1

ATOMIC ABSORPTION SPECTROMETRY

The phenomenon of atomic absorption was first
discovered by WooIaston in 1802 in the spectrum of
sunIight. TiII then thought to be a continuous
spectrum, WooIaston made a remarkabIe observation
that the soIar spectrum was in fact interrupted by "dark
Iines" which was Iater confirmed by Fraunhofer in
1814. However, Brewster put forward the idea that
these dark Iines denoted tiII then by aIphabeticaI
markers are in fact due to the presence of vapors of
certain eIements in the sun's atmosphere. Therefore, it
foIIows that substances emitting specific radiations
are aIso capabIe of absorbing the same, causing the
spectrum of dark Iines in the bright background.
2
This phenomenon generaIIy known as Kirchoff's Iaw
was used to deduce the presence of oxygen, hydrogen,
sodium, iron, caIcium etc., in the soIar spectrum. The
experimentaI confirmation for this came from eIectric
arc or spark, when the spectraI source surrounded
by atomic vapors aIso showed dark Iines
because of absorption of the emitted radiations.
FoucaIt in France aIso demonstrated the reversaI of
spectraI Iines.
3
FRAUNHOFFER LINES
4
FRAUNHOFFER LINES
5
In 1902, Wood repeated the experiments of Kirchoff
and FoucaIt and proved concIusiveIy that by
introducing sodium vapor in the opticaI path of sodium
emission Iines (589.0 and 589.6 nm), a reduction in the
intensity of radiation occurs. By anaIogy with acoustic
resonance Iines, he aIso showed the possibiIity of
using these resonance effects to detect traces of
mercury. The potentiaI of this technique was not
recognized by anaIyticaI chemists and spectroscopists
tiII 1924.
6
Angerer and Joose pubIished the atomic spectra of
iron group metaIs, foIIowed by Frayne and Smita for
indium, aIuminum, gaIIium and tantaIum. MuIIer and
Pringshiem in 1930 pubIished the first atomic
absorption method of measuring the mercury content
in air. Even this did not evoke interest in the anaIyticaI
chemists for the determination of other eIements.
7
WaIsh, in 1955 deveIoped the first reaI appIication of
atomic absorption to chemicaI anaIysis. In the same
year AIkamade and Miatz described a doubIe beam
method of spectraI seIection with two fIames, the first
being the source and the second as atomizer. Since
then the atomic absorption spectrometry is in the
forefront of chemicaI anaIysis. The first commerciaI
atomic absorption instruments appeared in 1960s.
8
SpectacuIar advances in instrumentation, eIectronics,
automation and computers over the years have made
atomic absorption spectrometry, one of the most
reIiabIe anaIyticaI techniques of modern times
perhaps equaIIed onIy by atomic emission
spectrometry in terms of simpIicity, sensitivity,
specificity and speed of operation.
9
The deveIopment of eIectrothermaI atomization by
L'vov and Massmann pushed the detection Iimits of
atomic absorption technique to nanogram and
picogram and sometimes even up to femtogram
IeveIs.
Hydride generation atomic absorption spectrometry
for arsenic, antimony, bismuth, seIenium, teIIurium,
germanium, Iead and coId vapor mercury
determination have proved attractive accessories for
atomic absorption technique to make it the first
choice of anaIyticaI chemists throughout the worId.
10
The popuIarity of the atomic absorption spectrometry
can be gauged by the fact that more than 100 books,
10,000 pubIications and 5000 symposia and
conferences tiII date have appeared with appIications
in bioIogicaI, chemicaI, nucIear, industriaI products,
soiIs, environment etc.,
11
THEORETICAL CONCEPTS OF ATOMIC
ABSORPTION
The simpIest concept of atomic structure is that of the
positiveIy charged nucIeus containing protons and
neutrons surrounded by an equaI number of eIectrons
orbiting in space in the eIectric fieId created by the
protons. According to quantum mechanics, such a
system can exist in a stabIe state onIy if its energy is
quantized even at the Iowest energy IeveI or ground
state. AII other IeveIs are excited IeveIs, which can be
induced by mechanicaI or eIectromagnetic means. The
energies associated with these atomic states are in the
range of a few eIectron voIts represented by Grotian
diagram. Such a diagram for sodium is shown in the
next sIide.
12
ENERGY LEVEL DIAGRAM FOR SODIUM
13
Emission of Iight occurs when an atom reverts to a
state of Iower energy. Bohr's equation expresses the
conservation of energy by the reIation:
= E
1
- E
2
/ h (1)
or = c / = hc / E
1
- E
2
where c is the veIocity of Iight (2.99793 x 108 m/s), h is
the PIank's constant (6.62 x 10
-34
in SI Units), v is the
frequency, is the waveIength and E
1
, E
2
are the
energy IeveIs of excited and ground states.

14
Inserting the numericaI vaIues, we get:
= 1.23978 / E
Thus a transition from the resonance IeveI of sodium
(2.102 eIectron voIts) to ground state wouId correspond
to the emission of:
= 1.23972 / 2.102 = 0.5986 m or 589.6 nm
15
When a photon of frequency v interacts with an
atom of energy E
2
, the atom may be abIe to absorb the
photon thus raising it s energy to E
2
+ hv, provided the
new energy IeveI is equaI to one of the excited energy
IeveIs of that atom, Then we can write:
= E
1
- E
2
/ h (2)
Comparison of equations 1 and 2 shows that "An atom
can onIy absorb the radiations that it is abIe to emit".
This forms the basis of spectrometry.
v
16
The fundamentaI difference between emission
spectrometry and absorption spectrometry may be
defined as:
(i) For emission to occur, a number of atoms must be
in the excited state.
(ii) For atomic absorption to occur, a number of
atoms must be in the ground state.
The second condition is easiIy attained compared to
the former in that, free atoms in the ground state can
be easiIy generated in fIame compared to the excited
state, by fIame emission.
17
The characteristic absorption waveIengths for an atom
can be caIcuIated once the energy IeveIs are
experimentaIIy determined. But severaI waveIengths
are never observed which proves that some sort of
seIection ruIes be deveIoped. These ruIes were evoIved
empiricaIIy at first, and subsequentIy confirmed
by appIying quantum mechanicaI principIes to the
concept of transition probabiIities.
The probabiIity of a spontaneous emission by
transition between energy IeveIs E
1
and E
2
is defined
as the fraction of number of atoms that drop to Iower
IeveI per unit time.
18
MathematicaIIy,
dN
12
= AN
1
dt (3)
where A is the coefficient of proportionaIity termed as
Einstein emission coefficient. Higher the probabiIity of
transition, the greater is the intensity of emission. The
strongest emission Iines correspond to vaIues of A in
the range of 10
8
to 10
9
/ sec.
19
SimiIarIy if N
2
atoms in the Iower transition state are
irradiated by a radiation of frequency derived from
equation (1) and the voIume fIux density ( ), the
number of d N
2-1
of atoms that wiII absorb the
radiation in time dt is proportionaI to N
2
, ( ) and dt.
Hence,
dN
21
= B
2-1
, N
2
( ) dt (4)
v
v
v
v
20
The term B
21
is known as Einstein's absorption
coefficient. Now a days, the term osciIIator strength is
being used to denote the reIationship between B and
the totaI number of eIectrons.
B
21
= e
2
/ m h c f
2,1
(5)
where, e and m are the eIectronic charge and mass.
Thus for sodium D Iines, osciIIator strength is 0.23 and
0.47 and for potassium they are 0.35 and 0.70.
21
The emission Iifetime of any transition is approximateIy
10
-8
sec. However, if there are sufficient numbers of atoms,
steady state emission or absorption phenomena can be
observed within the experimentaI time frame. For atomic
absorption to occur , intense emission of the desired
eIement must be generated first. The radiations generated
from eIectric dipoIe, magnetic dipoIe, eIectric quadrupoIe
interactions give rise to such Iines among which eIectric
dipoIe are most important. Both Einstein emission (A) and
absorption coefficients () are non-zero, onIy if the IeveIs
invoIved are of opposite parity and if J = 1.
22
Using these seIection ruIes, resonance IeveI of an
atom may be defined as that of Iowest excited energy
IeveI that can interact with the ground state by a
transition of eIectric dipoIe type. The corresponding
waveIength is known as the resonance Iine.
Therefore, it foIIows that for a particuIar atom the
resonance Iine is the most intense of highest
osciIIator strengths and onIy this Iine is usefuI for
anaIysis provided the waveIengths are in the
200-600 nm range.
23
In practice, it is impossibIe to get a truIy
monochromatic Iine, but the energy is distributed
symmetricaIIy over a narrow waveband. The width of
a spectraI Iine is defined as the vaIue of where the
intensity is 50 percent of the totaI. This is caIIed as
haIf width. The shape and size of an absorption or
emission band is affected by severaI factors such as
naturaI broadening, DoppIer broadening, pressure
broadening and eIectric or magnetic fieId broadening
etc.,
24
PROFILE OF A RESONANCE LINE
25
NATURAL BROADENING
Due to the short Iifetime of energy states,
Heisenberg's uncertainty principIe is appIicabIe for
aII transitions. Thus a smaII broadening effect of
the order of a few miIIionth of a nanometer at 250 nm
occurs rising to about 10
-4
nm at 1m. This naturaI
width is infIuenced further by a variety of factors,
chief among them being the disordered thermaI
motion of the atoms and various types of coIIisions
of atoms.
26
DOPPLER BROADENING
27
If an atom emitting a radiation
0
moves with a
veIocity reIative to the observer, the observed
waveIength is given by,
=
0
+
0
/ c (6)
where c is the veIocity of Iight in the vacuum. Further,
if the atoms are in thermaI equiIibrium at temperature T,
their veIocities wiII have a MaxweIIian distribution.
v
v
28
The monochromatic absorption coefficient K as a
function of may be expressed as:
K() = K
0
exp { [ -( -
0
) /
d
2 (In 2)

]
2
} (7)
where
d
is the DoppIer haIfwidth reIated to T and the
atomic mass M by the equation:

d
= 7.16 x 10
7

0
( T/M )
1/2
(8)
The Iine is thus shown to have a Gaussian profiIe. It is
possibIe to caIcuIate the vaIues of
d
at 2000, 2500 and
3000 K and the Iine widths for these temperatures are of
the order of 30-50 mA.
0
29
PRESSURE BROADENING
Since the atoms in the vapour state are in a perpetuaI
state of motion, coIIision of atoms is inevitabIe
causing radiation quanta of sIightIy differing
frequencies to be absorbed or emitted. SeveraI types
of particIes may be invoIved in the coIIisions.
Interaction of eIectricaIIy charged particIes causes
Iine broadening known as 'Stark effect'. CoIIisions
with uncharged atoms Iead to van Der waaI's effect.
CoIIisions between atoms of the same type Ieading to
resonance broadening effect is referred as
'HoItsmark' effect. Since it is difficuIt to differentiate
between these three effects they are coIIectiveIy
referred as 'Lorentz' broadening.
30
The broadening of spectraI Iines reduces the Iifetime of the excited
state of the atoms. It aIso increases the Iine profiIe of the radiation.
The monochromatic absorption coefficient of the em radiation at a
waveIength is given by:
K() = K
0
/ 1 + [2 ( -
0
) L]
2
(9)
where K
0
is the maximum absorption coefficient and L is the haIf
width. The profiIe of this distribution is fIatter than DoppIer
broadening but both are aImost of the same order. The haIf width L
is thus a fraction of the frequency of coIIision (Z), which in turn is a
function of the temperature and the effective cross section defined
by:
= Z
0
2
/ C (10)
31
It may be noted that both DoppIer and Lorenz
broadening occur simuItaneousIy resuIting in a simiIar
but broader profiIe known as Voigt profiIe (K) which
may be mathematicaIIy expressed as:
(11)
Where a =
L
/
D
( In 2 )
1/2
,
w = -
0
/
D
2 (In 2 )
1/2
,
y = 2 /
D
(In 2 )
1/2
and
= distance to the point at which K() and
K
0
are the caIcuIated and the maximum
vaIue of the coefficient.
dy y) - (w a / e / a K ) (
2 2
-
y2 -
o

K
32
The curves are symmetricaI with a maximum at
0
.
Apart from DoppIer and Lorenz effects, Iine broadening
aIso occurs due to hyperfine structure exhibited by
many resonance Iines due to nucIear spin. Isotope shift
of the resonance Iines aIso contributes additionaIIy
to the Iine broadening. These effects are aIso
significant but not as prominent.
In essence, the sum totaI of aII these Iine broadening
effect is of the order of 0.0005-0.005nm, which
increases with increasing temperature and pressure.
The significance of peak width at haIf the peak height
has a profound effect on the emission characteristics
of radiation sources, (especiaIIy hoIIow cathode Iamps)
which wiII be discussed Iater.
33
MEASUREMENT OF ABSORPTION
Based on quantum physicaI description given earIier,
rigorous mathematicaI expressions have been derived
to determine the absorption coefficient, its variation
with N.f.I, effect of monochromator band width and
aIso of opticaI density. However, for practicaI
anaIyticaI purposes a physicaI understanding of these
phenomena is more reIevant which may be
Interpreted as foIIows.
34
A very narrow frequency intervaI is essentiaI for the
absorption of resonance radiation. However, it is
impossibIe to isoIate and obtain high intensity of
iIIumination in the range of 0.0005 - 0.005 nm from
continuum radiation sources. It wouId be too weak to
be of any practicaI use. To overcome this difficuIty, WaIsh
recommended that the radiation source shouId be made
of the anaIyte eIement onIy. Therefore onIy the resonance
Iine need to be separated from other spectraI Iines by a
monochromator.
35
Assuming that a monochromator isoIates a spectraI band
S covering the absorption Iine
0
(resonance Iine), the
totaI spectraI energy received by the detector is :
(13)
= I
0

S
(14)
= Area of the rectangIe ABCD

2 /
2 /
0 0
0
0
d I
S
S
I

36
Now if a homogeneous gas having an absorption K()
is interposed in a Iength of the radiation beam, the
energy within the band wiII decrease by the same
amount but the spectraI profiIe wiII have the same
shape.
37 37
Instead of considering the radiation per unit voIume, if
the totaI radiant fIux () is considered, then it may be
proved that the absorption factor and hence opticaI
density is proportionaI to the concentration of the free
atoms and to the path Iength in the absorbing medium
provided that the concentration is Iow and the spectraI
bandwidth is narrow. This is nothing but Beer - Lambert's
Iaw which can be expressed as:

