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Atomic Absorption Spectroscopy: .! Introduction
Atomic Absorption Spectroscopy: .! Introduction
.! Introduction
Since its introduction, by ‘Alan Walsh in the mid-1950's,(atomic
absorption spectroscopy has proved
itselfto be the most powerful instmumental technique for the ovantitanive
Sti eee ae
tativedetermination of trace metals in
oT
es wm ‘ s
yee U the total amouat of light Tbsorbed = ——N/ 13.1
= mc
where e is the charge on the electron of mass m, c the speed of light, N the total number of atoms that
wan absorb at frequency vin lie light path and f the oscillator strength or ability for each 2tom to absorb
at frequency, v. As 2, e, m and c are constants, equation (13.1) can be simplified to the following expression:
— Total amount of high absorbed = constant*N =/ 132
From expression (13.2), it follows that
(a) Firstly, there is no term involving the wavelength (or {fequency) of absorption other than the
7 indication of the actual absorption wavelength.
A(b) Secondly, there is no-term involving the tempe ure
From above, it follows thatRbseriicn by ator is independent of the wavelength of absorption and
the temperature of the atoms. These two. features provide atomic absorption spectroscopy distinct
advantages over flame emission spectroscopy.
In should be pointed out, however, that although the temperature does not affect the process of
absorption by atoms, it does affect the efficiency with which atoms are produced from a sample and
therefcre indirectly affects the signal quite significantiy. Furthermore, some atoms, particularly those of the
alkali metals, easily ionize ct high tempecatures. lons do not adsorb at atomic absorption waveleagtns
Atoms that become ionized are effectively removed from the absorbing pepvlation, resulting in = loss uf
signal.
oo TNE 98 ore omen re tt em or or ee eee
ee
2 2 2 2. 2,
eo "1 "2 cd ;
- fi: T “T T 7
V L
$0 /7 Be.
na 3ao :f
& oy:
n PD Rie!
he
= 20} Ifo fay
= 3 if Lf
& EF fh
my 20- fi of f
. fay /
fo) fs/
ote te
oe
gf!
10 ? ie 4
if
’,
o L i i j
Ground state
weer
Fig. 13.1 Partial Grotrlan diagram for sodium.
lee aeens ee
Under narmal conditions atoms exist in their lowest possible energy state, the ground state. Very few
toms are normally in the higher energy-states. For-exaiaple, it can be calculated from the Boltzmann
distribution law that if zine vapor with a resonance line at 213.8 nm is heated to 3000 K, there will be only:
one etom in the first excited state for every 10! atoms in the groundstate. Zinc atoms need a considerable
umount of energy to became excited. On the other hand, sodium atoms are excited more easily dian the
atoms of most other ciements. Nevertheless, at 3000 K only I sodium atom is excited fot every 1000 atoniz
in the ground state. At room temperature the 1etio the number of excited to unexcited atoms is greatly
veduced, In a normal siom population, therefore, there are very few atoms in sistes E,, E,, Ey, The
rota! amount or radiation absorbed depends, among other things, on howmany atoms tere are availabic
to absorb, Consequently the total amount of radiation absorbed at frequencies v,¥,, and s9 on, is
exceedingly small and nut useful aialytically,
For practical purposes, all absorption is by atoms in the ground-state Icvei, This greatly restricts the
yniuber of absorption lines that can be used in atomic absorption. Quite frequently only three or four usef!
luaes are avatiable in the UV spectrai region for each element, and in some cases less than that. The wave-
length of these absorption lines can be deduced from the Grotrian diagram of the element being determined.
