1

Prepared by:
Wan Elina Faradilla Wan Khalid
Faculty of Applied Science
UiTM Negeri Sembilan

Propertie of electromagnetic
radiation

Electromangnetic pectrum

Tranmittance

Aborbance

!eer" #a$

#imitation of !eer" #a$

2

The tudy of the interaction bet$een

ELECTROMAGNETIC (EM) RADIATION and
MATTER

Meauring amount of radiation

produced/absorbed by molecular%atomic pecie
3
ATOMIC
SPECTROSCOPY
MOLECULAR
SPECTROSCOPY
covers
What i Electromagnetic &adiation'

i a form of energy that ha both

Wave and Partice Propertie(

For e)ample: Ultra*iolet+ *iible+

infrared+ micro$a*e+ radio $a*e(
,
Wa*e-li.e
propertie
Wa*e-li.e
propertie
Particle-
li.e
propertie
/photon or
0uanta1
Particle-
li.e
propertie
/photon or
0uanta1
5
Photon: unit of ener! e"u#$ to hv %h is &$#nc' const#nt ( f is fre"uenc!)

Energy radiated in the form of a

WA2E caued by an electric 3eld
interacting $ith a magnetic 3eld

&eult of the acceleration of a

charged particle

4oe not re0uire a material medium

and can tra*el through a *acuum
*

EM radiation i con*eniently modeled a

$a*e coniting of perpendicularly
ocillating electric and magnetic 3eld+ a
ho$n in the diagram(

At 567 to the direction of propagation i an

ocillation in the E#E8T&98 F9E#4(

At 567 to the direction of propagation and

567 from the electric 3eld ocillation
/orthagonal1 i MA:NET98 F9E#4 ocillation(
+
,
Period (p) ; the time re0uired for one cycle to pa a 3)ed point in
pace(
Frequency (v) ; the number of cycle $hich pa a 3)ed point in pace
per econd(
v ! <%p /
-<
= >?1
v depend on the ource+ but i independent of the propagating
/tranmitting1 material(
-
Amplitude /A1 The ma)imum length
of the electric *ector in the $a*e
/ma)imum height of a $a*e1(
Wavelength (") ; The ditance
bet$een t$o identical ad@acent point
in a $a*e /uually ma)ima or minima1

1.
Velocity of propagation (v
i
)
The rate at $hich a $a*e front mo*e
through a propagating medium in meter
per econd /m
-<
1( *
i
= vA
i
2elocity of light
-
i gi*en pecial ymbol+ c = B(66 <6
C
m
-<

= B(66 <6
<6

cm
-<
8 = vA = B(66 <6
C
m
-<

11
Wavenumber /v1 ; The number
of $a*e per cm in unit of cm
-<

(
12
Speed of light = Wa*elength )
Fre0uency

c = 2

= c%2

2 = c%
<B
For Electromagnetic Wa*e the Speed
/c) is a Constant
c = 3.00 x 10
8
m/sec = 3.00 x
10
10
cm/sec
c = 3.00 x 10
8
m/sec = 3.00 x
10
10
cm/sec

Thi 8ontant Speed Mean a 4irect+

9n*ere &elationhip !et$een
Wa*elength and Fre0uency
D <%V

The #i$%er t%e &re'ue(c) t%e

*%orter t%e Wavee($t% ( The
#onger the Wa*elength the #o$er the
Fre0uency(
<,
Wa*elength i i(verse)
proportio(a to fre0uency
Wa*elength i i(verse)
proportio(a to fre0uency
<E
800 nm
9nfrared
radiation
2 = B(FE ) <6
<,

-<
Ultra*iolet
radiation
2 = F(E6 ) <6
<,

-<
Pic 1/
Pic 2

Wa*e theory failed to e)plain phenomena

aociated $ith the aborption and emiion
of radiation of radiant energy(

Thu+ EM i *ie$ed a a tream of dicrete

particle of energy called photon(

We can relate the energy of photon to it

$a*elength+ fre0uency and $a*enumber by
E = hv = hc = hcv

h ; Planc." contant = G(GB <6
-B,
H(
1*
9!M cientit ha*e de*eloped a
prototype computer chip that operate at
a fre0uency of BE6 :>?( 8alculate the
energy in @oule(
Solution:
E = h* = G(GB ) <6
-B,
H( ) BE6 ) <6
5
>?
= G(GB ) <6
-B,
H( ) BE6 ) <6
5