tr
=
0
e
-x
v
N I
(16)
Where
0
and
tr
are the radiant fIuxes before and after
absorption in the path Iength I, x
v
is the spectraI
absorption coefficient and N is the number of atoms.
38 38
This expression may be rearranged in the famiIiar form,
Absorbance = A = Log
0
/
tr
= 2.303 x
v
N L (17)
The totaI number of free atoms in opticaI path cannot
be determined but it is not necessary for routine
appIications, as atomic absorption is a reIative
technique Iike any other spectroscopic techniques.
39 39
The physicaI conditions for highest sensitivity may be
summarized as foIIows:
The absorption Iine shouId have Iowest energy state and
highest popuIation of the atoms in the ground state.
If severaI resonance Iines are there, the one with highest
osciIIator strength has to be chosen.
EmpIoying a source of radiation, that emits a Iine of the
same waveIength but with Iower haIf width.
Path Iength may be increased within practicaI Iimits in
the absorbing medium since B-L Iaw states that the
absorption aIso increases according to the path Iength.
40 40
EmpIoying these conditions, we can in principIe, construct
an atomic absorption spectrometer using a hoIIow cathode
Iamp made of the same eIement as the anaIyte, an atomizer
to produce a popuIation of ground state atoms, a
monochromator with an entrance and exit sIit for coIIection,
dispersion and seIection of resonance Iine, a detector for the
measurement of radiation intensity foIIowed by an ampIifier
and a read out device. A schematic diagram of such a
system is shown here.
Source
Absorption
CeII
Monochromator Detector
AmpIifier DispIay
41 41
Depending upon the choice of the components and method of
operations severaI variants of atomic absorption spectrometers
resuIt, which are enumerated beIow,
1) SingIe beam DC instrument - This is the simpIest arrangement.
The earIiest AAS instruments were of this type.
2) SingIe beam AC instrument - By appIying the puIsed current to
the radiation source or by mechanicaIIy chopping the radiation
before it enters the absorption ceII.
3) DoubIe beam AC instrument - By using a rotating mirror/chopper
arrangement, the radiation is passed aIternateIy through the
fIame and around the fIame. Then it is possibIe to construct a
doubIe beam instrument. Both beams are recombined by a
semitransparent mirror pIaced behind the fIame. The eIectronics
of the system is designed to yieId directIy the ratio of the
transmitted radiation fIux to that of the incident radiation. The
stabiIity is aIso better.
42
SCHEMATICS OF ATOMIC ABSORPTION
SPECTROMETERS
43 43
4) MuIti eIement SimuItaneous AAS - Use of radiation
sources containing resonance Iines of severaI
eIements focused in to the absorption ceII permits
simuItaneous determination of severaI eIements.
However the optics and eIectronics need to be
suitabIy modified to handIe various signaIs readout
and printouts.
5) EIectrothermaI AAS - By substituting the absorption
ceII (i.e fIame) with an eIectricaIIy heated graphite
furnace, very efficient means of producing atomic
vapor can be achieved. This technique has gained
wide popuIarity since Iast 15 years permitting the
quantitative determination in ppb IeveIs (10
-9
g).
44 44
6) Hydride Generation AAS - Arsenic, antimony,
bismuth, seIenium, teIIurium, germanium, Iead etc,
are capabIe of forming their respective hydrides in
acidic medium. These compounds easiIy dissociate
into their metaIIic and non-metaIIic components
which, when introduced into the fIame (absorption
ceII ), permit not onIy their separation but aIso
estimation in ppb IeveIs (10
-9
g).
7) Mercury coId vapor AAS - Mercury has a unique
property of being reduced to metaIIic form directIy
from its combined state and aIso has a significant
vapor pressure which permits its determination at
room temperature. It onIy needs to be transported
to the absorption ceII. This technique is known as
coId vapor technique.
45 45
Over the years atomic absorption spectrometry as an
anaIyticaI technique has been accepted as a standard
method of anaIysis aII over the worId. An enormous
amount of Iiterature on the instrumentation, radiation,
sources, atomization techniques, optics, signaI handIing
and data presentation has been deveIoped. The advent
of computers has made it possibIe for maximum use of
automation, instrument controI and statisticaI data
evaIuation. On an average, more than 500 research
papers are being pubIished on the appIication of AAS to
various matrices every year.
Now we shaII discuss the detaiIed aspects of atomic
absorption spectroscopy.
46
AAS is the measurement of the absorption of em radiation
by the atoms in the gaseous state.
Free atoms do not undergo vibrationaI & rotationaI
transitions but onIy eIectronic transitions. Such excited
eIectron may return to ground state by atomic
emission, atomic fIuorescence or atomic absorption
phenomena.
The various energy states of an atom are described by n,I
and inner quantum number J.
SeIection ruIes permit L = 1 and n = any number.
47
For sodium atom the most IooseIy bound eIectron is
designated by,
3s
2
S
1/2
3 p
2
p
1/2 ,3/2
589.593 nm / 588.996 nm
4 p
2
p
1/2,3/2
330.294 nm / 330.234 nm
n p
2
p
1/2,3/2
In emission spectrum aII possibIe Iines are obtained.
48
Since aII eIements can be excited to their next higher
energy IeveI ,in theory any eIement can be determined by
atomic absorption spectrometry.
However, beIow 200 nm, anaIysis of As, Se, I, S , P etc., is
difficuIt owing to the incipient absorption by oxygen and
hot fIame gases. Cerium ,Thorium and other refractive
eIements aIso present difficuIty. ArtificiaI and radioactive
eIements can not be anaIyzed by atomic absorption
spectrometry.
49
THERMAL EXCITATION
It must be appreciated that for atomic absorption to occur ,
we have to produce a popuIation of atoms in the ground
state. This can be achieved by exposing a sampIe of the anaIyte
to high temperatures. At high temperatures prevaiIing in the
fIames, compounds decompose into ions, which in turn pick up
eIectrons to produce atoms.
The ratio of number of atoms N
j
in an excited state j to the
number of atoms in the ground state N
0
is given by,
N
j
P
j
N
0
P
0
where P
j
& P
0
are the statisticaI weights of the excited and
ground states , k is the boItzmann's constant and T is the
absoIute temperature .
=
. e
-Ej/KT
50
Since this equation is inverseIy proportionaI to the
absoIute temperature, increase in N
j
/N
0
with T is
exponentiaI. However N
j
is aIways smaII compared to
N
o
. Therefore N
j
can be negIected and we can
assume that the number of atoms in the ground state is
independent of the energy of the excitation E
j
and
nominaI temperature of the fIame.
ExampIe : Iet us caIcuIate the number of atoms in the
cadmium excited state.
For nS
1/2
n P
3/2
transition occurs at 228.8nm.
51
Pj /Po = 3
= c / = 2.998 x 10
10
cm /sec = 1.310 x 10
15
sec
-1
2.288 x 10
-5
cm
E
j
- E
o
= h = 6.626 x 10
-27
erg.sec x 1.310 x 10
15
sec
= 8.682 x 10
-12
erg
N
j
/ N
o
= 3 exp -8.682 x 10
-12
erg
1.3805 x 10
-16
erg k
-1
(2730) k
= 4.5 x 10
-11

52
At the hottest fIame temperature of ~ 4000 k, the popuIation of the excited
state atoms is very smaII. Given beIow are the aIkaIi and aIkaIine earth
metaI characteristics at different temperatures.
6.65x10
-7
4.82x10
-10
3.82 3248 Cu
1.50x10
-7
3.35x10
-11
4.35 2852 Mg
6.04x10
-4
3.69x10
-5
1.21x10
-7
2.93 4227 Ca
4000 k 3000 k 2000 k ev Resonance
Iine
EIement
1.48x10
-6
5.38x10
-10
7.29x10
-15
5.80 2139 Zn
1.31x10
-6
2.29x10
-9
3.33 3720 Fe
4.44x10
-3
5.88x10
-4
9.86x10
-6
2.11 5890 Na
2.98x10
-2
7.24x10
-3
4.44x10
-4
1.46 8521(nm) Cs
53
In emission, one measures the difference between zero
signaI and the sampIe signaI. The Iimit of detection is
governed by eIectricaI noise.
In AAS, the difference between the noise IeveI of the
bIank & finite signaI is measured. Hence sensitivity is
governed by noise IeveI of the signaIs.
54
Free atoms do not undergo vibrationaI and rotationaI
transitions. They undergo eIectronic transitions
onIy. The excited eIectrons may return to the ground
state by atomic emission, or by atomic fIuorescence or
by atomic absorption.
Atomic absorption spectrometry invoIves the
measurement of the absorption of eIectromagnetic
radiation by the atoms in the gaseous state.
If the excitation is by opticaI radiation the atoms
absorb the radiation of definite frequency. The
absorbed energy is subsequentIy in the form of heat.
55
The absorption spectrum of an eIement consists of a
number of Iines which appear cIoser and cIoser
together and decrease reguIarIy in intensity untiI the
Iines merge together and onIy continuous absorption
is observed.
In the spectrum of sodium so far 57 absorption Iines
have been observed. In contrast, emission Iines are
more numerous and do not exhibit the same reguIarity
of the absorption spectrum.
56
The energy IeveI diagram for sodium is shown here.
Each Iine represents an energy IeveI.
SPECTROSCOPIC CONSIDERATIONS
57
If the sodium vapour is excited thermaIIy using a hot fIame or
eIectricaIIy terms with arbitrary n and I can be attained and the
emission spectrum can contain aII the emission spectrum can
contain aII the Iines starting from 3s
2
S
1/2
. SimiIarIy compIex
emission spectrum can be obtained for aII other eIements.
The energy IeveI diagram of sodium indicates that atomic
absorption can occur onIy for those Iines which originate from
the ground term of the neutraI atom. These Iines are caIIed as
resonance Iines since they can come into resonance with
opticaI radiation of suitabIe frequency. The most intense and
easiIy excited Iine shouId be of Ieast energy and hence Iowest
frequency. This is a very simpIe and cIear cut situation
appIicabIe onIy to very simpIe atoms. For transition eIements
the exact resonance Iine is more compIex and usuaIIy
determined by experiment.
58
In order to anaIyze a spectrum it is necessary to know
which spectraI term corresponds to the spectraI Iines.
This information is provided by the seIection ruIes of
LS coupIing(J) where J vaIue has to change by 1 unit
and n, the vaIue of the principIe quantum number can
aIter by any amount.
59
Let us recapituIate our knowIedge about the energy
states of an eIectron in an atom. They are defined by
four quantum numbers n, I , m and s.
The state of an eIectron in an atom is described by L,S
and J.
The orbitaIs of an eIectron in any atom have shapes of
s,p,d,f and g aIbeit with variance in their energy IeveIs.
The magnetic quantum number m
I
can assume 2I+1
integer vaIues from -I to +I. the magnitude of the
anguIar momentum vector is given by
2 / . ) 1 ( h l l
60
Spin anguIar momentum (s) is aIso quantized
according to
The quantization Iaw for spin momentum is that the S
z
can have haIf integraI muItipIes of h/2 so that S
z
have
vaIues of +1/2 or -1/2 onIy (S
z
= 1/2).
TotaI anguIar momentum (j) of one eIectron is the
vector sum of I & s. Thus
j = I + s
2 / 1) s(s h s
61
The totaI anguIar momentum quantum number is given
by,
j can have z components defined as
j
z
= j , (j-1) , (j+2) ...1/2
when I = 1 and s = , j can have vaIues 3/2 or 1/2
Since j
z
= I
z
+ s
z
the summation of z components yieIds,
j
z
= 1+1/2 , 1-1/2, 0+1/2, 0-1/2, -1+1/2 and -1-1/2
= 3/2 , 1/2, 1/2, 1/2 , -1/2 , -1/2 and -3/2
h/2 1) j(j j
62
Thus for p eIectron ( I = 1), the orbitaI and spin momenta
combine to give a totaI momentum of j = 1/2 15
(when I & s reinforce) or 1/2 3 when I and s oppose each
other. These states spIit into doubIet with sIightIy
deferring energies and represented as
2
P
3/2
or
2
P
1/2
.
SimiIarIy for I= 2,3,4 we get doubIets (
2
D
5/2,3/2
)
(
2
F
7/2
,
2
F
5/2
),(
2
G
9/2
,
2
G
7/2
) etc.
63
The totaI orbitaI anguIar momentum of an atom is the
vector sum of aII quantized anguIar momenta of
individuaI eIectrons. These states are aIso quantized.
The orbitaI anguIar momentum can interact with the
magnetic moment due to spin. This is termed as
RusseI Saunders coupIing(RS) or simpIy LS coupIing.
The LS interaction gives muItipIe spIitting of each term.
The coupIing scheme for heavy atoms is caIIed jj
coupIing.
64
n=1 1s
2
S
1/2
n=2 2s
2
S
1/2
2p
2
P
1/2
;
2
P
3/2
n=3 3s
2
S
1/2
3p
2
P
1/2
;
2
P
3/2
3d
2
D
3/2
;
2
D
5/2
n=4 4s
2
S
1/2
4p
2
P
1/2
;
2
P
3/2
4d
2
D
3/2
;
2
D
5/2
4f
2
F
5/2
;
2
F
7/2
n ns
2
S
1/2
np
2
P
1/2
;
2
P
3/2
nd
2
D
3/2
;
2
D
5/2
nf
2
F
5/2
;
2
F
7/2
L =0(s) L = 1(p) L = 2(d) L=3(f)
LS COUPLING FOR S AND P ELECTRONS
65
TERM SYMBOLS
1. II coupIing : OrbitaI anguIar momentum of eIectrons
are added vectoriaIIy and the resuIting L vaIues are
designated as S,P,D,F and G.
2. ss coupIing : Spin anguIar momentum of individuaI
eIectrons are added vectoriaIIy to give totaI s.
S = (s
1
+s
2
), (s
1
+s
2
-1), ....s
1
-s
2

The muItipIicity of the term is then(2S+1)

