mol ecules i s
progr essivel
ydi ssociatedt ogiveneut ralat oms
orradi cals-theat omisationstep.Thes eneut ral
atomsar ethes pecieswhi chabs orbinAASand
AFSandar ethepot enti
allyemitti
ngs pecieson
FES.The ef f
iciency wi th whi ch the f lame
producesneut ralat omsoft he analytei sof
equal i mpor t
ance i n eac h of t he f lame
techni que.
4. A por t
ion of t he neut ral atoms may be
Anal
yti
calTechni
ques 6.
39

thermal l
y excited by col l
isi
ons wi th parti
all
y
burntcomponent si nthef lamegas es,oreven
i
onis ed.Thef r
actionex cit
edi simportantinFES
butanui sanceinAAS.
5. Someoft heneut ralatomsmaycombi newi t
h
ther adi
calsint hef l
amegas est of orm new
gas eouscompoundss uchasmet aloxides.Thi
s
givesr is
et ot hechemi calinterf
erenceswhi ch
areofnui sanceinal lt
het hreef l
amet echniques.

FUELGAS
 Nat ural gas, Pr
opane, But
ane, Acetyl
ene or
Hydrogencouldbeused.
OXIDANT
 Air,Ox ygenorNi
tr
ousoxi
decouldbeused.

Fueloxi
dantmi x:
 Forel ement seasi
lyconver ted into atomics t
at e,
exampl e –Cu,Cdet c.,l
ow temper atureflamesar e
required which i
spr ovided byNat uralgas–ai r
mi x
ture.
 Element sformingoxidesr equi
reshotf l
amewhi ch
arepr ovidedby Acet yl
ene-ai rmi x especial
lyfor
alkali
neear thmetalsand Ni tri
cox ide–acet ylene
mi x especial
lyforelement sformings tableoxides
li
keAl etc.

CHOPPER
 Circulardi
scwithalternat equadrantsremoved
Funct
ion
Thei ntens
ityofthes ourceismadet of l
uct
uateata
const
antf requency.Thispr ocessiscal l
ed modulati
on.
Thusrotationoft hedi s
catcons t
ants peedpr ovi
desa
beam thati schopped tot he desir
ed frequency,thus
modulat
ingt heradiat
ionfrom t hesource.
6.
40 Engi
neer
ingChemi
str
y-I
I

FILTER
 Gr at
ingsar eused.
Funct i
on
Mini
mi ze the flame backgr ound emissi
on and
res olvetheat omicemi ssi
onlinesfrom nearbyli
nesand
mol ecul
arfines tr
ucture.Thuspr ovidesa narr
ow band
wi dt handi
s olat
elinesthatint
erfer
ewi thanal
ysi
s.

SLI
TS
 Adj
ust
abl
esl
i
ts
Anal
yti
calTechni
ques 6.
41
6.
42 Engi
neer
ingChemi
str
y-I
I

Entr
ance s li
t i s pl aced between the f lame and
monochromat orwhi chper mit
sonlytheradiat
ioncoming
fr
om thefl
ame&mi rror.
Exi
tsli
tiskeptbet weent hemonochromat oranddetect
or
whichpreventstheent ryofint
erf
eri
ngli
nes .
Functi
on
Togivegr eaterintensi
ty

DETECTORandi t
sFuncti
on
 ThePhotomul
ti
pli
ertubes,Photocel
letc.
.
Funct
ion
Itconvert
sthe radiati
on signal
si nto el
ect
ri
cal
si
gnal
s .

AMPLIFIER&RECORDERandt heirfuncti
ons
Si
ncethecur
rentcomingoutf rom thedet
ect
ori
s
weak,amplif
ieri
sus
edtoampl i
fythecurrentandwhi
chi
s
recor
dedusingapen/digi
tal
recorder.

6.
9ATOMI
CABSORPTI
ONSPECTROSCOPY

I
NTRODUCTI ON
Thist echniquei nvolvest hes tudyoft heabs or pt i
on
andr adi ationbyneut ralat omsi nt hegaseouss t
ate.Thus
i
nt heAAS,whenas oluti
onhavi ngami xtureofmet alli
c
species i s i ntr
oduced i nto t he f lame, t he s ol vent
evapor at esandvapour sofmet al
licspeciesar eobt ai ned
andt hent heabs orpti
onofr adiationbyt heat omi cvapor
i
s meas ured at a s elect ed wavel engt h whi ch i s
charact eristi
cofeachi ndividualel ement .Thet echni quei s
als
ocal ledasabs orptionf lamephot omet r
y,becaus eal l
the anal yte appl i
cati
onsofat omi c absorption invol ve
sprayingt hes ol
uti
onoft hes ampl eintoaf l
ame.I nAAS
the unexci ted at oms s er ve as t he basisf orat omi c
absor ptionmeas urement s.
Anal
yti
calTechni
ques 6.
43

Principl
e
When a s ol
ution havi ng a mi xture ofmet al li
c
species i s int r
oduced i nt o t he f lame, t he s ol vent
evapor atesandvapour sofmet al
lics peci esar eobt ained,
foll
owedbyt heat omi zationoft hevaporandt hent he
abs orpti
onofr adiati
onbyt heunexci tedat omsi nt he
atomi cvapori smeas uredatas elect edwavel engt hwhi ch
i
schar acteri
sticofeac hi ndivi dualel ement .The f lame
gas esaret r
eat edasamedi um cont aini ngf r
ee,unex cited
atomscapabl eofabs orbingr adiationf rom anex ter nal
sour c
e.Thi s occur s when t he r adiat ion cor r
es ponds
exact l
yt ot he ener gy r equi red f ora t ransi
t i
on oft es t
elementf rom gr oundel ect rons tatet ot heex ci
teds t at e.
The unabs orbed r adi ation pas ses t hrough a
monochr omat ort hati solatest heex citing spect r
all ines
andi ntoaphot odetector.Abs orptioni smeas uredbyt he
differ
encei nt ransit
ions ignali nabs enceandpr esenceof
testelement .