-<

= I(BI ) <6
-II
H
1+

For electromagnetic radiation $ith a

$a*elength of EGI nm J

i1 8alculate the fre0uency in >?(

ii18alculate the energy of thi
radiation(
1,
< nm = <) <6
-5

m

The electromagnetic pectrum co*er a $ide

range of $a*elength and fre0uencie(

The di*iion are baed on the method ued to

produce and ober*e the *ariou type of
radiation(
1-
Re$io( Wavee($t%
Ra($e
U2 <C6 ; BC6 nm
2iible BC6 ; FC6 nm
Near-9&
6(FC ; I(E m
Mid-9&
I(E ; E6 m
&egion of the U2+ 2iible and
9& Spectrum
2.
Re$io( +(it De,(itio
( (-)
L-ray Angtrom
unit+ M
<6
-<6
m
Ultra*iolet
%*iible
Nanomete
r+ nm
<6
-5
m
9nfrared Micromet
er+ m
<6
-G
m
Wa*elength Unit for 2ariou
Spectral &egion
21
Type of pectrocopic method baed
on EM radiation
1 0 1 1.
21.
3 1 1.
2,
c3
1 n3 1 1.
2-
3 1 1.
2+
c3
1 3 1 1.
2*
3 1 1.
24
c3
22
Nou ha*e
to
remembe
rOO

Name four /,1 type of

electromagnetic radiation
23

*pectroscopist use t%e i(teractio( o.

radiatio( /it% -atter to obtai(
i(.or-atio( about a sa-pe0
Absorptio( o. Radiatio(1 Aborption occur only if :-

There i an interaction bet$een the

electromagnetic radiation and the material(

Sample uually timulated by applying energy in

the form of heat+ electrical energy+ light or a
chemical reaction(

The timulu then caue ome of the analyte

pecie to undergo a tranition to a higher energy
tate from ground tate
24

Meaure the amount of EM radiation

emitted a it return to the ground tate%
meauring the amount aborbed a the
reult of the e)citation

9
o
Sample 9

9 P 9
o
/aborption depend on
concentration of aborbing molecule and
path length1
25

Quantitati*e aborption method re0uire t$o po$er

meaurement:

one before a beam ha paed through the medium that

contain the analyte /P
o
1 and the other after the ample /P1(

T$o term+ $hich are $idely ued in aborption

pectrometry and are related to the ratio of P
o
and P+ are
tra(s-itta(ce and absorba(ce(
2*

T = P% P
o
/*alue from 6 to <1

Tra(s-itta(ce1 The tranmittance T of the medium i

the fraction of incident radiation tranmitted by the
medium(
$here+ P
o
i the incident po$er of the beam and P i the
po$er of the beam after aborbed by the ample(
Tranmittance i often e)preed a a percentage+
RT = P% P
o
) <66 R /*alue from 6 to <661

Absorba(ce1 The aborbance A of a medium i de3ned

by the e0uation+
A = -log
<6
T = -log P% P
o
= log P
o
% P = log <%T
2+
re-e-b
er
2,
<( 8on*ert the follo$ing percent
tranmittance data into aborbance:

i1 BB(G ii1 5I(< iii1 <(FE
An$er: i1 6(,F,
ii1 6(6BEF
iii1 <(FG
2-
i1 RT = BB(G
T = BB(G % <66
= 6(BBG
A = - log T
= - log 6(BBG
= 6(,F,
3.
I( 8on*ert the follo$ing aborbance
data into percent tranmittance:
i1 6(BFE ii1 <(BIE iii1 6(6<I
An$er: i1 ,I(IR
ii1 ,(FBR
iii1 5F(BR
31
#o/ to
sove22
A(tio$ 3