66
3. LS coupIing
J = (L+S) , (L+S-1)..L-S
The J vaIue is subscripted to the Ieft of the term symboI.
4. The term symboI for a particuIar atomic state is
expressed as
2S+1
L
J
ExampIe : Derive the term symboIs for carbon atoms (p
2
)
SoIution : C 1s
2
, 2s
2
, 2p
2
For two equivaIent eIectrons I
1
= I
2
= 1 and s
1
= s
2
= 1/2
67
Hence,
L = 2,1,0 and S = 1,0
Terms corresponding to these vaIues are caIcuIated by
spin muItipIicity (2s + 1).
For S = 1, spin muItipIicity is 3 (tripIet)
S = 0, spin muItipIicity is 1 singIet
Hence we get 6 states defined by 3
D
, 3
P
, 3
S
and 1
D
, 1
P
and 1
S
68
Corresponding J vaIues wiII be:
3D with J vaIues of 3,2,1; give rise to 3D
3
, 3D
2
and 3D
1
3P with J vaIues of 2, 1, 0; gives rise to 3P
2
, 3P
1
and 3P
0
3S with J =1 ; gives rise to 3S
1
1D with J = 2 ; gives rise to 1D
2
1P with J = 1 ; gives rise to 1P
1
1S with J = 1 ; gives rise to 1S
0
69
The corresponding energy IeveI diagram of sodium can
be shown to contain 56 transition Iines for sodium,
106 for Iithium, 124 for potassium and 294 for rubidium
etc.
70
SCHEMATIC DIAGRAM OF ATOMIC
ABSORPTION SPECTROMETER
Source Detector
Absorption
ceII
Monochromator
AmpIifier DispIay Data handIing
71
1. RADIATION SOURCES
1.1 HOLLOW CATHODE LAMPS
72
A hoIIow cathode Iamp (HCL) consists of a
gIass cyIinder fiIIed with an inert gas (neon or
argon) under a pressure of 1-5 torrs into which
an anode and a cathode are fused. The cathode
is made of the anaIyte eIement in the form of a
cyIinder and the anode is a thick wire usuaIIy
made of tungsten or nickeI.
73
A voItage of severaI hundred voIts is required to Iight
the Iamp. The appIied voItage generates 5 -15mA current
and sets up a gIow discharge of the carrier gas. A
stream of positive ions strikes the cathode and reIeases
the atoms of the cathode materiaI by coIIisions. This
process is known as sputtering. These atoms contain
atoms in the excited states which emit their
characteristic radiation as they return to the ground
state. EventuaIIy the metaI atoms diffuse back on to the
cathode surface or redeposited on the gIass waIIs of
the tube.
74
The cyIindricaI configuration of the cathode
concentrates the emitted radiation and enhances the
possibiIity of reposition of the atoms on to the cathode
rather than the gIass waIIs.
The efficiency of the HCL depends upon the geometry
and operating voItage. Higher the voItage, higher the
current and greater is the intensity. This advantage is
some what offset by an increase in DoppIer broadening
of the emitted radiation. Further increased number of
unexcited atoms in the gas cIoud in turn are capabIe of
absorbing the same excited radiation. This process is
known as 'seIf reversaI' and Iowers the intensity of the
emitted radiation.
75
A variety of hoIIow cathode Iamps for most of the
eIements are avaiIabIe commerciaIIy. By using an aIIoy
of 2-5 metaIs as cathodes more muIti eIement
determination is possibIe.
76
1.2 VAPOUR DISCHARGE LAMP
77
Very voIatiIe materiaIs Iike mercury, thaIIium, zinc,
aIkaIi metaIs can be determined using Iow pressure
vapour discharge Iamps. They can Iow cost and give
high radiant intensity. They emit strongIy broadened
Iines owing to seIf absorption and seIf reversaI.
Therefore VDLs must be operated as highIy reduced
currents. However this Ieads to instabiIity of the Iamp.
78
1.3 ELECTRODELESS DISCHARGE LAMP
Quartz Window
Ceramic HoIder
RF CoiI
Lamp
79
EIectrodeIess discharge Iamps (EDLs) exhibit highest
radiant intensity and narrowest Iine widths compared
to HCLs. They consist of a seaIed quartz tube of 5-10
mm dia and 4-5 cm Iength, fiIIed with a few miIIigrams
of the anaIyte eIement or its saIt. The tube is fiIIed with
argon.
The Iamp contains no eIectrode but it is energized by
an intense fieId of radio frequency. The tube is mounted
within the coiI of a high frequency generator 2400 (MHz)
and excited by an output of about 200 watts. Ionization of
argon takes pIace.
80
EDLs are ideaI for eIements whose resonance Iines are
beIow 200 nm. Such eIements incIude As, Se, P. EDLs
are now avaiIabIe for most of the voIatiIe eIements
incIuding Cs, Rb. The detection Iimits with EDLs are
2-3 times Iower than HCLs. They are aIso very stabIe
during operation and have Iong Iife times. HCL and
EDLs are compIementary to each other.
81
1.4 CONTINUUM SOURCES
Continuum spectrum of hydrogen , xenon and haIogen
Iamps offer good stabiIity. They are cost effective and
exhibit muItieIement capabiIity. However owing to the
Iow intensity of the chosen waveIength, high demands
on the monochromator to produce 0.002 nm waveIength
accuracy, risk of spectraI interferences etc., they have
not become popuIar.
82
2. ATOMIZERS
Atomizers transform a Iiquid sampIe into atoms. This is
easiIy accompIished by spraying the anaIyte soIution
into a fIame where the ions or moIecuIes are converted
into atoms. Other techniques of atomization incIude
eIectro thermaI evaporation, hydride technique and
coId vapour technique which wiII be discussed Iater.
The success or faiIure of AAS determination is virtuaIIy
dependent upon the efficiency of atomization i.e the
totaI number of atoms that are formed.
83
Numatic nebuIizer is very usefuI to spray the sampIe into a
fIame in a continuous manner to maintain a steady suppIy of
atoms. UsuaIIy nebuIizers are connected to the fIame
burner which can be considered as a singIe unit even
though, both parts are detachabIe and serviced
independentIy and reconnected. TypicaI design of a Laminar
fIow burner is shown here.
Laminar fIow burner uses a concentric tube nebuIizer
in which oxidizer and the fueI gas combine to produce
an aerosoI of the sampIe. The sampIe passes through a
number of baffIes and fIow spoiIers. OnIy the fine mist
and mixture of gases are Ied into a sIotted burner of 5 cm
width. The fIame height is approximateIy 5 - 10 cm.
84
NEBULIZER AND BURNER
85
Both the fueI and the oxidant fIows are independentIy
and accurateIy controIIed and combined in stoichiometric
proportions. FIow rates are usuaIIy controIIed by doubIe
diaphragm pressure reguIators foIIowed by needIe vaIves.
Rotameters are used to adjust the gas fIows to the desired
voIumes.
The nebuIizer - fIame combination is of two types:
Pre-mix burner and totaI combustion burner.
86
Pre-mix burner TotaI combustion burner
Laminar fIow, controIIed. Entire sampIe is aspirated.
Uniform dropIets. Oxidant - FueI gas ratio is
Low turbuIence and Iess fixed.
eIectricaI noise. CooIing and Ioss of
dropIets.
High soIids cIog the burner. Noisy fIames.
ExpIosion hazard. FIow rate is 1mI/min.
FIow rate is 3 - 10 mI/min. High soIids can be
handIed.
Atomization efficiency 10 -15%. Low S/N ratio.
COMPARISION OF PRE-MIX AND TOTAL COMBUSTION
BURNERS
87
TYPES OF FLAMES
Common fueIs and oxidants used in AAS are Iisted beIow.
88
FLAME STRUCTURE
89
A typicaI fIame structure contains a primary combustion
zone, inter zonaI region and the secondary combustion
zone. The primary combustion zone is bIue in coIour due to
the band emission of C
2
, CH and other radicaIs. This region
is not of anaIyticaI interest because thermaI equiIibrium
conditions are not obtained here.
The interzonaI area has a height of severaI centimeters. It
contains free atoms and stabIe moIecuIar oxides.
In the secondary combustion zone, the products of
interzonaI area are dispersed into the surroundings.
90
TEMPERATURE ZONES IN A FLAME
91
FLAME ABSORPTION PROFILE
92
Air - acetyIene fIame is the most common fIame used
in AAS. This fIame is compIeteIy transparent above 230 nm
but shows about 65% absorption around 193.7nm. NormaI
temperatures of 1100
0
C - 2400
0
C are obtained which is
quite sufficient for the atomization of most eIements
except refractory sampIes. AIkaIi metaIs do ionize to an
appreciabIe extent at these temperatures. This fIame is
operated under stoichiometric or weakIy oxidizing
conditions (excess of air) for Au, Ir, Pd, PI, rh. AIkaIine
earth metaIs are determined in a sIightIy reducing fIame
(excess of fueI gas - green or bIue fIame).
93
An important deveIopment in AAS is the introduction
of nitrous oxide/ acetyIene fIame operated with a sIight
excess of fueI gas. This fIame has a 2 - 4 mm high
bIue - white primary reaction zone above which 5 - 50 mm
red reducing zone is present. The red reducing zone is
suitabIe for the anaIysis of refracting eIements such as
Mo, W, V and rare earth eIements. It is IargeIy free of
interferences. The burning fueI produces a carbon
monoxide environment according to the reaction,
3N
2
O + C
2
H
2
2CO + 3N
2
+ H
2
O
94
Nitrous oxide - acetyIene fIame has two disadvantages:
Due to high temperatures (2550 - 2800
0
C) appreciabIe
ionization occurs for many eIements resuIting in Iowered
sensitivity.
The fIame aIso emits strong broadband emissions of CN,
CH, NH bands which can introduce errors due to their
contribution at the anaIyticaI Iine. It aIso introduces
"emission noise" which can affect the precision of the
anaIysis.
95
In addition to the composition of the gas mixtures, their
burning veIocities are aIso important. If the gas fIow rate
does not exceed the burning veIocity, the fIame
propagates back into the burner giving a 'fIashback'.
At high fIow rates, the fIame rises and eventuaIIy
reaches a point where it bIows off the burner. Therefore
it is very important to adjust the fIow rate of the
fueI - oxidant mixture untiI it reaches a point above
the burner where fIow veIocity and burning veIocity are
equaI.
96
ATOMIZATION PROCESS
97
The atomization step converts the anaIyte within the
aerosoI into free ground state atoms. Various process
occur during the conversion. These incIude:
DesoIvation
VoIatiIization
Dissociation
Excitation
With so many processing occurring, it is not
surprising that atomization is the most criticaI step in
fIame AAS which determines the sensitivity and
precision of an anaIysis.
98
FLAME TYPES
1. TurbuIent - FIow Burner
The characteristic of this type of burner is that the fueI gas
and the combustion supporting gas are not mixed untiI the
point at which they enter the fIame and the soIution to be
sprayed is aIso introduced at this point. Thus the burner is
actuaIIy a combination nebuIizer burner. It is aIso known as
'direct injection' or 'totaI consumption' burner since aII the
aspirated Iiquid enters the fIame and is converted into a
spray at the point of entry. SeveraI workers have used it for
atomic absorption . The turbuIent fIow burner gives a taII
narrow fIame which provides a very short Iight path for
atomic absorption.
99
A typicaI burner consists of a tube usuaIIy made of
titanium or stainIess steeI or other chemicaIIy resistant
and non - corrosive metaI, containing either an array of
hoIes or grooves as a sIot in order to minimize saIt
deposition , as the underside of the burner surface and
aIso to ensure stabIe absorption reading.
100
TURBULENT - FLOW BURNER
101
An ingenious way of utiIizing the height of the fIame to
achieve Iong Iight-path and hence greatIy improved
sensitivity is to direct the fIame into a tube, made of
suitabIe heat resistant materiaI such as quartz or
ceramic.
The Iong tube technique is IikeIy to be used for those
metaIs which do not readiIy form oxides in the fIame.
Sensitivities of 10-100 times those obtainabIe in an
ordinary fIame have been reported for Cd, Zn and the
nobIe metaIs.
102
The requirement that the Iight beam must pass entireIy
through the fIame, Iimits the geometry of the Iatter
somewhat. IdeaIIy, the Iight beam shouId be very narrow to
aIIow the use of a fIame burning at a Iong, narrow sIot
which wiII give highest sensitivity. The need for the
monochromator to accept sufficient height to give a
satisfactory signaI-to-noise ratio usuaIIy means that a
Iight beam of finite width is required and this needs a short
wider fIame.
103
The turbuIent - fIow burner gives a fIame, which is taII
and narrow. WhiIe ideaI for AAS, it provides a much
shorter Iight path and hence exhibits poorer sensitivity
than a Iaminar- fIow burner. The uptake of soIution by
the turbuIent fIow burner is usuaIIy Iess than that of the
Iaminar fIow system and since aII the aspirated soIution
enters the fIame, it shouId be a more efficient producer of
atoms than the Iaminar - fIow system. However, there is
evidence that some of the aspirated Iiquid in the totaI
consumption burner passes through the fIame without
being fuIIy vaporized.
104
OPTICAL COMPONENTS
AAS covers the UV-visibIe waveIength range. It is
necessary to empIoy proven monochromators in AAS,
since atoms are onIy capabIe of absorbing radiation within
a very narrow frequency intervaI. The sources are found to
be weak if the intervaI of interest is considered. For this
reason, some authors recommend that the radiation source
used for absorption measurement shouId aIso emit the
spectrum of the eIement to be determined. With such an
arrangement the required resonance Iine mereIy has to be
separated from other spectraI Iines of the same eIement by
means of a monochromator.
105
ABSORPTION MECHANISM
106
The spectrum of the eIement under study is emitted
from the HCL. In the fIame, a portion of the resonance
Iine, corresponding to the concentration of this eIement
is absorbed. Lines that do not occur in absorption are
not attenuated. After dispersion of the radiation in a
monochromator, the resonance Iines are separated by
the exit sIit and aII other Iines are masked.
One of the greatest advantages of AAS nameIy its
specificity is based on the use of specific radiation
source that emits the spectrum of the anaIyte eIement in
the form of very narrow spectraI Iines. The abiIity of
AAS to differentiate between different eIements is soIeIy
dependent on the haIf intensity widths of the emission
Iines (0.002-0.005nm). This range Iies beyond the scope
of the resoIving power of normaI monochromator.
107
When hoIIow cathode Iamp is used as a source of radiation
the monochromator in AAS has the important task of
separating the resonance Iine of anaIyte eIement from other
emission Iines of the source. If sIit widths are Iarge in AAS,
Iower sensitivity and increasing non-resoIved muItipIets
resuIt (severaI resonance Iines passing through the exit sIit).
It is observed that for a number of eIements a spectraI
band pass of 0.2 nm is necessary to obtain good
sensitivity and Iinearity of anaIyticaI curve. For other
eIements the resonance Iine is more or Iess separated
so that Iarger sIit width can be used without disadvantage.
108
FoIIowing figures show the infIuence of the spectraI band
pass width on the sensitivity, signaI-to-noise ratio and
curvature of anaIyticaI curve. Resonance Iines of siIica
Iie between 250 - 253nm. With a sufficientIy smaII sIit
width every resonance Iine gives a Iinear anaIyticaI curve
within the observed range.
109
RESONANCE LINES OF SILICA
110
ANALYTICAL CURVE OF THE RESONANCE LINES
111
The signaI to noise ratio is optimum at a spectraI band
pass of 0.2nm and cIearIy decreases on both sides as
shown in figure,
S\N
112
Two requirements have been pIaced on the monochromator
of an AAS. FirstIy a spectraI band pass of 0.2nm is required
and secondIy the entrance sIit shouId have as wide a
geometric width as possibIe. However, the entrance sIit and
exit sIit of the monochromator must have the same
mechanicaI dimensions. In AAS, the image of the radiation
source is found at the entrance sIit, (radiation beam of
severaI nm faIIs on the sIit). It can be seen from the figure
that the geometric width of the entrance sIit determines the
amount of radiation that faIIs on the dispersing eIement and
subsequentIy on the detector. This means that the noise
aIways accompanying the signaI is reIativeIy smaII
compared to the signaI. At the same time Iower
ampIification can be empIoyed so that contribution to the
noise are reduced. For the anaIyst, Iow noise means a
stabIe signaI and hence good precision and Iower detection
Iimit.
113
IMAGE OF THE RADIATION SOURCE ON THE
ENTRANCE SLIT
114
PRISMS AND GRATINGS
They serve to disperse the radiation into individuaI
waveIengths. Prism based monochromators are
waveIength dependent at a fixed geometric sIit width. In
gratings, monochromators are dependent on the grating
constants and these improve as the number of Iines
passing increases.
The two most important mountings are the simpIe
Littrow (A) monochromator and modified Czerny-
Turner (B) form.
115
LITTROW MONOCHROMATOR
116
CZERNY- TURNER MONOCHROMATOR
117
In this connection, it shouId be mentioned that fiIter