=absorpti
oncoeffi
cient
x=pathlength
I=t
ransmitt
edi nt
ensi
ty
I
0=Inci
dentintensi
ty
c=concentrat
ion

RADIATIONSOURCE
 Holl
ow cathode l
amp withtungst
en anode and
cyli
ndr
icalanal
ytemetalcat
hodeinagl asstube
withfi
l
lergasas NeorAr,
isused
Functi
on
6.
44 Engi
neer
ingChemi
str
y-I
I

Whenapot enti
ali sappl iedacr osst heel ectrodes
i
onisati
onoft hegasoc cursandt hecur r
entf l
owsast he
i
onsmi grat
et ot heel ectrodes .Ifpotent ialislarget he
gaseouscat i
onacqui r
eenoughki neti
cener gytodi sl
odge
someoft hemet alatomsf r
om t hecat hodes urfaceand
produceanat omiccl oudcal l
eds putt
er i
ng.A por t
ionof
thes putt
eredmet alatomsar ei ntheex citedstateand
thusemi tt hei
rchar act eri
sti
cr adiat
ion.Event uall
yt he
met alatomsdi ff
us e backt ot he cat hode s urface and
redeposit
ed.Toremovei nterferencesmodul ati
onisdone.

CHOPPER
 Circulardi
scwithalt
ernat equadrantsremoved
Funct
ion
Thei ntens
ityofthesour ceismadet of l
uct
uat eata
const
antf requency.Thispr oces siscal l
ed modul at
ion.
Thusr ot
ation oft he di
sc atcons tants peed provi
des
abeam thati schopped tot hedes i
red f
requency,thus
modulati
ngt heradiat
ionfr
om t hesource.

FUELGAS
 Nat ural gas, Pr
opane, But
ane, Acetyl
ene or
Hydrogencouldbeused.
OXIDANT
 Air,Ox ygenorNi
tr
ousoxi
decouldbeused.

Fueloxi
dantmi x:
 Forel ement seasi
lyconver ted into atomics t
at e,
exampl e–Cu,Cdet c.,l
ow temper atureflamesar e
required which i
spr ovided byNat uralgas–ai r
mi x
ture.
 Element sformingox i
desr equi
reshotf l
amewhi ch
arepr ovidedby Acet yl
ene-ai rmi x especial
lyfor
alkali
neear thmetalsand Ni tri
cox ide–acet ylene
mi x especial
lyforelement sformings tableoxides
li
keAl etc.
Anal
yti
calTechni
ques 6.
45

BURNER
 Tur bul
entfl
owort otalconsumpti
onburner
,
 Lami narPremixburner
 Non- fl
ameat omizeri
sus ed.
Tur
bulentfl
owort otal
cons umpt i
onburner
:
Heret henebuli
serandt heburnerarecombi
ned
i
ntoas ingl
eunit.Thes amplei sdrawnupt hecapi
l
lar
y
andthefueland
6.
46 Engi
neer
ingChemi
str
y-I
I
Anal
yti
calTechni
ques 6.
47

ox i
dantar ecar r
iedt hroughs eparatepas sagest omeet
andmi xwi t
ht heanal yteatt hebas eofaf lame.
Lami narPr emixbur ner
The s ampl ei s aspirated by t he s tream oft he
ox i
dant.Ther es ulti
ngaer osoli sthenmi xedwi thfueland
thens entintot hef l
ame.
Non- fl
ameat omi zer:
Instead off l
ame,el ect ri
call
yheat ing devi cesar e
used.
Funct i
on
Vapour isationoft hel iquidsampl eoccur sfoll
owed
byt heatomi zat i
onoft heel ement s.Theel ectronsoft hese
element sabs or b energyf rom t hel i
ghts our ceandget
excitedfrom gr ounds t
ate.Thi sthenemi tst heener gyand
returnstot hegr ound state.Theunabs orbed r adi
ation
pas ses through a monochr omat or that i s olates the
exciti
ngs pectral l
inesandi ntoaphot odetect or.

FI
LTER
 Glassfi
l
ter
scangener
all
ybeused
 Fil
ter
ss i
mil
art ot
he UV-Vi
si
ble Monochr
omator
s
couldbeused.
Functi
on
Provi
desanarrowbandwidt
handi s
olat
eli
nest
hat
i
nterf
erewithanal
ysi
s.

DETECTORandi t
sFunct ion
Thedet ectorsthatar eus edar es ameasi nUV-
visi
bles pectrophot ometers,ex ampl ethePhotomul t
ipl
ier
tubes .Bothnullpointanddi r
ectr eadingmeter
scalibr
ated
i
nt ermsofAbs orbanceort ransmi t
tanceareusedwhi ch
receivesal t
ernatings i
gnal sfrom s ourceandcont i
nuous
one f r
om t he flame whi ch are conver t
ed t
o electri
cal
signals. AC par t of t he s ignal is amplif
ied and
unmodul at
eddcs ignali
si gnored
AMPLI FIERANDRECORDER
6.
48 Engi
neer
ingChemi
str
y-I
I

Si
ncethecur
rentcomingoutfr
om thedet
ect
ori
s
weak,ampl
if
ieri
sus
edtoampl i
fyt
hecurr
entandwhi
chi
s
r
ecordedus
ingapen/digi
tal
recor
der
.