!eer" #ambert #a$

ho$ linear relationhip bet$een

aborbance+ concentration of the
pecie meaured+ ample path length
and the aborpti*ity of the pecie(
= molar aborpti*ity+ liter mol
-<
cm
-<
b = ample path length+ cm
c = concentration+ mol per liter
A = bc
32
33
A = abc
Aborbance
Aborpti*ity
/#g
-<
cm
-<
1
Pathlength
/cm1
8oncentration
/g%liter1
- The term SaT i a proportionality
contant called aborpti*ity(
- Aborpti*ity i a contant for a
gi*en chemical pecie at a peci3c
$a*elength(
34
E(g(
<( What i the concentration of an aborbing
pecie if it molar aborpti*ity i <E66
#%mol(cm and the meaured aborbance in a
<(66 cm cu*ette i 6(F,I'
An$er:
A = bc c = A % b
c = 6(F,I = ,(5E <6
-,
M
/< cm1/<E66 #%mol(cm1
35
E(g:
I( The meaured aborbance of a ample in
a <(66 cm cu*ette i 6(E,,( 9f the
concentration i <(,6 <6
-B
M+ $hat i the
molar aborpti*ity for the pecie'
An$er:
A = bc = A % bc
c = 6(E,, = BC5
#%mol(cm
/< cm1/<(,6 <6
-B
mol%#1
3*
E(g(:
B A ample in a <(6 cm cell i determined $ith a
pectrometer to tranmit C6R light at a certain
$a*elength( 9f the aborpti*ity of thi ubtance at thi
$a*elength i I(6+ $hat i the concentration of the
ubtance'
An$er:
The percent tranmittance i C6R( So+ T=6(C6( 2alue for
A = 6(65G5
A = abc
- log T = I(6 #%g(cm < cm c
- log 6(C6 = I(6 #%g c
c = 6(65G5 = 6(6,CE g%#
I(6 #%g
3+

A IE(G mg ample of a compound $ith a molecular

$eight of B<F(<F g%mol $a diol*ed $ith ol*ent
in a B66 m# *olumetric Ua.( The aborbance of
thi olution at IBC nm $a 6(GI, in a <(66-cm
cu*ette( 8alculate the molar aborpti*ity of thi
compound

M = mol%#

An: I(BI ) <6

B
# mol
-<
cm
-<
3,
Need to ,(d
t%e
co(ce(tratio(
(-oarit)) o.
t%e sa-pe
,rst
A = abc

8oncentration

Width of cu*ette

9nherent ability for aborbing

pecie to aborb light
3-

9nherent ability for the aborbing pecie to

aborb light

8hemical pecie *ary $ith repect to thi

inherent ability ince aborption depend on
indi*idual electronic and *ibrational tranition
a*ailable in a gi*en pecie(

Width of cu*ette

Wider cu*ette more

aborbing pecie
preent in the path of
the light+ hence
aborbance i greater
b
b
4.

Applying !eer" #a$ to Mi)ture

-
!eer" la$ alo applie to olution containing more
than one .ind of aborbing ubtance+ pro*ided
there i no interaction among the *ariou pecie(
-
Total aborbance for a multicomponent ytem at a
ingle $a*elength i the um of the indi*idual
aborbance(
A
total
= A
<
V A
I
V WWWWV A
n

=
<
bc
<
V
I
bc
I
V WWW V
n
bc
n
41

4e*iation are fre0uently ober*ed

from the direct proportionality
bet$een aborbance+ A and
concentration+ c $hen pathlength+ b
i contant(
42
4e*iation may be due to:
<( Fundamental%&eal de*iation
I( 9ntrumental de*iation
B( 8hemical de*iation
43
<( Fundamental de*iation
-
&eal limitation to the la$
-
At high concentration /X 6(6<M1 each
particle aYect the charge ditribution of
it neighbour(
-
Therefore+ thi interaction alter the ability
of analyte pecie to aborb a gi*en
$a*elength of radiation(

8auing de*iation from the linear relationhip

bet$een aborbance and concentration(
44
I( 9ntrumental de*iation

due to polychromatic radiation

!eer" #a$ trictly applie $hen

meaurement are made $ith
monochromatic ource radiation(

9n practice+ polychromatic ource that

ha*e a continuou ditribution of
$a*elength are being ued(
45
I( 9ntrumental de*iation

due to preence of tray radiation

4ue to intrument imperfection(

Thi tray radiation i the reult of

cattering and reUection oY the urface
of grating+ lene or mirror+ 3lter and
$indo$(

The $a*elength of tray radiation diYer

greatly from the principal radiation Z
may not ha*e paed thru" the ample(
4*
B( 8hemical de*iation
-
[ccur $hen the analyte undergo
diociation+ aociation or reaction $ith the
ol*ent to gi*e product that aborb
diYerently than the analyte(