monochromators cannot be empIoyed in atomic
absorption spectrometry, since the required resoIution
cannot be obtained Ieading to the difficuIties
mentioned above.
The opticaI requirements for AAS are simpIe. From the
fIame, radiation is passed through mirrors/Iens
combination. Focusing the radiation from the fIame to
monochromator in AAS is aIso simpIe. From the
materiaIs standpoint, quartz or fused siIica Ienses are
required because of the UV transmission characteristics.
118
SPECTRAL BAND SELECTION
The term monochromator is in reaIity, a misnomer.
Monochromatic radiation is the radiation with onIy one
waveIength. AII spectraI band seIection devices pass a
band of waveIengths that may be Iarger or smaIIer according
to the quaIity of the device.
The basic requirement for a waveIength seIector is the
abiIity to separate the desired resonance Iine from other
Iines emitted by the sharp-Iine source. If any background
radiation is emitted by the source, a curved caIibration
graph wiII be obtained, but curvature can be minimized by
using a narrow-pass monochromator to reduce the
propagation of unabsorbed Iight.
119
For aIkaIi metaIs a simpIe gIass or geIatin fiIter shouId
be sufficient. For other metaIs interference fiIters are
satisfactory. Sets of fiIters with seIected cut-offs are
commerciaIIy avaiIabIe.
The commonest and most versatiIe waveIength seIector
is a monochromator which can be set to pass any
waveIength between 200-900 nm simiIar to an ordinary
spectrophotometer.
120
DETECTION SYSTEM
A detection system incIudes the detector, associated
power suppIies, an ampIifier and read out devices. The
read out devices incIude anaIog meters, digitaI meters
or strip chart-recorder. However , today computers are
incorporated in aII but the Ieast expensive, bottom of
the Iine instruments.
121
DETECTORS
The intensity of the resonance Iine emitted by the
monochromator is measured with and without sampIe in
the fIame by photoeIectric detector such as photomuItipIier
or photoceII. A photomuItipIier tube is essentiaI if best
resuIts are to be achieved in the determination of metaIs.
However, for generaI use it is desirabIe to moduIate the
output of the Iight source either with mechanicaI "chopper"
or more convenientIy by suppIying the source with AC or
moduIated DC, and feeding the detector output to an
AC ampIifier which is rectified before being fed to a meter.
In this way any signaI caused by continuous emission from
the fIame is rejected.
122
However, any fIuctuation in fIame emission may give rise
to an appreciabIe AC component and it is best to tune the
ampIifier fairIy cIoseIy to the moduIation frequency of the
Iight source.
In singIe beam AAS instruments the accuracy of
absorption in measurement is Iimited by the fIuctuation and
drift in the Iight source. Therefore a doubIe beam technique
is preferabIe. In such instruments the Iight from HCL is spIit
into a sampIe beam moduIated at a frequency 'f' which is
passed through the fIame and the reference beam is
moduIated at frequency '2f' which is passed through an
equivaIent air path. SubsequentIy the two beams are
combined at the exit sIit of the monochromator and the
photomuItipIier output is fed to an ampIifier.
123
The ampIifier signaIs from two beams are separated
and their ratio is recorded on the pen recorder.
The demand for rapid routine anaIysis of Iarge number
of sampIes has Ied to the deveIopment of digitaI read-out
and print outs whose output can be read directIy in
concentration units. These devices are used in conjunction
with an automatic sampIing device, so that the instrument
can work unattended for considerabIe period of time.
124
The PMT (photomuItipIier tube) has the abiIity to
transduce radiation into an eIectricaI signaI with very
high gain (of the order of 10
6
). FIuctuations in the number
of atoms in the fIame dominate the noise in these systems.
The shot noise associated with PMT's is an insignificant
noise source for the system. Modern PMT's exhibit very
good spectraI response throughout the UV-visibIe range.
TiII date no other detectors have been used in commerciaI
instruments.
125
READ OUT ELEMENTS
The most common type of ampIifier eIectronics used in
AAS is the Iock-in ampIifier. This type of device "Iocks
in" on any signaI of a specific moduIation frequency,
and therefore does not respond to signaIs at other
frequencies. The radiation from the source (HCL or
fIame) is moduIated at a fixed frequency that is
synchronized with Iock-in ampIifier. This means that
onIy signaIs of interest are ampIified and the signaI to
noise ratio wiII be improved. The ampIified signaIs can
then be fed into a strip chart recorder or meter for
evaIuation. In more modern instruments it is converted
into a digitaI signaI and is fed to a computer for
evaIuation.
126
COMPUTERS
Most of the commerciaI instruments being marketed today
have a dedicated computer. This provides maximum
fIexibiIity for data evaIuation and signaI processing. In
addition, a computer gives the anaIyst many other
desirabIe features. A computer can store information
required for the instrument parameters for many eIements.
In recent advanced instruments, the computer provides
controI over the instrument variabIes and can set
variabIes to optimum conditions for a particuIar
determination. This aIso provides anaIyticaI caIcuIation,
curve fitting, concentration read out, standard addition
etc. With computer optimization program even more
sophisticated background correction and interference
correction are aIso avaiIabIe.
127
AUTOMATION
The AAS is a very rapid anaIyticaI technique that has
received greatest impetus and generaI recognition. The
first automatic anaIyzer was introduced in 1996. Courner
constructed an instrument for the anaIysis of trace
eIements consisting of a commerciaI atomic absorption
spectrophotometer to which an automatic sampIe changer,
a digitaI evaIuator and printer were connected. This aIso
consisted of an automatic diIutor, a sampIe changer, 200
sampIe viaIs, digitaI readout and a printer.
128
AII stages of an AAS determination were carried out
automaticaIIy and the resuIts were printed out directIy in
concentration units. Modern AAS are provided with faciIities
for operation with auto sampIers and often have the interface
capabiIities for direct on-Iine operation with an externaI
computer. The spectrophotometer and aII peripheraI
instruments are controIIed by a centraI processor that aIso
provides printout of a compIete anaIyticaI report.
129
Automation in fIame AAS does not bring any substantiaI
savings of time. Savings of time can onIy be expected
when severaI eIements are to be determined in the same
sampIe soIution. Automation of sampIe introduction
brings an improvement in the precision as weII as
faciIitating operation. For AAS, automation is required to
change from one eIement to the next. MuItieIement Iamps
offer certain advantages such as change of radiation
source, setting other instrumentaI parameters such as
waveIength sIit, gain etc., and performing caIibration etc.,
as these are the most time consuming procedures and
aIso most difficuIt to mechanize and automate.
130
NevertheIess, modern microprocessor technoIogy and
stepper motors for waveIength drive etc., have made
possibIe fuIIy automatic eIement change.
For simuItaneous mutieIement determination time
dependent absorbance changes are required.
131
Increasing shortage of Iaboratory staff, centraIization
of Iaboratories in Iarge agricuIturaI, environmentaI,
bioIogicaI and cIinicaI research institutes has Ied to
an increasing need for semi-automatic or compIeteIy
automatic anaIyticaI method. In order to meet this need,
a number of automatic instruments have been deveIoped
which offer considerabIe advantages compared with
manuaIIy operated instruments when Iarge number of
measurements have to be made.
132
THE TECHNIQUE OF FLAME AAS
ChemicaI anaIysis with fIame AAS is performed by
introducing standard soIutions of the anaIyte into the
fIame through a pneumatic nebuIizer into a spray chamber.
The aerosoI is carried into the fIame where a number of
processes take pIace cuIminating in the production of the
ground state atomic cIoud. The atoms absorb the radiation
and the decrease in the intensity of the incident is recorded
as the absorbance. Using the absorbance data a caIibration
curve is constructed and the sampIe concentration is
determined by referring to the caIibration curve.
133
ATOMIZATION PROCESSES
134
REACTIONS IN THE FLAME
MeX Me + X X = CI, Br, I etc.
Me Me
+
+ e
-
Me + Y MeY
Hydrated chIorides, carbonates , suIphates can form
oxides upon eIimination of HCI.
Phosphates Pyrophosphates
135
Temperature of the fIame pIays an important roIe in the
voIatiIization of saIts after which the thermaI dissociation
process of moIecuIes into atoms begins. This is a phase
where non spectraI interference occur.
In the fIame, a variety of combustion products such as
CO
2
, CO, C, H
2
O, O, H
2
, H, OH, N
2
, NO
X
etc., are present.
SoIvent and other possibIe substances aIso evaporate.
Atoms, radicaIs, ions etc., are formed by temperature
dependent equiIibrium reactions.
In principIe, the fIame can be considered as a soIvent in
which traces of metaI atoms are found which Ieads to
absorption.
136
Therefore chemicaI environment, the temperature and
the residence time of the chemicaI species have greatest
infIuence on the concentration of the atoms in the fIame.
CO and hydrogen do not have sufficient free energy to
reduce metaI oxides but during the oxidation of C or H
radicaIs enough free energy is avaiIabIe to reduce more
stabIe oxides.
C
2
and CH radicaIs are found onIy in the Iower zones of
the fIame. H radicaIs remain Ionger in the fIame and
hence they pIay an important part in the production of
atoms via thermaI dissociation.
137
INTERFERENCES IN ATOMIC ABSORPTION
SpectraI interferences
Transport interferences
SoIute - voIatiIization interferences
Vapour - phase interferences
SpatiaI distribution
138
SPECTRAL INTERFERENCES
SpectraI interferences occur in AAS when the emission
waveIength from the primary radiation source or
absorption of a concomitant eIement overIaps, with that of
the anaIyte waveIength.
Sometimes in presence of higher concentrations of
concomitants (in g/Iiter) substantiaI Iine broadening
occurs. Radiation scattering of particIes in the fIame or
moIecuIar absorption by chemicaIs and radicaIs aIso
introduces spectraI interference when there is resonance
Iine overIap.
139
For exampIe CaOH band in air-acetyIene fIame in the
determination of barium is a case in point.
AIkaIi haIides cause spectraI interferences beIow 300 nm.
e.g NaCI in the determination of iron in serum.
When the spectraI Iines overIap or Iie outside the resoIving
capacity of the monochromator, the interference is more
serious. For exampIe vanadium Iine 308.211 nm interfers
with the aIuminum Iine of 308.215 nm.
SimiIarIy magnesium Iine of 285.200 nm and chromium Iine
of 285.203 nm.
140
TRANSPORT INFLUENCES
Transport interferences are caused by aIterations in the
mass fIow of the aerosoI through the horizontaI cross
section of the fIame at the observation height.
This depends on the rate of aspiration, physicaI
characteristics such as viscosity, surface tension, vapour
pressure and density of the soIution. The causes incIude:
a) Increase in the saIt concentration above 1% (greater
dropIets)
b) Organic macromoIecuIes such as proteins and sugars
c) Organic soIvents - enhancements in the signaI
141
0.1 M hydrochIoric acid 1.0
MethanoI 40% 1.7
EthanoI 40% 1.7
Acetone 40% 2.0
Acetone 80% 3.5
Acetone + IsobutanoI 20% + 20% 2.35
EthyI pentyI ketone 2.8
MethyI isobutyI ketone 3.9
EthyI acetate 5.1
SoIvent ReIative sensitivity*
EFFECT OF ORGANIC SOLVENTS IN THE
DETERMINATION OF COPPER
* Referred to water
142
SOLUTE VOLTILIZATION
Interaction of soIute particIes containing the anaIyte with
concomitants can infIuence voIatiIization and cause
enhancement or attenuation of the signaI. They are generaIIy
specific and the signaI depends on the properties of the
compounds formed. Hence they may aIso be caIIed chemicaI
interferences.
In premix burners, Iaminar fIame voIatiIization begins as
soon as they enter the primary reaction zone. Therefore
the occurrence of interference depends on the observation
height. The anaIyte can combine with anions or Iigands or
simpIy form refractory oxides.
143
EFFECT OF OBSERVATION HEIGHT
Magnesium saIts
144
EFFECT OF OBSERVATION HEIGHT
CaIcium saIts
145
Oxides of group III & IV of the periodic tabIe form three
dimensionaI poIymer structures even in presence of
hydrochIoric acid. SpineI types (MeO.Me
2
O
3
) or iImenite
or pervoskites(MeOMeO
2
) form very stabIe Iattices.
ExampIes incIude titanium, zirconium, hafnium,
moIybdenum etc. the signaI depression occurs for :
suIphates > chIorides > nitrates
Formation of carbides aIso foIIows the series:
M(VI) > Me(V) > Me(IV)
If the metaI oxide is more voIatiIe than the metaI or the
carbide, signaI enhancement occurs.
146
VAPOUR-PHASE INTERFERENCES
The equiIibrium and incompIete conversion of the anaIyte
into spectroscopicaIIy active form (atoms) resuIting in the
attenuation of the signaI may be considered as vapour
phase interference. Such aIterations occur in the primary
reaction zone.
Diatomic and triatomic compounds (NaOH, BaOH, BeO etc),
cyanides or oxides (Cu
2
O) can aIter the degree of
ionization markedIy.
147
Dissociation processes frequentIy take pIace between
the chemicaI species and fIame gases. Variation in the
concentration of haIides, free radicaIs, O, OH, CN, H in the
fIame gases can infIuence the dissociation equiIibria.
MO + CO M + CO
2
MO + C
2
M + CO + C
2CO + O
2
2CO
2
CN + e CN
CHO CH
+
+ O
These ions suppress the ionization of the anaIyte.
-
-
-
148
SPATIAL DISTRIBUTION INTERFERENCES
These interferences are caused by the changes in the
fIow rate or fIow pattern of the sampIe in the fIame. The
quantities of combustion products can change the
mass fIow rate or fIow pattern which in turn are
infIuenced by the size and rate of voIatiIization of the
particuIates. ExampIes incIude signaI enhancement of AI,
Ba, Ca, Li, Sr etc.,
149
In generaI severaI types of interferences can occur in
fIame AAS due to severaI factors. Therefore even in the
absence of specificity stiII signaI enhancement or
attenuation can occur.
150
BACKGROUND CORRECTION ON FLAME AAS
Most of the spectraI interferences and aII other types of
interferences resuIt in the attenuation of AAS signaI to
some extent. In generaI the attenuation varies from
negIigibIe to severaI percent depending upon the matrix.
This signaI is known more commonIy as background
absorption which can be easiIy estimated by aspiring a
cIoseIy matching reference soIution which does not contain
the anaIyte. The absorbance of the reference (or bIank as it
is known) must be subtracted from that of the caIibration
standards as weII as the sampIes. AIternateIy radiation from
a deuterium Iamp can be measured at the resonance
waveIength to determine the background absorption.
151
A schematic configuration of a deuterium Iamp background
corrector can be measured at the resonance waveIength to
determine the background absorption.
152
In this figure the exit sIit of the monochromator separates
the resonance Iine from the emission spectrum of the HCI
equivaIent to the bandpass width of 0.2 or 0.7 nm.
The intensity I
PS
of the primary source is equaIized to the
intensity I
CS
of the continuum source before the
determination so that I
PS
/I
CS
ratio is unity.
For normaI measurements Iess than 1% absorption from
the continuum source is negIected (I
CS
). At higher
absorbance, I
PS
is attenuated proportionaIIy to the
concentration of the anaIyte. In effect I
CS
serves as a
reference beam.
153
MECHANISM OF BACKGROUND CORRECTION
154
Background correction with continuum sources are
incapabIe of correcting more than 0.5 absorbance.
Further the noise increases by a factor of two or three.
155
ZEEMAN EFFECT BACKGROUND CORRECTION
When an atomic vapour is pIaced in a magnetic fieId (~ 10 kg)
the energy IeveIs (terms) spIit, which manifests as spectraI
Iine spIitting. In the simpIest case the spectraI Iines spIit into
three components: the centraI component whose energy
and frequency is unchanged and two components are
shifted to the right and Ieft of the centraI component. The
separation of the components are of the order of 0.01 nm.
The distribution of energy between and components,