Pouensee
(Grotrian diagrams correctly predict that the energy required to reach even the first excited stare of
nonmetals issu yreat that they cannot be excited by ultrs siolet radiction. Their resonance lines are ii the
vacuum UV.Consequently, atomic absorption cannot be used for the direct determination of nonmetals,
alitiough with the use of a capillary discharge larnp, iodine has been measured directly However, nonmeia’:
have been determined by indirect miettods, Forexample,chtoridesprecipitated as silver chloride:
from the subsequent determination of silver, the chloride can be calculated,
IS. * Differences Between Atom*c Absorption Spectroscopy and Flame Emission Spectroscopy
"
The main differences between atomic absorption spectroscopy and flame emission spectroscopy are
as follows
(a) In fame emission spectrascopy, the atonys when’put in a flame, become executed: The exened atom,
which is instable, quickly emits 2 photon of light and retums to'a lowes energy state, event! l\’
—
Atomic Absorption Spectroscopy 2343
basis of ame
reaching wv: unexctted sizte [he sigasursment of this-ematted rad:onon forns we
emission spechoscopy. Analytical siqnal ij n flame emission is the Sunn of all erogics ensitied «>
excited atoms dep to the ground som © signal cownes entirely feom the emuinne atone
ly atomic abserpuion spectroscopy, the signal is obtained froin Wie difference between the intensity
of the source in the absence of metallic elements present in the Iiguyd and the decreased intensity
obtained when metallic elements are present m the opticalpath, , os
(b) In flame emisston spectroscopy, the emission Thtensity is dependent upon the number of exciting
atoms and is, therefore, gPeatly influenced by temperature vananons
In atomic absorption spectroscopy, atomic absorption depends upon the number of unexcited atoms
and the absorption intensity coes not depend upon the temperature of the flame directly
(c) In atomic absorption spectroscopy, the relation between absorbance and concentration 1s nearly
linear, that is, Beer's law is obeyed over a wide concentration range. Thisis not true in cases of flame
emission spectroscopy
_ @) \ The
2atomic
ome Seis meen: because ine atoms ofa ‘panicnta element can¢'
absorb,radiation oftheir owncharacteristic wavelength. Theconverse isbisotrue, 7 e., the light . oF
‘particular
ilarfrequency can easilybe absorbed by the s ecific “element
toto which it is characteristic
Spectral interferences which occur in ‘flame emission spectroscopy Therefore vccur rarely,
(b) Because of the muchlarger number of metalatoms.that contribute to an atomigabsorpnon sign!
variation in flame ttemperatures showsrelatively less effect in atornic absozption spectroscopy i:
flame emission
nspectroscopy
inwhich the smallernumber of atorsare producingdicernkesionssaiek
Inskort,it means that atomic absorption Spectrescopy is independent of flame tempcsarure
(c) In terms of detection limitsatomic adsorption and flame emissiun are quite similar, /.¢, soune eleriz: 1
possess lower detectionlisnits by flarne emission and others by atomic absorption Table 13.1 jives
the list of elements in three categories which are as follows: *
(f) those more
senstave by fame emission,
(i) “those of3about equal sensitivity by emission5 anid absorption, and
(fff) those more sensitive by atomic absorption.
haere 8 ee
ryu2 Ppeteeerecrs tat ieiny
=
Acetylene “7
Air
Phote cell
To drain
cathode. The impact with the cathode vaponzes sume of the sodium atonis, These are excited and
uon Returning to thegroundstale givetise teHe sedium emissionspectrum
of (he
: The manudacduser’s recommended curred! for the lamp should nat be exceeded or the |)ferime
$ lamp may be considerably shortened. Excess current may alco give misc 4 3 s¢lf-absorpoon process
: wherein the sputtered ground-state atoms absorb some of the emitted energy, resulting ina lessening
of intensity of the emined the (see Figure 13.4), Og she Wcr hand, if the source lamp is run below
the recommended current, a loss of intensity anda corresponding loss of sensinvity wif result,
~~
4
p= Sodium
emission spectrum
Quartz or
glass window >
| Vaporized atoms
inertcarriergas [~~ me
(NQe’ A)
+ ye
Anode “Sy 2h oj. etal cathoda (Na)
AS
:
’
Fig. 13.4 ; Schematle diagram of a hollow cathode source lamp tor atomic absorption of sodium.
1 O40
0.39 -
3
ad
.