Eg: a0ueou olution of acid-bae indicator

>9n >
V
V 9n
-
color <

color I
4+
<( Aborption pectrum
I( Emiion pectrum

Aborption pectrum

A plot of aborbance *eru $a*elength

Emiion pectrum

A plot of the relati*e po$er of the

emitted radiation *eru $a*elength(
When radiation pae through a ample certain
fre0uency may be electi*ely remo*ed by
absorptio(+ a proce in $hich electromagnetic
energy i tranferred to the atom+ ion or molecule(
Absorptio( pro-otes t%ese partices .ro-
$rou(d state to o(e or -ore %i$%er e(er$)
states( The energy of the e)citing photon mut
e)actly match the energy diYerence bet$een the
ground tate and one of the e)cited tate of the
aborbing pecie( Since thee energy diYerence are
uni0ue for each pecie+ a tudy of the fre0uencie of
aborbed radiation pro*ide a mean of
characteri?ing the contituent of a ample of matter(
4-

Ato-ic Absorptio(1 The paage of polychromatic

ultra*iolet or *iible radiation through a medium that
conit of monoatomic particle reult the aborption of
a fe$ $ell-de3ned fre0uency( Such spectra is ver)
si-pe due to t%e s-a (u-ber o. possibe e(er$)
states .or t%e absorbi($ partices0

Moecuar Absorptio(1 Aborption pectra for

po)ato-ic -oecues are co(siderab) -ore
co-pe4 t%a( ato-ic spectra because t%e (u-ber
o. e(er$) states o. -oecues is $e(era)
e(or-ous /%e( co-pared /it% t%e (u-ber o.
e(er$) states .or isoated ato-s0 The energy E of a
molecule i made up of three component+
E = E
electronic
V E
*ibrational
V E
rotational
5.

The t$o pea. arie from the

promotion of a B electron to the t$o
Bp tate
E<
Absorptio( *pectru- o. Na

The harpne of molecular

aborption pectra alo
depend on the tate of the
ample(

Figure /b1 ho$ an absorption

band due to tranition
bet$een electronic-*ibrational-
rotational tate

Figure /d1 ho$ a continuous

spectra due to the ample i in
the condened tate( 9n
condened tate the pectra
broaden due to molecular
colliion(
EI

Atomic tranition are uually *ery dicrete

change of electron from one 0uantum tate to
another energy le*el /hell+ pin+ etc1

[nly electronic tranition i 0uanti?ed(

No *ibrational or rotational tranition(

E
6
; lo$et energy electronic le*el or ground
tate
E
<
+ E
I
; higher-energy electronic le*el
5 When an atom change energy
tate+ it aborb or emit energy
e0ual to the energy diYerence
\E = E
<
; E
6
5The $a*elength or fre0uency of
radiation aborbed or emitted
during a tranition proportional to
\E
\E = hv = hc

produce i(e pectra

53

Mo$ecu$#r tr#nsition consists of 3

&rocesses:
2 Rot#tion#$ tr#nsition
2 6i7r#tion#$ tr#nsition
2 E$ectronic tr#nsition
8E 1 8E
e$ectronic
9 8E
vi7r#tion#$
9 8E
rot#tion#$

:ue to vi7r#tion#$ #n; rot#tion#$

tr#nsitions 2 &ro;uce band s&ectr#
Energ
y
54

Rotatio(a Tra(sitio(
- Molecule rotate about *ariou a)e
-
E
rotation
being at de3nite E
le*el
-
Therefore+ the molecule aborb radiation and be raied to a higher
rotational energy le*el(

5ibratio(a Tra(sitio(
-
Atom or group of atom $ithin the molecule *ibrate relati*e to
each other
-
E
*ibration
occur at 0uanti?ed le*el
-
Therefore+ the molecule aborb radiation and be raied to a higher
*ibrational energy le*el(

Eectro(ic Tra(sitio(
- Electron of a molecule may be raied to a higher electron energy (
55

E-issio( o. Radiatio(1 Electromagnetic radiation i

produced $hen e)cited particle /atom+ ion+ or
molecule1 rela) to lo$er energy le*el by gi*ing up
their e)ce energy a photon( &adiation from an
e)cited ource i characteri?ed by mean of an
emiion pectrum(
L L
]
L V h

E)citation can be done by ;

<( !ombardment $ith electron
I( Electric current ac par.
B( >eat of a Uame
,( An arc or a furnace /produce u*+ *i or ir radiation1
E( !eam of electromagnetic radiation
5*
T%ree t)pes o. e-issio(
spectra1
<( #ine Spectra
I( !and Spectra
B( 8ontinuum Spectra
5+
EC
Emiion pectrum of a brine ample