+
: :
-
is 25:50:25, which is known as zeeman effect.
156
SimuItaneousIy the radiation is aIso poIarized. The extent
of poIarization depends upon the direction of the magnetic
fieId. Some eIements spIit into onIy 3 components. This is
known as normaI zeeman spIitting (Ba, Be, Ca, Mg, Hg, Pb,
Pd etc). Some eIements spIit into more components but
odd numbers. Some eIements spIit into more even number
of components. These are known as anomaIous zeeman
spIitting. This effect can be used for background correction.
157
ZEEMAN SPLITTING OF COMMON ELEMENTS IN AAS
158
If the magnetic fieId is appIied at right angIes to the
radiation beam, component is poIarized paraIIeI to
the appIied fieId and components are poIarized
perpendicuIar to the appIied fieId. This configuration is
known as transverse zeeman effect.
When the magnetic fieId is paraIIeI to the radiation
beam, it is caIIed IongitudinaI zeeman effect. In this
configuration component is missing and onIy two
components are seen with fifty percent intensity.
159
SCHEMATICS OF ZEEMAN EFFECT
160
When the magnetic fieId is appIied to the radiation
source, it is known as direct zeeman effect. The
magnetic fieId can aIso be appIied to the atomic cIoud.
This is known as inverse zeeman effect.
In the inverse zeeman effect, the energy IeveIs of the
absorbing atoms are spIit and the absorbance vaIues
aIso change since the components are rotated out of
the radiation Iine and onIy component absorbs which
can be measured.
For the direct zeeman effect absorption can be measured
at both and component waveIengths aIso.
161
If a magnetic fieId is appIied by a permanent magnet or
via a direct current, a rotating poIarizer must be appIied
to measure the totaI absorbance.
By appIying an aIternating current, aIternating
magnetic fieId is generated which spIits the energy
IeveIs onIy when the fieId is on. Thus eight possibIe
configurations are possibIe.
162
Fixed poIarizer AIternating
Rotating
poIarizer
Constant PerpendicuIar
(transverse)
No poIarizer
required
AIternating
Not appIicabIe
in AAS
Constant
ParaIIeI
(IongitudinaI)
At the
Atomizer
(inverse)
Fixed poIarizer AIternating
Rotating
poIarizer
Constant PerpendicuIar
(transverse)
No poIarizer
required
AIternating
Rotating
poIarizer
Constant ParaIIeI
(IongitudinaI)
At the
Radiation
Source
(direct)
ParticuIarities Type of
magnetic fieId
Orientation of
magnet to
radiation beam
Location of the
magnet
VARIOUS CONFIGURATIONS OF ZEEMAN EFFECT IN AAS
163
AAS instruments with inverse zeeman effect (magnet at
the atomizer) are preferabIe but a rotating poIarizer is
required if a constant magnet is used. Therefore
aIternating magnetic fieId is used.
In this configuration absorbance is measured with fieId
off (normaI AAS) and with fieId on (background). This
is a true doubIe beam technique since both beams
originate from the same source, measurements are
made at the same frequency, foIIow the same opticaI
path and faII on the same detector. The sensitivity
remains unaItered.
164
SMITH HIEFTJE BACKGROUND CORRECTION
METHOD
This method is based on the seIf absorption behaviour
of radiation emitted from hoIIow cathode Iamps when
they are operated at high currents. AppIication of high
currents produces Iarge concentrations of unexcited
atoms in the hoIIow cathode Iamps. These atoms are
capabIe of absorbing the radiation produced from the
excited atomic species. High currents aIso broaden the
emission Iines of the excited species. Net effect is to
produce a Iine that has a minimum at its centre
(resonance Iine).
165
To obtain corrected absorbances, the Iamp is programmed
to run aIternateIy at normaI and high currents in quick
succession at the rate of every 5 miIIi seconds.
During normaI operations background and the atomic
absorption data is provided.
During the second part, when the absorption peak is at
a minimum, onIy the background is measured and
absorbance of the anaIyte is minimum.
166
The data acquisition system then subtracts the two
signaIs to give a corrected vaIue.
This is a remarkabIy simpIe means of background
correction which compares very weII with zeeman
effect method. SeveraI instrument manufacturers offer
Smith-Hieftje technique for background correction.
167
EMISSION LINE PROFILES IN S-H METHOD
168
Any anaIyticaI instrumentaI technique, however sensitive,
simpIe or rapid, is not free from aII interferences. Hence
as anaIyticaI chemists we must be aware of the origin or
the source of the interferences, so as to provide anaIyticaI
data very accurateIy and preciseIy. AAS is one such
anaIyticaI instrumentaI method and it has got much
inherent interference from the sampIe introduction stage
to the detector. OriginaIIy it was thought that AAS is free
from interferences as we measure very narrow resonance
Iine from the hoIIow cathode Iamp passing through the
atomizer either in the fIame or non-fIame.
CHEMICAL REACTIONS IN AAS - INTERFERENCES
169
The interferences may be cIassified as foIIows:
PhysicaI Interferences
ChemicaI Interferences
Ionization Interferences
SpectraI Interferences
Non-specific Interferences
The physicaI interference occurs at the sampIe
introduction stage and the remaining chemicaI,
ionization, spectraI and non specific interferences
occur in the fIame.
170
PHYSICAL INTERFERENCES
The PhysicaI Interferences are dominant at the sampIe
introduction stage in the transport of sampIe soIution to
the nebuIiser and from the nebuIiser to the spray chamber
and burner. The most important factors are viscosity
(infIuencing the sampIe aspiration rate), surface tension
(infIuencing the size of the aerosoI dropIets), and the
vapour pressure of the soIvent (infIuencing soIvent
evaporation rate). Because transport, affects aII the
eIements equaIIy, they constitute interferences not
specific to particuIar eIements.
171
The physicaI processes that occur during nebuIisation
have a Iarge infIuence on the sensitivity and seIectivity
of fIame methods of anaIysis. The nebuIisation
efficiency depends on the nature of the nebuIising gas
and the sampIe soIvent. The variation in the viscosity,
surface tension, density and temperature of the sampIe
soIution interfere in the nebuIisation process and
hence on the sensitivity.
This interference can be controIIed by preparation of
the standard soIutions used to construct the
caIibration curve at simiIar physicaI conditions of the
soIvent of the sampIe. These interferences can aIso be
eIiminated by diIuting the sampIe soIutions or by the
method of standard addition.
172
The presence of high concentrations of dissoIved saIts
in a sampIe can reduce the anaIyticaI signaI. It aIso
Ieads to the formation of incrustation of the nebuIizer
and the burner head and may Iead to high signaI noise
IeveIs. In generaI it can be said that the physicaI
interferences can resuIt if the sampIe and the standard
soIution vary greatIy in buIk composition. The normaI
sampIe soIution uptake rate is about 6-7 mI/min and the
nebuIisation efficiency in a pneumatic nebuIizer in
AAS is onIy 10%. So any change in these normaI
vaIues cause physicaI interferences and Iead to
spurious signaIs.
173
CHEMICAL INTERFERENCES
As it is aIready expIained that the physicaI
interferences occur from sampIe introduction stage
before nebuIisation tiII it reaches the burner, whereas
the chemicaI interferences dominate at the atomization
pIace, i.e., either in the fIame or in the eIectro thermaI
atomization. So to understand the chemicaI
interferences, we shouId know first of aII the various
stages that the sampIe soIution undergoes in the
fIame.
174
The Schematic Diagram as shown beIow represents
the various processes which must occur in producing
the atoms of some metaIIic eIement M from a soIution
of the saIt MX in the sampIe soIution.
175
FLAME ATOMIZATION PROCESS
176
The sampIe soIution first enters the nebuIisation where
it gets fragmented into fine dropIets of about 10 micron size
in the aerosoI. The bigger size dropIets go to the drain thus
giving nebuIisaiton efficiency of onIy 10%. The aerosoI then
enters into the fIame from the spray chamber. Here it
undergoes many changes before the production of the
atoms. First the soIvent moIecuIes get evaporated Ieaving
soIid particIes of the metaI saIts. These moIecuIes then
change into vapour stage and then dissociate into the metaI
atoms in the vapour phase.
177
These free metaI atoms can undergo a variety of reactions.
(i) It again associates with the O or H or C and forms the
respective oxides, hydrides or carbides
(ii) The metaI atom gets excited by the fIame temperature
(iii) The metaI atoms become cations due to ionization.
For the atomic absorption to give maximum sensitivity the
metaI atoms shouId remain in the free atom stage without
undergoing the compound formation or excitation or
ionization.
178
ChemicaI interferences are the most common interferences
encountered in atomic absorption spectroscopy. If the
sampIe being anaIysed contains a thermaIIy stabIe
compound with the anaIyte that does not dissociate at the
operating fIame temperature, a chemicaI fIame temperature,
a chemicaI interference exists. A chemicaI interference can
prevent, enhance or suppress the formation of ground
state atoms in the fIame.
179
As an exampIe Iet us consider the mechanism of
atomization of Ca atoms in the fIame. This is shown in
the figure.
180
CaIcium when present as CaCI
2
CaCI
2
.H
2
O Ca
0
+ CI
2
CaCI
2
.H
2
O Ca
0
+ 2HCI
CaO Ca
0
+ O
CaIcium when present as Ca (NO
3
)
2
Ca(NO
3
)
2
.3H
2
O CaO + NO
2
+ 3H
2
O
CaO Ca
0
+ O
181
In chIoride medium CaCI
2
dissociates into Ca atoms
and chIorine atoms. The formation of CaO from CaCI
2
in the fIame is very Iess. However, in the case of Ca(NO
3
)
2
it dissociates first into CaO and from this caIcium atoms
wiII come. So comparativeIy there is Iess number of Ca
atoms from nitrate medium than from chIoride medium.
As expIained earIier the most common chemicaI
interference is the compound formation. Most of the
eIements in particuIar the aIkaIine earth eIements Be, Ca,
Sr, Ba etc., form highIy refractory metaI oxides in the
fIame resuIting in the Ioss of these atoms avaiIabIe for
atomic absorption.
182
The dissociation of these metaI oxides back into free
metaI atoms depends upon the temperature of the fIame.
The higher the temperature of the fIame the more the
dissociation and hence the better sensitivity. The
air-acetyIene fIame gives a temperature of around 2600
0
C.
At this temperature most of the metaI oxides dissociates
except the refractory ones Iike aIkaIi earth eIement
oxides, Nb, Ta, AI, Zr etc. So a fIame which gives a
temperature higher than air-acetyIene is required. This is
obtained by the nitrous oxide-acetyIene, whose
temperature is around 2900
0
C. NormaIIy the eIements
whose dissociation energy is more than 5.0 ev cannot be
determined by air-acetyIene and Nitrous oxide-acetyIene
provides the necessary sensitivity. It is not aIways the
temperature of the fIame that is important.
183
Many a times the C/O ratio in the fIame determines the
sensitivity. Hence a reducing fIame providing more fueI
than the stoichiometric requirement is desirabIe for
many of these refractory metaI oxides. So one shouId
aIways optimize the fIame conditions in the fueI to
oxidant ration, height etc., to get maximum sensitivity.
In our Iaboratory we have carried out some investigations
using sugar to aIter the C/O ratio in the fIame favourabIe
for atomization.
184
It has been observed that for eIements Iike Mo, V, Ti,
AI, Ba, Y, Dy, Ho, there is enhancement in the
absorbance vaIues whiIe there is no enhancement in
the case of Iess refractory eIements Iike Cu, Cd, Co, Mi.
The other type of compound formation is the aIkaIine
earths forming refractory phosphates and doubIe oxides in
the fIame with AI, Si, etc., Strontium reacts with AI or Si
and forms refractory SrOAI
2
O
3
and SrOSiO
2
. SimiIarIy with
phosphate it forms Ca
2
(PO
4
)
2
during evaporation of Iiquid
dropIets in the fIame, this compound is converted to
caIcium pyrophosphate with heat and is very stabIe
in the air - acetyIene fIame.
185
This reaction reduces the free Ca atom popuIation in
the fIame as compared to that obtained from soIutions
in the absence of phosphate. This type of interference
can be eIiminated by the addition of a reIeasing agent.
The reIeasing agent such as Ianthanum preferentiaIIy
combines with the interfering ion, thus reIeasing the
anaIyte atom. In other cases the reIeasing agents such
as EDTA combines preferentiaIIy with the anaIyte atoms
and then dissociate in the fIame reIeasing the anaIyte
atoms.
186
The addition of Ianthanum or strontium reIeases the
caIcium atoms from the caIcium phosphate preferentiaIIy
forming La/Sr phosphates. The addition of EDTA
preferentiaIIy forms the caIcium EDTA compIex, an easiIy
voIatiIe compound which can dissociate reIativeIy easiIy
than the caIcium phosphate. We have pubIished a
research paper on the determination of indium in geoIogicaI
sampIes by adding a mixture of tripotassium citrate and
ascorbic acid in pIace of Ianthanum to eIiminate the
interferences. This type of interference can aIso be
eIiminated by the method of standard addition. In this
method the muItipIicative interferences can be taken care
of and not the additive interferences. This type of chemicaI
interferences aIways takes pIace in condensed phase.
187
IONISATION INTERFERENCES
This is aIso a type of chemicaI interference. WhiIe the
chemicaI interferences take pIace in the condensed phase,
the ionization interferences take pIace in the vapour phase.
When the anaIyte atoms get dissociated and vapourised,
these interferences are observed. The atoms of the
eIements possessing very Iow ionization potentiaIs can
become ionized at the fIame temperature. Thus instead of
having more number of ground state atoms for atomic
absorption, the ions of the anaIyte atoms wiII be more.
This again depresses the sensitivity and causes a Iot of
interferences in the finaI anaIyticaI measurements. AIkaIi
metaIs are more prone for this type of interferences
(Li, Na, K, Rb, Cs).
188
The anaIyte undergoes the foIIowing reactions in the
fIame.
M M
+
+ e
-
This interference can be controIIed by the addition of
excess of an eIement whose ionization potentiaI is very
Iow to both the sampIes and standards. Potassium
chIoride is preferabIy chosen due to its high purity and
Iack of visibIe emission in the fIame.
189
The ionization potentiaI of Ianthanum is very cIose to
Iithium and therefore Ianthanum in addition to being a
reIeasing agent aIso acts as an ionization buffer for
metaIs such as Ca, Mg, Si, AI etc., The addition of La or
K as ionization buffer provides more number of eIectrons
in the fIame and shifts the ionization equiIibria to the Ieft.
In other words, by providing more number of eIectrons,
the ionization is suppressed and free ground state metaI
atoms are restored.
190
ANALYTE OCCLUSION
There are other types of chemicaI interferences not
reIated to the stabIe compound formation or ionization.
Though there is no chemicaI reaction invoIved between
the anaIyte and the interferent, the occIusion phenomena
may be considered as chemicaI interference. When the
soIid particIes remaining after evaporation of the soIvent
consists of anaIyte atoms dispersed in the matrix of the
interferent, the voIatiIity of the matrix has an important
bearing on the yieId of free anaIyte atoms. Depression or
enhancement may be obtained, depending on whether the
matrix is Iess or more voIatiIe than that resuIting from
dissoIvation of the reference soIution.
191
An exampIe is the depression of chromium and moIybdenum
absorption in the presence of high iron concentration in the
air-acetyIene fIame. SeveraI observations indicate that there
is no specific compound formation between chromium or
moIybdenum and iron. The decrease in the anaIyte signaIs
IeveIs off onIy at high iron concentrations and the iron
anaIyticaI signaIs are not affected much by high chromium
concentration.
192
Hence it is thought that at high Fe/Cr ratios, the
chromium atoms are occIuded in an iron matrix
(b.p. 3000
0
C) which is incompIeteIy voIatiIized. In the
reverse situation when iron is determined in the
presence of an excess of Cr, the formation of the more
voIatiIe Cr matrix (b.p. 2400
0
C) does not aIter the
number of free iron atoms avaiIabIe for atomic
absorption. This type of interference effect can be
overcome by the use of nitrous oxide-acetyIene fIame
or by the addition of ammonium chIoride, sodium
suIphate or boric acid and suIphosaIicyIic acid.
193
BIBLIOGRAPHY OF INTERFERENCE STUDIES
194
SPECTRAL INTERFERENCES
Atomic absorption spectrometry is remarkabIy free from
spectraI overIap interferences. As you aII know that the
atomic absorption phenomena is based on the very
narrow resonance Iine absorption. The hoIIow cathode
Iamp emits atomic emission radiation of a specific eIement
which is abIe to induce absorption by atoms of that
eIement onIy in the sampIe. This arrangement has been
caIIed Iock and key effect. Hence, unIike emission
technique the spectraI interferences are very Iess in atomic
absorption spectrometry.
195
A spectraI interference can occur when an absorbing
waveIength of an eIement present in the sampIe but not
being determined faIIs within the bandwidth of the
absorption Iine of the eIement of interest. ResuIts wiII
be very high due to the contribution of the interfering
eIement to the anaIyte signaI. In AAS the spectraI
interferences may be cIassified into three groups:
(1) More than one absorption Iine in the spectraI band pass
(2) Non absorbed Iine emitted by excitation source
(3) SpectraI overIap in atom source. Atomic spectraI
interferences observed in fIame AAS and reported
Iiterature are shown in foIIowing tabIe.
196
NON SPECIFIC ABSORPTION
The non-specific interferences enhance the actuaI
readings obtained, but the sensitivity is not improved. In
this case a spurious absorbance is added to the true vaIue.
The non-specific absorbance is seen either by scattering
the absorption Iine by the soIid particIes or the absorption
of the resonance Iine by undissociated moIecuIes i.e.
moIecuIar absorption. The scattering phenomena is
anaIogous to the turbidity in moIecuIar spectrophotometry.
The soIid particIes are formed by the inabiIity of the fIame to
vaporize aII the dissoIved soIids of the sampIe soIution or
may be due to the formations of carbon particIes in the
fIames. The magnitude of this effect varies considerabIy with
the wave Iength at which measurements are being taken.
NormaIIy Iight scattering effects particuIarIy those eIements
that absorb at Iower wave Iengths.
197
The moIecuIar absorption occurs when a moIecuIar
species in the atomizer has an absorption profiIe that
overIaps that of the eIement of interest. This probIem is
most serious in the wave Iength region beIow 300 nm.
MoIecuIar absorption bands are reIativeIy broad
compared to atomic absorption profiIes. The moIecuIar
absorption and Iight scattering are aIso known as non
specific or back ground absorption. This background
interference can be detected if the Beer's Iaw graph does
not pass through the origin.
198