2 ozo} 3 “
Hoses 0.10} A a
Ae i C; A. paonphies +
2 4 6 & 19 12
1
i: Lampcumert,mA
i| Fig. 13.4; Typical sisorbance vs. lamp current curves ter holice cathose lamps.
mA
| Note that the famp which gives curve C would have an ostimum current at BS
i
| a = Ss —_ *
When a de vollage of 300-500 V as put across the anode and the cathode, ihe avonis Of th ohh
eas underge ionisation at the anode and are rapidly attracted by the cathode, Then, the fast trove
ions sinke the suriace of the cathoce-and physically displace the surface metal atoms: of tic cut!
into neon (92 agton) gas Further coilisicns of the vaponsed metal atoms from the oathede vii
energetic filled gas jons sesult in excitedmetal atoms which emit the characiessuu speckoum 2) 1
used to constauct the cathode. Thus. the emissisn spectum produced by a holaw athode
Jomp is a sharp line spectrum of the cathode materia! and the filled gas. The neanor het gus tilled
in the hollew cathode lamp performs three functions ;
(7) T¢ is the main source of current-carrying capacity in the hollow cathode.
(ii) It dislodges atoms from the surface of the cathcde.
(iii) tt ts primarily responsible for excitation of the ground state metal atoms.
The pressure maintained in the hollow cathode lamp is | to 5 tort, If higher pressures are mauilsi icc
the discharge tends to be unstable and if lower pressures are maintained, the vaporisation of the hollow
cathode metal increases-and the operating temperature ‘also increases.
The spectral lines produced by the hollow cathode lamp are so narrow that they are completely
absorbed by the atoms. By this method, one can easily detect and measure the atomic absorption.
Rach hollow cathode lamp emits ‘the spectrum ofthat metal which is used in the cathode. , For
exareple, cooper cathode emits the copper spectrum, zinc cathode emits the zine spectrum and soon, Az
he Sails time, the narrow spectral lines emitted by copper cathode are only absorbed by the copper'atoms
present in the sample to be analysed vy atomic absorption spectroscopy. Similarly, zinc atoms will ab orb:
speuitul lines emitted by zine cathode. For this reason, a different hollow cathode lamp has to be js ¢ fo)
cach clement to be analysed by atomic absorption spectroscopy, This is not very convenient
In atomic absorption specirophotometer, gaseous discharge lamps are also used. These zr¢ also
alled arc lamps, Gaseous discharge lamps contain an inert gas ai low pressure and a meta! or mici2) s3h:
these lamps are useful for the alkali metals, zinc, cadmium and mercury.
_—_—...
th) Sleerradetess Discharge Lamp. tis dificult to make stable hellow cathodes from certain elemenits,
curleufarty those ibit are volani¢, such a2 arsenic, germaniwan, of selenium. An alternative light
sources has been developed tn the clectrodeless discharge lamp (EDL). ‘Vhis is tllustrated in Fry. 23 5,
ts
Hy consist: of aa evacuated tube in which the metal of interest is pleced. The: tubeis fitied with arger
| low pressure urid staled off. The sealed tube is then placed in a microwave discharge caviry, Urde.
ese ronditions the argon becomes a plasma and causes excitation of the metal ssated inside the
lute The ¢mission from the meial is that of its spectrum, including the resonance line. she inicus!ly
——
ut thess lamps is very high, and they nave been made quite stable in recent years.
womes.
Hene: WOkucounn Spree vcapy 7
(2) Chopper. A totatiog vibect is Uderpased between the hatlew cathode lamp and the time.This
wepingwhei l skeown as choppas ard 1s pntespased tobreak the steady light feom lamp into an
} idtent ot pulsatingThispjves a.pulsaung current in the photocell. ere 15 alse a Steadycyiyen|
steady cyt
hused bylight whichis emitted by a flame. But only the pulsating (or aliermating) curren. is amplified and
pe znd._thus the absorption of light willbemeasured wathout”interference fromth. light enuiiedby
the flame itself. * ;
3. Atomisers. In order t% achieve absorption of atoms, it becomes necessary to reduce the sample
to the atomic state. Thus is done by
(2) flame atomisers
(b) non-flame atomisers.
Flame Atomisers. The most common wayis to use a flame which is used for convernng the liquid
sample into the gaseous state and also for conversion of the molecular entities into an atomic vapour. There
are two types of burners in commonuse, the total consumption burner and the premixed burner.
In the total constrmption burners, the sample solution, the fuel and oxidising gases are passed through
senatate passages to meet at the opening of “2 bes of the flame: As the sample containing nevallic
clement to be estimated by atomic spectrosc7py is a liquid, the flame breaks up the quid sample into
droplets which are then evaporated or burnt, leaving the residue which is reduced to atoms. Total
consumption burners do use oxygen, with hydrogen or acetylene, and give very hot Mames. A rypical tora!
consumption bumeris sllustrated in Fig. 13.6.