The non-specific absorption was initiaIIy attributed to
Iight scattering by saIt particIes, but strong evidence
has been produced to indicate that scattering is often
insignificant by comparison with moIecuIar absorption
both in fIame and non fIame situation. Thus background
absorption pIays a vitaI roIe in the determination of
trace eIements in varied compIex matrices. Hence
different methods have been worked out by the
manufacturers to controI the background absorption.
199
Methods for background absorption correction:
High temperature fIame
SeIection of a non-absorbing Iine.
Deuterium Iamp
Zeeman effect
Smith Hieftje
200
I Background absorption can be controIIed to some
extent but not fuIIy by using a higher temperature
fIame, which brakes down the absorbing moIecuIar
species.
II It can aIso be controIIed by seIecting a non-absorbing
Iine about 10 nm away the resonance Iine. The signaI
from the non-absorbing Iine shouId be deducted from
the signaI obtained from the absorbing Iine. The
seIection of the non-absorbing Iine. The seIection of
the non-absorbing Iine is such that it shouId not be
absorbed by the sampIe matrix.
201
III The most wideIy used method for background
correction is by deuterium Iamp. As it is aIready
pointed out that the atomic absorption Iines are very
narrow of the order of 10-50 nm. When an atomic Iine
from a hoIIow cathode Iamp passes through an
atomizer it wiII be absorbed by both the atoms and
moIecuIar absorption remains the same, however, the
atomic absorption contribution is aImost niI
(SBW=0.2-0.5). So by subtracting the background
vaIue from the totaI absorption, the true absorption by
the free atoms is obtained.
The deuterium Iamp which is used for this purpose gives
a broad continuum up to about 300nm.
202
The method of back ground correction works as foIIows:
The absorbance of the sampIe occurring with the hoIIow
cathode Iamp is A
c
i.e., sum of atomic absorption (A)
and background absorption (A
b
).
A
c
= A+A
b
.
The absorbance with the deuterium Iamp is onIy
background absorption (A
d
).
A
d
=A
b
.
InitiaIIy both the signaIs from hoIIow cathode Iamp and
deuterium Iamp are made equaI.
203
Hence True absorbance = A
c
- A
d
(since A = Iog I
o
/ I
t
)
= Iog I
co
/ I
ct
- Iog I
do
/ I
dt
= Iog I
co
. L
dt
/ I
ct
. I
do
InitiaIIy I
co
= I
do
(originaI signaIs made equaI)
Therefore true absorbance = Iog I
dt
/ I
ct
Intensity of transmitted Iight from deuterium Iamp
= ------------------------------------------------------------------------------
Intensity of transmitted Iight from hoIIow cathode Iamp
204
In this method the speed of background correction is
criticaI. There must be minimum deIay time between
the totaI absorbance and the background absorbance.
The magnitude of the back ground signaI can change
rapidIy with time. For exampIe within 20 miIIi seconds
the background vaIue can change up to 0.2 absorbance.
So, if the difference between the measurements is about
10 miIIi seconds it Ieads to an error of 0.1 absorbance. In
uItra puIse system the time gap is onIy 1 miII seconds
and hence the error is onIy 0.01 units.
205
ADVANTAGES OF ULTRA PULSE
BACKGROUND CORRECTION
Description UItra PuIse Smith Hieftje Zeeman
Sensitivity Ioss None Upto 6 Upto 3
FIame Furnace Yes Yes No
& vapour generation
CaIibration Linearity NormaI Reduced NormaI
Dynamic Range NormaI Curved Curved
No of sampIe 200 10 50
readings per sec
Background 1ms 4.5 ms 10ms
measurement deIay
206
SOME OF THE DRAWBACKS OF THE DEUTERIUM
CORRECTION ARE:
Incorrect resuIts in the presence of structured
background
No correction for spectraI interference
Different geometricaI and opticaI paths
Loss of Iight
207
SMITH HIEFTJE EFFECT
It has been known that when an excess current is
passed through a hoIIow cathode Iamp, its emission
Iine is broadened and seIf reversaI takes pIace. Hence
in this method the Iamp is first run at Iow current and
its Iight is absorbed by the anaIyte as weII as by the
background. Then a brief puIse of much higher current
is passed through the Iamp causing seIf reversaI which
is absorbed by the background onIy. By subtracting
one from the other the true absorbance is obtained.
208
Advantages of the method are:
(a) Background correction can be appIied in the UV
and visibIe range.
(b) Accurate correction for structured background.
(c) A singIe Iight source is used.
(d) Correction of spectraI interference is possibIe.
(e) No bending of caIibration curve.
209
MODULATION
The signaI received by the detector consists of the
resonance radiation from the hoIIow cathode Iamp and
the resonance emission Iine at the wave Iength of
absorption from the atom source. For atomic
absorption measurements onIy the resonance radiation
originating from the source Iamp is to be measured. To
achieve this seIectivity the Iamp output is therefore
coded by moduIation and the post detector ampIifier is
tuned to the same moduIation frequency. This prevents
the DC emission signaI form the fIame being measured.
The moduIation can be done either by a square wave
AC suppIy current or by interposing a synchronous
chopper in the Iight beam before fIame.
210
THE HYDRIDE GENERATION
AAS TECHNIQUE
211
Arsenic, antimony, bismuth, seIenium, teIIurium, Iead,
mercury and a number of other eIements of the
periodic tabIe beIonging to group IV, V and VI are
known to form voIatiIe covaIent hydrides with nascent
hydrogen. Marsh's test and Gutzeit's test have been
empIoyed for the detection of arsnic since more than
100 years.
The property of voIatiIization as a gaseous hydride can
be utiIized to advantage for the separation and enrichment
of the anaIyte eIement which aIso accompIishes the
reduction and even compIete eIimination of interferences.
212
In the earIy 1950s a number of anaIyticaI methods
based on coIorimetry were introduced for the
determination of arsenic and other hydride forming
eIements.
The hydride was formed in acid soIution using zinc
powder and the gaseous reaction products were
conducted into soIutions containing ammonium
moIybdate or hydrazine suIphate which formed
characteristic coIored compIexes with the hydride.
Some of these techniques are stiII in use even today.
213
HoIak in 1969 was the first to appIy hydride generation
technique to AAS. He generated arsenic hydride and
coIIected it in Iiquid hydrogen. SubsequentIy he warmed
the trap and conducted the arsine with a stream of
nitrogen into an argon-hydrogen fIame to measure
atomic absorption. SeveraI papers were pubIished in the
foIIowing years describing modifications and
optimization of the technique. However the technique
found wide acceptance onIy after the reIiabIe
accessories were introduced in the market.
214
HYDRIDE GENERATION TECHNIQUE
The most commonIy used method to generate nascent
hydrogen is addition of zinc or aIuminum to
hydrochIoric acid. Mixtures of titanium trichIoride and
magnesium have aIso been used for the generation of
nascent hydrogen.
MetaI acid reactions have a number of disadvantages
such as:
1) Requirement of high purity metaIs
2) High vaIues of bIanks
3) Low reIease of hydrogen (onIy 8%)
215
Most of these disadvantages have been overcome by
the introduction of sodium borohydride as a reductant.
ReproducibiIity and controI over the reaction can be
easiIy achieved with the addition of sodium
borohydride soIution stabiIized in sodium hydroxide
soIution. In 6M HCI soIution and using nitrogen stream
to reIease hydrogen, yieId can be increased to 40 - 60%.
216
APPARATUS FOR HYDRIDE GENERATION
217
The reIeased hydrogen is coIIected in a trap cooIed with
nitrogen which is warmed to vapourize it. Before freezing
the hydride must be dried properIy using caIcium chIoride.
The Iatter deveIops a high heat of hydration that prevents
hydride from being dissoIved or absorbed.
For routine determination direct 'onIine' introduction
into the fIame through a quartz tube is quite satisfactory.
Peak area integration frees the method from kinetic
interferences.
218
ATOMIZATION OF THE HYDRIDE
Soon after the deveIopment of the hydride technique,
the use of eIectricaIIy heated quartz tube or heated in a
fIame for atomization of the hydrate were proposed.
Some workers used a quartz tube with seaIed quartz
windows. The tubes were heated to 1100
0
C. With this
procedure a very high degree of atomization (~ 100%)
can be obtained.
219
The reactions can be summarized as foIIows:
Zn + HCI ZnCI
2
+ H
2
NaBH
4
+ HCI NaCI + BH
3
+ H
2
Se + H
2
SeH
2
SeH
2
Se + H
2
1100
0
C
220
As of now the procedure can be easiIy automated to obtain
a high throughput of 30 sampIes per hour! The hydride
technique has a decisive advantage over other systems
because onIy the anaIyte can be separated as a voIatiIe
hydride from the sampIe matrix. The reIativeIy smaII
number of other components reaching the atomizer make
their interference rather unIikeIy.
The greatest advantage of hydride technique is that it is an
absoIute technique and not concentration dependent. The
sampIe voIumes required for anaIysis are very Iow. OnIy 10 mI
of the reagent and 0.5 mI of the sampIe are sufficient.
Most reaction vesseIs for hydride technique are designed to
accept 50 - 100 mI but aIso require a minimum voIume of
5 - 10 mI. In practice 10 mI of the reactant voIume and 0.5 mI
of the sampIe are satisfactory.
221
ATOMIZATION MECHANISMS
Atomization is brought about by free radicaIs produced
in the primary reaction zone of the diffusion fIame.
H + O
2
OH + O
O + H
2
OH + H
OH + H
2
H
2
O + H
In presence of excess hydrogen onIy OH and H radicaIs are
formed . The Iast reaction is very rapid and the concentration
of H radicaIs is severaI orders of magnitude higher than that
of OH radicaIs.
.
.
.
.
.
.
.
.
222
SeH
2
+ H SeH + H
2
H = - 189 KJ/ moI
SeH + H Se + H
2
H = - 131 KJ/ moI
A corresponding reaction
Se + H SeH H = - 305 KcaI
is aIso possibIe. But this reaction is strongIy exothermic
and needs a third partner to take up the energy. It can be
reasonabIy assumed that this reaction is very much
sIower than the formation of Se atoms.
SimiIar mechanisms can be prevaiIing for other hydride
forming eIements.
.
.
.
223
INTERFERNCES
For absorption in fIames, variations in the transparency
occasionaIIy occur when the hydride aIong with hydrogen
enters the fIame. But this signaI is very smaII and
constant and caused by HCI, it can be subtracted Iike a
bIank vaIue.
Kinetic interferences occur in direct on-Iine systems
and caused by varying rates of formation or Iiberation of
the hydride from soIution. For exampIe very dense foam
produced by the addition of the aIkaIine sodium
borohydride retains a portion of the hydride.
224
For eIements of VA group, the sensitivity difference in
peak heights between +3 and +5 oxidation is Iess than a
factor of 2. This difference can be partIy eIiminated by
peak area integration.
For arsenic, +5 state gives an 80% signaI as compared
to arsenic (III). SimiIarIy for antimony (V) there is 50%
reduction in the signaI as compared to antimony (III).
For group (VI) eIements, +4 and +6 oxidation states
exist and +4 gives a measurabIe signaI.
225
In practice a pre-reduction of seIenium and teIIurium is
aIways required in hot 4 M or 6 M HCI medium.
HCI, H
2
SO
4
and HNO
3
depress the signaI if present in
high concentrations.
226
EFFECT OF NITRIC ACID
227
EFFECT OF SULPHURIC ACID
228
INTERFERENCES
EIements from group VIII and IB of the periodic tabIe
owing to the formation of precipitates, and some
eIements Iike nickeI, pIatinum etc., absorb the hydrogen.
Transition eIements interfere in ionic forms at high
concentrations. EDTA, cyanides and thiocyanates mask
the interference. AII hydride forming eIements interfere
mutuaIIy. Thus interference is dependent upon the
absoIute concentration but not on the anaIyte/ interferent
ratio. As-Se interference is gas phase type which can be
eIiminated by using a buffer to deIay the transfer of arsenic.
229
INSTRUMENTATION
230
DETERMINATION LIMITS OF METAL
HYDRIDES
As 0.02
Bi 0.02
Sb 0.1
Se 0.02
Sn 0.5
Te 0.02
EIement Hydride Technique
231
AUTOMATION
High sensitivity of the hydride technique and the
environmentaI poIIution potentiaI of arsenic, seIenium,
Iead etc., have prompted researchers to automate the
hydride technique. Nowadays the automated hydride
accessories are avaiIabIe which empIoy peristaItic
pumps for mixing the reagents and use nitrogen for
hydride transport. These operations can aIso be
integrated into the software of AAS and throughputs of 30
sampIes per hour is possibIe.
232
MERCURY COLD VAPOUR TECHNIQUE
233
Mercury is the onIy metaIIic eIement that exists in the
atomic state at ambient temperature. It has a vapour
pressure of 0.0016 m bar at 20
0
C which corresponds to
about 14 mg per cubic meter. Given the environmentaI
poIIution potentiaI of mercury, attempts have been made
since 1939 weII before the deveIopment of AAS, for the
determination of mercury in air. The most successfuI
among these was the eIectroIytic deposition of mercury
using a mercury vapourization ceII.
234
PoIIuktov and Vitkun were the first to use the stannous
chIoride to reduce mercury in sampIe soIutions which
resuIted in an usuaIIy Iarge absorbance signaI for
mercury in AAS. SubsequentIy they eIiminated the
fIame and nebuIizer and passed onIy air to conduct the
vapour through a 30 cm quartz ceII mounted in the
opticaI path of the radiation beam in AAS. With this
technique they obtained detection Iimit of 0.5 ng
mercury.
235
A generaI scheme of generation of mercury vapour is
shown here.
236
Nowadays the determination of mercury is carried out
by an apparatus simiIar to that of hydride generator but
provided with some modifications.
When stannous chIoride is used as a reductant, air
must be pumped through the soIution to agitate as weII
as transport the mercury to the absorption ceII. The
dynamic signaI generated in this way shows a sIightIy
Iower absorbance compared to sodium borohydride -
acid soIution.
237
With sodium borohydride a great quantity of hydrogen
is Iiberated when acid is added. This hydrogen in fact,
transports the majority of the metaIIic mercury to the
absorption ceII. Further, the reaction with sodium
borohydride is much faster so that peak height
measured with the open system is aImost equaI to that
of stannous chIoride (SnCI
2
) in a cIosed system.
238
MERCURY COLD VAPOUR SIGNAL
239
By using a weII designed reaction vesseI with a conicaI
bottom and by introducing the reductant near the
bottom of the vesseI thorough and turbuIent mixing of
the reductant ensures compIete dispIacement and carry
over of the mercury. The time required for the reaction
is onIy one to two minutes.
Since mercury vapour is in contact onIy with tubes and
other components of the apparatus onIy for a reIativeIy
short time exchange reactions pIay onIy a minor roIe.
In contrast, on a cIosed system Iosses occur through
adsorption and carry over probIems from one sampIe to
the next are more.
240
The necessity of determining mercury in uItra trace
quantities has Ied to the deveIopment of enrichment and
separation techniques. The fact that mercury forms stabIe
amaIgams with nobIe metaIs such as copper, siIver or goId
can be used to advantage for enrichment.
The mercury vapour is mereIy coIIected by amaIgamation
on a goId gauze for a sufficientIy Iong time to concentrate
it . SubsequentIy the gauze is heated up to 500 - 700
0
C and
the vapour is carried over to the absorption ceII for
measurement. Thus an enhanced signaI is obtained as
compared to direct anaIysis.
241
ENHANCEMENT OF SENSITIVITY
242
Since the amaIgam technique preconcentrates the
mercury, the method becomes independent of the
voIume of the sampIe and absoIute determination is
possibIe. In this way the detection Iimit of the coId
vapour technique is aIso improved.
243
INTERFERENCES
VirtuaIIy there are no spectraI interferences in the
determination of mercury .
Systematic errors occur to a Iarge extent owing to the bIank
vaIues, contamination due to the reagents, Iaboratory gIass
ware, Iosses due to voIatiIization, adsorption or chemicaI
reaction. In the extreme cases these phenomena can Iead to
substantiaI errors. In non-contaminated regions in the
atmosphere, the concentration of mercury rareIy exceeds a
few nanograms per cubic meter.
However in the Iaboratory atmosphere, vaIues of 100 ng/ m
3
are not uncommon.
244
TypicaI sources of errors are Iisted beIow:
During the storage of sampIe (e.g soiIs, gIass ware etc).
Diffusion of mercury through pIastic foiIs.
Adsorption of mercury on to the gIass waIIs of the
containers.
Contamination of the reagents and acids.
During sampIing, digestion, storage or actuaI
measurement.
Precipitation of mercury on nobIe metaI surfaces.
ChemicaI exchange reactions with rubber tubing, PVC etc.
CaCI
2
is an unsuitabIe drying agent . Magnesium
perchIorate is better.
245
CHEMICAL INTERFERENCES
0.005 0.005
10 0.25
10 0.25
10 0.25
0.003 1
1 2.5
0.005 0.5
Limiting concentration (weight%) of mercury
SnCI
2
reduction NaBH
4
reduction
EIement
Ag
As
Bi
Cu
I
Sb
Se
246
PROCESS INTERFERENCES
GoId, pIatinum, rhodium and ruthenium interfere in the
determination of mercury when present at 1g/L
concentrations in the anaIyte soIutions. This is due to the
reduction of these metaIs and subsequent amaIgamation
with mercury. SimiIarIy copper and siIver interfere. SiIver
interference can be eIiminated by adding bromide to form
siIver bromide(AgBr) whiIe mercury remains in soIution as
tetra bromo mercurate ion (HgBr ) .
Iodide interference is noticeabIe when the sampIe is
treated with nitric acid (as in sea weeds).
HydroxyIamine hydrochIoride which is added to reduce
permanganate can have a substantiaI infIuence on mercury
at higher concentrations. In this case mercury is not
Iiberated at aII!
2-
4
247
SuIfhydryI groups (e.g cestine etc.) interfere when
the sampIe is not compIeteIy ashed.
Organomercury compounds are voIatiIized and onIy
partiaIIy reduced by sodium borohydride but the
sensitivity of determination decreases in the order:
Inorganic mercury (Hg
2+
) > CH
3
Hg
+
> C
6
H
5
Hg
+
However above 700
0
C the sensitivities are identicaI.
Poisoning of the goId gauze by other gases causes
incompIete amaIgamation. Therefore frequent
reconditioning of the goId gauze is necessary.
248
FLAME ATOMIC EMISSION
SPECTROMETRY
249
ThermaI excitation of atoms as dipicted by the equation,
N
j
= P
j
N
o
P
o
has been used to demonstrate the Iower sensitivity of
fIame AES. The ratio of the non-excited atoms is more
unfavourabIe in the short waveIength range of the
spectrum than in the Iong waveIength range.
e
-Ej/KT
250
ATOMIC CONCENTRATION AT 2500 K
251
However it is not correct to state that AAS is aIways more
sensitive than AES because the number of the excited
atoms is aIways smaIIer than the number of atoms in the
ground state. In fIame AES, apart from N
j
, the Iifetime of
the excited atoms is aIso more important. Experience has
shown that AAS is more sensitive than AES onIy when
the excitation potentiaI is greater than 3.5 ev. With Iower
potentiaIs fIame AES is usuaIIy more sensitive.
FIame AES and AAS are more compIementary to each other
than competitive. Majority of commerciaI atomic absorption