\
\
2
=
Gu
o «
e <+—— Oxidantin
° Laceianbeut
é <— Fue! in
“a
S
=i
Sample
A total coasumption burner is noisy and hard to use. The efficiency of this burner 13 not very good
A typical permixed burner is illustrated in Fig, 13.7
In the premuxed hurnsr, a mixture of the sample (liquid) and premixed gases (C,H,+0,) is allowed to
enter the base hf From the base M, the pases enter the region A From the region A the unbunt
hycrocarbor woscous mixture and liquid droplets are allowed to enter the region B which is.a region of
free heating and about linn in thickness In tie region B, the Wiquid uw esaporated leaving a residue VAs
heating in uus region is dom: by uve heat phtained ffom tae tegion C by cofluction and convecnon aad
= uu FU ALI PUOR OPEC LON
a Solid Samples
Types of s
In general, solid samples ninst first be Giesolvesd and the sojurign hes arsalyzed
have been analyzed after disswlution include metals, alioys, soils, antimat tissue, piaat nrotertal, fectil ore
nin judy neuen Gearcah. dee Darts 357
b. Liquids
Frequentlyliquids can be analyzed. Typical samples that have been analyzed directly include blood,
urine, electroplating solutions, petroleum prot:acts, Wines, and pollutants in water. A calibration curve
should always be prepared from @ solution of the same solvent as the sample. If the samples are too
concentrated, they may be diluted prior to analysis. If they are too dilute, they may be evaporated down
or concentrated by, solvent extraction.
¢. Gas Samples
{n conventional samples the metal components mustfirst be collected from gas sainples by absorption
or by wapping in a solution. The absorbant or solution may then be analyzed. Metais in air samples have
been analyzed by atomic absorption after first trapping the metal componentin a sustable solvent,
Hydride Analysis. Some mews are first converted to a gascous hydinde, These are introduced directly
into the atomizer and analyzed the normal way using special equipment, Metals commonly analyzed this
way include arsenic, selenium, and ‘2!sriun.
a. Atomic absorption spectroscopy finds valid applications in every branch of chemical analysis, The
ee)is already a firm!;established procedure in analytical chemistry, ceramics, mineralogy, biochemistry,
ies, metaliurgy and soil analysis. Some of these uses are discussed below:
Qualitative Analysis. In atomc absorpuonspectroscopy,2differenthollow.cathoc is to be
used for each element tobetested. [t means that auS elemect which is ised in the construction of cathode
ot the bofiowcathode iamp, can be derected only As qualitative analysis involves the checking of one
slement ata_tme, it means shat the processisverylaborncus. Theretore, atomic absorption spectroscopy
Se caateneee
is scldon: used in practice for dis]purpose.
,GQuaatitativeAnalysis. The technique of quantitative analysis is based on the determination of the
amount of radiation absorbed bythesample. If the value of radiation absorbed 1s substinited in equation
43,1. tievatieofN, the number ofabsorbing atoms ia the light path, can be determined. As the efficiency
of producing atoms from a sample cangot be ksnown, it means Gat N cannot be used to calculate the
concentration of the element in the sample, In practice, quantitative measurements are generally based on
calibration curves. ; 4
Calibration Curves. The first job in quanntative analysis is the preparation of colibration curve. In
order to prepare this curve, the read-out device should be adjusted to 109% transmittance with a blank
and 0% wansmittance when no radiant energy is entering the monochromator slit. The same type of
adjustment js also made if the read-out device is a cclart recorder. A series of standard samples of that
element which is to be determuned quantitatively is aspirated into the burner and percentage absorpnion
measured. Then, the absorbance values are plotted vs concentrations as shown in Fig, 13.24, If a linear
calibration curve is obtained, the slope of the calibration curve can be obiained end then and concentrations
of unknown solutions can be calculated by using the following equation,
A= mc
Or, Absorbance ™ Slope x Concentration
It is inyportant to remember that the sa ipie whose concentration is to be measuredis atomnised and
absorbanve treasured under exactly the same conditions as those used when the calibration curve was
prepared
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