spectrometers nowadays permit fIame emission
measurements aIso.
252
FIame emission spectrometry has been in use since
1900s. Combustion fIames provide a means of
converting anaIytes into vapour forms by suppIying the
energy necessary to promote the eIectrons from the
ground state to the excited state. The intensity of the
radiation emitted by these excited states whiIe
returning to the ground states provides the basis for
anaIyticaI method.
253
The basic components of the fIame spectrophotometers
incIude:
1. SampIe deIivery system
2. FIame as excitation and emission media
3. Optics to isoIate the desired spectraI Iines
4. Detectors and
5. Recorders
254
THE SAMPLE DELIVERY SYSTEM
EssentiaIIy simiIar considerations as we had discussed for
fIame AAS prevaiI in the fIame emission systems aIso. The
most popuIar sampIe deIivery system is the numatic
nebuIization. The sampIe is introduced through a capiIIary
of 0.5 mm diameter tube into a high veIocity gas jet of the
oxidant (usuaIIy butane in FAES or acetyIene in the case of
AAS). In the spray chamber the Iarger dropIets are broken
into an aerosoI of Iiquid and gas carried into the burner.
TypicaIIy dropIets bigger than 20 m diameter are coIIected
and discarded. The distribution of the drop size is a
function of the soIvent as weII as the concentration of the
components.
255
256
AAS NEBULIZER
257
A typicaI fIame photometer is composed of a pressure
reguIator and fIow meter for fueI gases, an atomizer,
a burner, mirror, sIit, opticaI system, photosensitive
detector and recording output for the detector. Nowadays
microprocessor controIIed fIame photometers are the norm.
258
OPTICAL DIAGRAM OF THE FLAME
PHOTOMETER
259
Pressure reguIator and fIow meter are used for proper
adjustment of the pressure and fIow of gases. A 10 Ib
gauge for fueI and 25 Ib gauge for oxygen are needed.
DoubIe diaphragm and needIe vaIves are used to
controI the pressure. A rotameter is inserted in the gas
Iine to obtain 2 - 10 ft/ hour of gas fIow.
260
FLAME REQUIREMENTS
i. The fIame shouId possess the abiIity to evaporate
the Iiquid dropIets from the sampIe soIution
resuIting in the formation of soIid residue.
ii. It must be capabIe of decomposing the soIid into
atoms.
iii. It must be capabIe of exciting the atoms to higher
energy state.
Mecker burner, totaI combustion burner, premix or
Iaminar fIow burner are empIoyed.
261
The radiation from the fIame is coIIected from a concave
mirror pIaced behind the burner. The focaI point of the mirror
Iies at the entrance of the monochromator sIit. The exit sIit is
kept between the monochromator and the detector.
The opticaI system functions as a coIIector and the
monochromator focuses it on the detector. Use of absorption
fiIters or interference fiIters is more common in dedicated
fIame photometers. However better isoIation of the emitted
radiation Iine is achieved using a monochromator.
Most of the dedicated fIame photometers use photoceIIs with
ampIifier units to boost the output. However photomuItipIiers
offer best sensitivity.
262
SCHEMATIC ARRANGEMENT OF A
FLAME EMISSION IN AAS
263
A grating spectrometer equipped with a Iaminar fIow
burner and good detection read out system as in AAS
serves equaIIy weII for fIame AES. For this reason
fIame emission is routineIy offered as an aIternative
operation mode in most of the AAS instruments. Since
most of waveIengths usuaIIy faII into the visibIe or
uItravioIet region photomuItipIier tubes offer best
detection Iimits for aIkaIi and aIkaIine earth metaIs.
264
Both singIe beam and doubIe beam fIame emission
spectrophotometers are avaiIabIe in the market.
SingIe beam fIame spectrometers contain onIy one set
of optics. In doubIe beam spectrometers a second Iight
path for the Iight emitted by the internaI standard
eIement which is added to each test soIution and
caIibration.
The signaI from one detector opposes that of the other
through a suitabIe indicating device to produce a ratio
method of comparing the Iight intensities between the
anaIyte and the internaI standard.
265
OPERATION OF FLAME AAS
Just Iike AAS, AES is aIso a reIative technique.
Therefore a series of standard soIutions need to be
prepared. The standards and the anaIyte are fed into
the fIame sequentiaIIy and the response is fitted into a
Iinear or a poIynomiaI curve. The concentration of the
anaIyte is read off from the caIibration curve.
266
INTERFERENCES IN FLAME PHOTOMETRY
Not many spectraI interferences are known to occur in
the determination of aIkaIi and aIkaIine earth metaIs.
Interference may aIso arise from the background
emission due to hydroxyI and cyanogen radicIes. This
is usuaIIy in the form of a scatter which can be
controIIed by measuring against a matrix matching
soIution.
SeIf absorption can be significant at Iow concentrations.
This effect is more pronounced for Iowest resonance Iine.
267
CHEMICAL INTERFERENCES
1. StabIe compound formation or refractory oxide
formation. This Ieads to incompIete dissociation.
2. By increasing the fIame temperature this interference
can be reduced. Another method of reducing the
interference is by adding reIeasing agents.
M - X + R R - X + M
Addition of excess of R wiII shift the reaction to the right.
Hence if R-X is a stabIe product, this wiII resuIt in the
enhanced concentration of gaseous metaI atoms M.
268
3. Ionization causes serious interference. Thus determination
of caIcium, strontium and barium in acetyIene- air fIame
reduces the sensitivity.
This can be reduced by adding ionization suppressants.
For exampIe addition of potassium saIts reIeases a Iarge
number of eIectrons there by increasing the sensitivity of
caIcium, strontium and barium.
4. Anion interference.
5. Cation interference sodium intensity doubIes in presence
of potassium . Addition of radiation buffer reduces this
effect to a considerabIe extent.
269
6. Interference due to other eIement emission Iines. A
good quaIity monochromator reduces this type of
interference.
7. Interference due to saIts and acids. This effect can
be reduced to a Iarge extent by matrix matching.
e.g Sodium chIoride interferes (21.3.9 nm) in the
determination of zinc.
8. InstrumentaI errors.
270
INSTRUMENTAL ERRORS
Most of the instrumentaI errors in fIame photometry
arise from the instabiIity of the fIame. To obtain stabIe
fIame the fIow rate of the fueI and the oxidant must be
controIIed within 1%. The fIuctuations of the detector
and the ampIifier aIso Ieads to instrumentaI errors.
Another source of the anaIyticaI error is the atomizer
function . Quite often the capiIIary gets cIogged due to
the deposition of saIts. Therefore reguIar maintenance
of the instrument is very essentiaI.
271
APPLICATIONS OF FLAME PHOTOMETRY
1. QuaIitative anaIysis for aIkaIi and aIkaIine earth
metaIs.
2. Quantitative anaIysis
ExtensiveIy appIied for the determination of
sodium, potassium, Iithium, caIcium, magnesium,
strontium in the anaIysis of water, gIass, bioIogicaI
fIuids, petroIeum products, cement, metaIIurgicaI
sampIes, agrochemicaIs etc. TypicaI anaIysis range
varies from 1-50 ppm of the metaI ions.
272
ELECTROTHERMAL ATOMIC
ABSORPTION SPECTROMETRY
273
Atomic absorption anaIysis using fIame atomization
pre-supposes that the sampIe is in soIution. For the
anaIysis of soIids in ppm IeveI, bringing the sampIe in
soIution itseIf invoIves a diIution so that the concentration
of the anaIyte in ppm wiII become a smaII fraction of the
originaI content. Thus the Iimit of detection for a particuIar
eIement is directIy proportionaI to the concentration of
the atoms in the fIame, which is further dependent upon
the fIow rate of soIution, efficiency of nebuIization and
atomization efficiency. Since the fIow rate of the gases is
aIways high, the time spent by the free atoms in the fIame is
very short, of the order of 10
-4
sec. Increase of free atoms
by higher intake of the sampIe is restricted by the burner
design and moreover causes a deterioration of fIame
stabiIity.
274
AII these factors tend to Iimit the atomic concentration in
the fIame Ieading to a significant reduction of sensitivity
and Iimit of detection. Further when the sampIe size is very
smaII (5-10 I) it is necessary to work at absoIute detection
Iimits. (expressed as g ). Therefore non-fIame atomization
methods were investigated to overcome these probIems. The
main focus in this deveIopment is the direct voIatiIization of
the sampIe by direct heat. SeveraI techniques based on
appIication of eIectron bombardment, fIash method, Iaser and
pIasma have been tried but they have not gained popuIarity.
275
Among these, L'vov and Iater Massmann's design of an
eIectricaIIy heated graphite tube based on the voIatiIization
of the sampIe by direct heating of graphite cuvettes with
Iow voItage, high current in argon atmosphere have
evoIved into a powerfuI AAS technique popuIarIy known as
eIectrothermaI atomic absorption spectrometry which
can give detection Iimits of the order 10
-12
- 10
-14
g/ Iit.
In the L'vov design the graphite tube is mounted in a
chamber fiIIed with argon at reduced pressure. The
sampIe is deposited in the graphite cuvette, voIatiIized
and atomized by JouIe heating (resistance heating) at
3000
0
C. L'vov obtained typicaI detection of 10
-12
-10
-14
g
with this design. But this apparatus is very compIex and
cumbersome in operation.
276
L'VOV'S ARGON CHAMBER
277
Massmann constructed a simpIified graphite furnace in
which the tube was continuousIy fIushed with argon to
prevent oxygen interaction with graphite. But because
of continuous fIushing and sIower rate of heating the
detection Iimits were one or two orders of magnitudes
Iower than L'vov. NevertheIess because of its simpIicity
and ease of operation, most of the graphite furnaces in
use today are based on the Massmann design i.e they are
tube furnaces with resistance heating which offer
fIexibiIity in programmabiIity and operating convenience.
Massmann design is shown here.
278
MASSMANN GRAPHITE FURNACE
279
The tube is mounted in the opticaI path of the resonance
Iine in such a way that beam encounters onIy the
atomic cIoud unhindered by the tube geometry. The rest
of the instrumentation is same as that of fIame atomic
absorption except, the software which has to handIe
severaI other tasks that are typicaI of a dynamic signaI.
280
Introduction of the sampIe in to a graphite furnace
(5-100 I) foIIowed by voIatiIization and atomization
Ieads to an absorption versus time signaI which
resembIes a gas chromatography peak Iasting a few
seconds. The shape of the curve is dependant upon
the totaI number of atoms injected, residence time of
the atoms in the opticaI path and the response time of
the detector. Either the peak height or peak area ( abs.sec)
can be measured as a function of concentration, the Iatter
being more suitabIe for routine appIications.
281
GRAPHITE TUBE CHARACTERISTICS
For a good signaI the graphite tube shouId be as Iong
as possibIe and as narrow as possibIe. This faciIitates
Ionger residence time and hence good absoIute
sensitivity. The dimensions of the tube must be such
that the whoIe tube shouId have uniform temperature,
though this is seIdom the case.
Apart from good geometry, the tube materiaI and surface
characteristics are very cruciaI in ETAAS. It is weII
known that at high temperatures graphite surface is
highIy permeabIe to metaI atoms.
282
OPTIMUM DIMENSIONS OF GRAPHITE TUBE
d = b + I tan
283
Attempts to prevent the permeabiIity were directed
towards treatment of tubes with tantaIum, moIybdenum
and tungsten saIts which resuIted in better sensitivity
and reproducibiIity. This was attributed to the seaIing of
cracks and defects in the graphite surface. L'vov found
that tubes made of pyroIytic graphite had the same
properties. A dense, hard, impermeabIe and oxidation
resistant pyroIytic Iayer of about 30-50 mm is highIy
resistant to oxidation thus permitting the determination
of refractory eIements with highest sensitivity.
284
GRAPHITE SURFACE CHARACTERISTICS
285
I SYSTEM CONSIDERATIONS
It is important to use argon in ETAAS. The purge gas
performs the foIIowing functions.
i) Being inert, it prevents the ingression of atmospheric
oxygen into the graphite furnace thus proIonging the
Iife of the tube.
ii) It prevents metaI atoms reacting with atmospheric
oxygen to form refractory oxides which reduce
sensitivity.
iii) It physicaIIy transports the matrix components out of
the radiation beam before atomization, thus
eIiminating much of the background radiation.
iv) It is possibIe to preciseIy controI the fIow of purge
gas or even reduce it to zero during measurement to
obtain better sensitivity.
286
II TEMPERATURE CONTROL
In eIectrothermaI AAS it is possibIe to heat the tube and
hence the sampIe at a controIIed rate in a series of stepwise
increments. This permits the removaI of unnecessary matrix
components in a predetermined manner. Thus it is possibIe
to raise the temperature of the tube to 90
0
C within 1 second,
ramp it to 120
0
C at 2
0
C per second, hoId it for 10 seconds to
remove water etc.
SimiIarIy other temperature programmes may be
incorporated to remove organic matter, inorganic saIts etc,
untiI aII the concomitants are removed and onIy metaIIic
eIements are Ieft. For the atomization, a maximum heating
rate is seIected to obtain best sensitivity. AII such
pretreatments may be standardized in the preIiminary
experiments before optimizing the temperature
programme.
287
III THE STABILIZED TEMPERATURE PLATFORM
CONCEPT
It has aIready been mentioned that the detection Iimits
in L'vov furnace are 2-3 orders of magnitude higher than
the Massmann design. This is because the sampIe
after vaporization is not in equiIibrium with voIume or
time and temperature. Sturgeon and Chakrabarty found
that 60% of the atoms formed diffused to the cooIer ends
of the graphite tube which was 1500
0
C compared to the
middIe temperature of 2500
0
C . EquiIibrium with time is
even more difficuIt to achieve.
288
GRAPHITE TUBE AND PLATFORM ARRANGEMENT
289
Hence L'vov et aI. proposed that the sampIe be
dispensed on a IooseIy fitted pyroIytic pIatform in the
graphite furnace which wiII be heated onIy by radiation
but not by direct contact. Such an arrangement does
not permit heat conduction at right angIes to the pIane
of graphitization. In such an arrangement pIatform
temperature foIIows the tube temperature rather
sIuggishIy which permits better equiIibrium conditions.
In such a system it has been proved that interferences
are very few.
290
AUTOMATION
In graphite furnace the sampIe to be handIed is rather
smaII ( 5-100mI) but the sensitivity is rather high. The
sampIe has to be introduced exactIy in the same pIace
every time through a smaII hoIe (about 1 mm dia) in to the
graphite tube or on to the pIatform. There is aIso the risk of
sampIe contamination with the graphite hoIe edges and
pipette tips. AII these factors Iead to poor precision with
manuaI pipetting. It is aIso cumbersome. Therefore
automatic pipetting is preferred. SeveraI programmabIe
automatic dispensing units with tefIon capiIIary are
avaiIabIe in the market and aIso offered as a standard
accessory with graphite furnaces. The reproducibiIity with
automatic dispensers is about 1% with an RSD of
0.4% compared with 5% for manuaI pipetting with an RSD
of 3.2%.
291
SAMPLE CARUSEL
292
MANUAL VERSUS AUTOMATED PIPETTING
293
METHODOLOGY OF GRAPHITE FURNACE
TECHNIQUE
The ETAAS permits the anaIysis of Iiquid and soIid
sampIes. A known voIume or weighed quantity of the
sampIe is deposited on to the pIatform or directIy in the
tube where it is subjected to a series of stepwise
temperature programmes cuIminating in finaI rapid
increase in temperature for atomization. UsuaIIy
pretreatment steps are aimed at separating the
concomitants or the matrix components as much as
possibIe. The inert atmosphere enhances the reducing
properties of carbon Ieading to better atomization.
294
A majority of the eIements may be atomized around
2500-3000
0
K. Both pretreatment and atomization curves
may be optimized as a function of the absorbance signaI.
Since atomization emanates from the metaI, it is important
to reduce the sampIe to metaI earIy in the thermaI
pretreatment stage. However the pretreatment temperature
must stop beIow the decomposition temperature of the
metaI which is aIso the appearance temperature of the
metaI as evidenced by the absorption signaI.
295
CampbeII and Ottaway have postuIated a reduction
mechanism for many metaIs in ETAAS.
MeO + C Me + CO
They caIcuIated the free energy for the corresponding
reaction and compared the vaIues thermodynamicaIIy
with the appearance temperatures and found good
agreement.
296
Sturgeon and chakrabarty investigated atomization
mechanisms on the basis of a thermodynamic/kinetic
approach and proposed four mechanisms.
1) MO
(s)
M
(I)
1/2 M
2
(g) Mg
where M = Co, Cr, Cu, Fe, Mo, Ni, Pb, Sn, V
2) MO
x
M
(g)
+ x/2 O
2
(g)
where M = AI, Cd, Zn, Si
T
C
(s)
297
3) MO
(s)
MO
(g)
M
(g)
+ 1/2 O
2
where M = Cd, Mg, Mn, Zn
4) MX
2
MX
2
MX + g M + X
2
where M = Cd, Fe, Zn
Mechanisms 1 & 2 require intimate contact with graphite
surface but decomposition of oxides and haIides occur in
the vapour stage and hence are IargeIy temperature
dependent.
(s)
(I)
(g) (g)
298
Frech and Pearson have investigated the determination
of phosphorous in a graphite furnace. It has been
proved that PO (g) , PO 2(g) are present at 1800 K , so
that substantiaI Iosses must be expected at Iower
pretreatment temperature. Non-coated graphite tubes
are sufficientIy reactive to reduce partiaI pressure of
oxygen which wiII aIso reduce phosphorous Iosses. It
has aIso been shown that from the retained water
methinophosphide ( HCP (g) ) is formed. To prevent this,
atomization from pyroIytic graphite is carried out.
299
SPECTRAL INTERFERENCES IN ETAAS
Genuine spectraI interferences are as rare in graphite
furnace as in the fIame technique. However background
attenuation due to absorption of moIecuIar bands of
voIatiIized concomitants and radiation scattering of
sampIe particIes are quite frequent. Interferences aIso
occur by the interaction of the anaIyte eIement and the
condensed and vapour phases. Thus moIecuIar absorption
by aIkaIi haIides and radiation scattering are two important
interferences because the concentration of the
concomitants is more than 4-5 orders magnitude than
the anaIyte eIement is most cases. WhiIe medium
absorption is reproducibIe, radiation scattering can vary
from sampIe to sampIe but it foIIows moIecuIar absorption.
This they attributed to moIecuIes migrating to cooIer ends.
300
MoIecuIar spectra may be cIassified into dissociation
continuum and broad band eIectronic spectra. Long
waveIength maxima correspond to the dissociation of
moIecuIes into neutraI atoms whiIe the short waveIength
maxima are attributed to the dissociation into the excited
atoms. WhiIe the broad band spectra may be due to CN,
OH, NH
2
bands, the dissociation spectra aIways exhibits
sharp maxima as in the case of suIphite ions.
301
SO
3
+ h SO
2
+ O (
max
330 nm)
SO
2
+ h SO + O (
max
190 nm)
SO + h S + O (
max
245 nm)
SimiIarIy nitrogen containing moIecuIar bands exhibit

max
at 430 and 470 nm which aIso contribute to the
background absorbance.

302
Radiation scattering aIso can arise due to the formation
of smoke or soot during thermaI treatment of bioIogicaI and
organic sampIes or form the subIimed graphite at high
temperature. Most of these as weII as other moIecuIar
bands wiII not have much impact if the temperature is
carefuIIy controIIed at the atomization stage by the use of a
pIatform.
By seIecting suitabIe pretreatment temperature programme,
numerous matrix components can be effectiveIy reduced or
eIiminated. Then the anaIyte eIement can be anaIysed
without interferences.
303
BACKGROUND REDUCTION IN PLATFORM TECHNIQUE
304
If the anaIyte eIement is aIso voIatiIe, a Iow temperature
atomization must be considered even though it Ieads
to Iower sensitivity, but the matrix components wouId
not voIatiIize. Thus cadmium can be determined in
presence of 2% sodium chIoride at 750
0
C where NaCI
does not voIatiIize.
When the voIatiIities of the matrix and anaIyte are
simiIar thermaI pretreatment aIone can not guarantee
satisfactory separation of the eIement. In such cases,
phosphoric acid and nitric acid may be empIoyed as
'ashing additive' for bioIogicaI and organic sampIes.
305
Ammonium nitrate has aIso been routineIy used to
increase the voIatiIity of the matrix and simuItaneousIy
reduce that of the eIement.
The most probabIe reaction is:
NaCI + NH
4
NO
3
NaNO
3
+ NH
4
CI
Both reaction products can be easiIy decomposed or
subIimed around 400
0
C. Thus background attenuation
may be considerabIy reduced if not eIiminated by the
use of matrix modification.
306
The use of other gases such as hydrogen as the purge
gas reduces the spectraI interferences in the
determination of chromium in urine. SimiIarIy
background signaIs for NaCI and CaO couId be
substantiaIIy reduced if the graphite tube was fIushed
with hydrogen for 10 seconds before atomization.
SoIvent extraction and eIectroIytic deposition techniques
may aIso be used to remove matrix components, but
such steps need extreme precaution to prevent
contamination by externaI sources.
307
DETERMINATION OF LEAD IN STEEL
308
Despite the fact that continuum source background
correction are not ideaI to handIe spectraI interferences
quite a few investigators achieve success for majority of
cases. Some of these are tabuIated beIow.
EIement Interferent Matrix Cause Remedy
Se Iron(196nm) - rotationaI BG CORR
Iines Zeeman
As, Sb, CaIcium - P
2
rotationaI BG CORR
Se, Te phosphate bands Zeeman
Cd AIuminum AIuminum P signaIs Zeeman
BG CORR
309
VOLATILIZATION INTERFERENCES
VoIatiIization interference are quite compIex and have
not been understood compIeteIy. AII the processes
invoIving thermaI pretreatment, formation of carbides,
intercaIation compounds, subIimations, other
anaIyte-matrix interactions and kinetic effects pIay a
roIe in such interferences.
A simpIe carrier effect was observed with the
voIatiIization of NaCI in the determination of Iead. But
when iron is determined in presence of haIogenated
organic soIvents, voIatiIe iron chIoride was found to
be the cause of depressed signaI.
310
Even perchIoric acid decreases the signaI for aIuminum,
gaIIium and thaIIium by more than 95% when present in
0.5 M concentration. It forms a thermaIIy stabIe product
with graphite which decomposes onIy around 1700
0
C.
Thus a pretreatment at 1700
0
C is a must if the sampIe is
decomposed with perchIoric acid.
The interference of magnetism chIoride on the determination
of Iead couId be easiIy eIiminated by the addition of oxaIic
acid. Both oxaIic acid and fineIy dispersed carbon reduce
Iead oxide to metaIIic Iead. The interference can be termed
as a vapour phase effect.
311
The matrix modification technique proposed by EdIiger
is a major advance in handIing compIex systems which
causes the concomitants to be more voIatiIe and
converts the anaIyte into a Iess voIatiIe form. Use of
ammonium nitrate as a matrix modifier aIong with nickeI
saIts has been wideIy prevaIent for arsenic, seIenium and
bismuth. It has been proposed that nickeI forms arsenide,
seIenide and bismuthate which are stabIe up to 1400
0
C ,
1200
0
C and 1200
0
C respectiveIy. Therefore pretreatment
temperature may be raised to this IeveI, thus ensuring the
removaI of aII other matrix components. Copper, siIver
and moIybdenum saIts have aIso been tested as matrix
modifiers for arsenic and seIenium.
312
SeveraI other matrix modifiers have been investigated
over the years. These incIude Ianthanum ( for Pb),
phosphoric acid (Cd), caIcium nitrate (Mg), potassium
dichromate (Hg), magnesium nitrate ( Mn, AI , Cr, Co, Ni ).
Apart from increasing the stabiIization temperatures up
to 1200-1400
0
C numerous interferences are aIso
eIiminated when these modifiers are used.
WeIz and Mudakavi showed that a mixture of magnesium
nitrate and paIIadium nitrate couId act as a universaI
matrix modifier. They showed that Pd-Mg matrix modifier
couId be appIied to 21 eIements incIuding thaIIium and
mercury with stabiIization ranging from 1000-1900
0
C
whiIe decreasing the atomization temperatures by
200-300
0
C.
313
PRETREATMENT AND ATOMIZATION CURVES
314
PRETREATMENT AND ATOMIZATION
CURVES
315
PRETREATMENT AND ATOMIZATION
CURVES
316
It has been wideIy accepted that in any aqueous system,
water is retained even after 15 minutes at 1200
0
C in
vacuum. At higher temperatures the watergas equiIibrium
is prevaIent.
CO + H
2
O H
2
+ CO
2
Thus in an uncoated tube there is aIways a reIativeIy
high partiaI pressure of hydrogen. If chIoride saIts are
present (as in the case of Iead) then it is most IikeIy that
hydrochIoric acid is formed and expeIIed around 600
0
C.
But if the sampIe is present in nitric acid soIution, the
partiaI pressure of oxygen couId be quite Iarge Ieading to
the formation of Iead oxides and hence Ioss in sensitivity.
317
SimiIarIy if phosphoric acid and / or phosphates are
used as matrix modifiers PO, PO
2
and P
2
wiII be present
at Iower temperatures. OnIy at higher temperatures
phosphorous atoms wiII be present. Thus whiIe caIcium
phosphate couId be detected, phosphoric acid gave
no signaI! Frech et.aI, expIained this by the formation of
stabIe caIcium oxide formation according to :
Ca
3
PO
4
CaO
(s)
+ P
(g)
+ (PO,PO
2
,P
2
)
g
When pyroIytic graphite pIatform was used phosphorous
couId be detected easiIy because water can hardIy
penetrate the pIatform.
C
(s)
318
A number of authors have pointed that oxygen is
chemisorbed on graphite to form carbon-oxygen
compIexes with active sites where arsenic is attached.
These intercaIation compounds undergo Ioss of water
and oxygen thus reducing the stabiIity of interIameIIar
arsenic compounds. But such compounds are formed
at the defects sites in the crystaI Iattice which are very
difficuIt to atomize and even if possibIe the
absorbance-atomization curves show a Iong taiIing.
Such taiIing are actuaIIy seen in practice.
Since nitric acid aIso increases the distance between the
graphite Iayers thereby increasing the active sites the
signaI shouId be enhanced which has aIready been
proven. Other oxidants aIso behave in a simiIar way.
319
L'vov deveIoped a microkinetic theory of sampIe
voIatiIization for the graphite furnace. According to this
theory the sampIe is distributed in the form of
microcrystaIs, dropIets, particIes etc., weII separated
from each other. The sampIe penetrates into the
graphite tube by capiIIary action which is uniformIy
distributed in the width of the tube after drying. Upon
atomization the sampIe is physicaIIy removed from the
tube surface. In contrast with pyrocoated graphite the
sampIe is onIy distributed in space since it is inactive
and possesses a hard inert surface.
320
This theory gains credence when used graphite
tubes are examined by eIectron microscope after
treatment with Iead sampIes which showed the presence
of oxide or metaI embedded in a fiIm of carbon. A
simiIar treatment off the pyroIytic pIatform shows onIy
a heap of atoms of the matrix. SIovak and DocekaI
reported an interesting observation that such a heap
can aIso act as "minipIatform" deIaying the atomization
and increasing the sensitivity. L'vov and SIavin have
repeatedIy emphasized that for quantitative voIatiIization
of the sampIe under isothermaI conditions using a
pIatform with zeeman effect background correction,
peak area integration with maximum power and zero gas
fIow condition during atomization provides optimum
conditions for minimum interference.
321
SIGNIFICANCE OF DOUBLE PEAKS
It has been observed that doubIe peaks appear for a
number of voIatiIe eIements such as zinc and Iead.
When ascorbic acid or hydrofIuoric acid or hydrogen
peroxide is added to a Iead sampIe doubIe peaks
appear with a shift in time deIay. This has been
attributed to condensation in cooIer parts foIIowed by
deIayed revoIatiIization atomization . WhiIe this theory
does expIain peak broadening, it is stiII not satisfactory
for doubIe peaks.
322
Another pIausibIe theory is that, oxygen chemisorbed
onto the active sites of graphite tubes is responsibIe
for doubIe peaks and a shift in the appearance
temperature. MetaIs with voIatiIization temperatures
around 500
0
C and desorption around 950
0
C exhibit this
phenomenon. Atomization is preceded by reduction on
graphite surface. On the other hand when stabIe surface
oxides are formed. A different atomization mechanism
with higher activation energy is prevaIent.
DoubIe peaks cause errors in the peak height as weII as
peak area caIcuIation. Such doubIe peaks can be avoided
by matrix modifiers.
323
VAPOUR PHASE INTERFERENCES
In graphite furnace, just Iike fIame, dissociation and
ionization take pIace according to the Iaw of mass action.
However owing to high concentrations of free eIectrons,
ionization is quite sIow. Moreover the atmosphere in
eIectrothermaI atomization is reducing in contrast to the
oxidizing atmosphere in the fIame. Thus cyanides and
dicarbides are the predominant species for most of the
eIements.
324
The presence of sodium suIphate hinders the
quantitative atomization of a number of eIements. This
is aIso due to the presence of oxygen. Further proof is
obtained when oxygen is mixed with the purge gas
which aIso produce smaIIer number of atoms (hence
a smaIIer signaI) and deIayed appearance.
SimiIarIy excess nitrate in a sampIe aIso Ieads to the
errors when compared with nitrate free reference
soIutions. SaIts easiest to decompose decrease the
signaI where as others enhance the signaI. This is
quite important, because even the simpIest sampIes
contain nitrates.
325
Some other significant vapour phase interferences
have been tabuIated in TabIe 2. In concIusion it is cIear
that vapour phase interferences can be reduced or
eIiminated by the same means used for the eIimination
of many spectraI or voIatiIization interferences.
These measures incIude carefuI pretreatment
programming , matrix modification and highest possibIe
pretreatment temperature , foIIowed by peak area
integration.
326
ANALYSIS OF SOLID SAMPLES
According to L'vov's caIcuIations to obtain a reIative
detection Iimit of 10
- 6
% it is necessary to introduce
soIids at the rate of 1g/sec which is aImost impossibIe
in the fIame.
1
INDUCTIVELY COUPLED PLASMA ATOMIC
EMISSION SPECTROMETRY
2
When an atom is exposed to high temperature source
energy is transferred to the atom by coIIisions with
energetic particIes and aIso by the interaction with the
eIectromagnetic radiation. The excited atom decays to
a Iower energy IeveI with emission of its own
characteristic eIectromagnetic radiation. The
measurement of the eIectromagnetic radiation emitted
by the atoms, ions and isotopes can be accompIished
by empIoying suitabIe optics which aIso permits
concentration determination.
3
SCHEMATIC DIAGRAM OF ATOMIC EMISSION
ELEMENT
CONC
READOUT
EXCITATION
SOURCE
SPECTROMETER
DETECTOR
4
A. GENERATION OF EM RADIATION
ARC Discharge
SampIe is mixed with a conducting materiaI such as
graphite and packed into the crator of a carbon eIectrode.
A DC arc discharge between the sampIe eIectrode and the
counter eIectrode vapourizes the sampIe, decomposes
moIecuIar species produced in the pIasma and atomizes
the anaIyte. The atoms are excited to higher energy by the
energetic particIes in the pIasma.
5
ARC DISCHARGE
6
The DC arc is generated from a rectified power suppIy
which provides 5-30 A
0
and 10-25 V, generating
temperatures from 4000 - 6000
0
k. However the arc tends to
wander resuIting in poor anaIyticaI precision. As the arc
temperature is determined by the species in the arc pIasma,
the composition and temperature changes with time and
space. MoIecuIar species such as cynogen etc., exist in the
pIasma.
Many of these Iimitations can be minimized or eIiminated.
The DC arc is more suited for quaIitative anaIysis which
finds extensive appIications in foundries, steeI &
metaIIurgicaI industries.
7
An AC arc provides more uniform sampIing of the
eIectrode compared to DC arc. It operates at voItages
ranging from 1100 - 4400 V .The poIarity of the discharge
is reversed at each haIfcycIe and the discharge is
extinguished when the voItage drops to zero. The
sampIing is random, resuIting in improved precision
compared to the DC arc. The sensitivity is Iess that of the
corresponding DC arc.
8
HV SPARK
The circuit consists of HV transformer used to charge an
oiI fiIIed capacitor and an auxiIiary controI gap to initiate
and controI the discharge. A potentiaI of 15000 - 45000 V
deveIops across the anaIyticaI gap. An HV spark discharge
between the metaI sampIe and counter eIectrode generates
sufficient energy to vapourise the sampIe and generate
atoms and excite them. The emitted radiation is monitored
through a quartz window mounted on the excitation stand.
A thoriated tungsten eIectrode is used as a counter eIectrode
and argon is used to purge the gas chamber.
The spark technique is usefuI for major, minor and trace
eIements in metaIs and aIIoys for anaIysis and production
controI. The intensity of the emission is measured reIative to
iron and pIotted against the concentration ratio to eIiminate
errors resuIting from the fIuctuations. TypicaI detection Iimits
are of the order of 0.001 to 0.1% by weight.
9
SPARK DISCHARGE
10
GLOW DISCHARGE
It consists of a fIat sampIe cathode and cyIindricaI anode
mounted in a seaIed chamber fiIIed with argon.
At 600 - 1800 V , the gas is ionized and acceIerated to the
cathode. CoIIisions with the cathode surface causes
vapourization of the sampIe materiaI and excitation. The
emitted radiation is viewed from a quartz window.
The cathode bIock which is in direct contact with the sampIe
is water cooIed to remove excess heat. The sampIe is
pressed against the open end of the cathode body and heId
in vacuum. After evacuation the chamber is fiIIed with argon
to 5-15 torr pressure. Standard caIibration curves for the
determination of trace eIements in pure materiaIs are Iinear
over three orders of magnitude in concentration.
11
LASER INDUCED PLASMA
PuIsed Iaser beams have been used in AES of
extremeIy smaII sampIes and occIusions on surfaces
of metaI aIIoys Iaser beam is focused on sampIe
surface and the materiaI is vapourized. The pIasma
pIume formed above the target passed through an
auxiIiary eIectrode gap and is excited by a Iow voItage
spark discharge.
HoIIow cathode discharge :
0.06-10 ppm for soIid sampIes and from 0.2-1 ppm
for soIutions.
12
The eIectromagnetic radiation is resoIved with a
spectrograph and the spectra are recorded photographicaIIy
or measured with an array detector. SoIid state Nd gIass
Iaser, a spark source, a mirror and focusing Iens to direct
the Iaser beam on to the surface of the sampIe constitute the
instrumentation.
A Iaser puIse with 0.1 - 1.0 J and a duration of 2 sec
produces a crator of 25 - 250 m. The detection Iimit is
10
-9
- 10
-11
g.
13
PLASMA SOURCES
High temperature pIasmas generated from eIectricaI
power sources where coIIisions are induced by
eIectricaI currents are usefuI for the anaIysis of soIid,
Iiquid and gaseous sampIes. They are Direct Current
PIasma (DCP), Inductivity CoupIed PIasma (ICP) and
Microwave Induced PIasma (MCP).
A DC pIasma source consists of a DC arc discharge
between two eIectrodes in which argon is introduced.
Gas is introduced in a tangentiaI fIow so that the
resuItant gas is constricted, resuIting in increased
current density and higher temperature. The DC pIasma is
operated at a current 5 - 30 A
0
and gas fIow rates up to
70 Iitres/minute. Temperatures in the pIasma range from
4700-11000 K.
14
The sampIe is introduced as an aerosoI by means of a
neubuIizer positioned between the eIectrodes (anodes).
The opticaI measurement region is Iocated near the
base of the confIuence to eIiminate high background
from the arc pIasma.
It is usefuI for anaIysis of soIutions containing 45% of the
totaI dissoIved soIids. The advantage is that it is a Iow
cost DC power suppIy. However continuous operation
for Ionger periods is not possibIe because the
eIectrodes erode. ConsequentIy eIectrodeIess pIasma
sources such as inductiveIy coupIed pIasma are
common in ICP - AES.
15
PLASMA TORCH
16
INDUCTIVELY COUPLED PLASMA
The energy to form the pIasma is generated by a high
frequency magnetic fieId. It is anaIogous to that of a
transformer in which primary winding is an induction coiI
with an osciIIatory current from a RF generator. The
secondary winding (or Ioad) is the ionized argon gas which
is coupIed inductiveIy to the radio frequency source. The
pIasma torch consists of two concentric quartz tubes with
Ar gas fIowing tangentiaIIy between the inner and outer
tubes to provide cooIing and a water cooIed induction coiI
near the periphery of the outer tube. Argon gas fIowing
through the smaIIer tube interacts with the magnetic fieId
when sufficient externaI energy is appIied to ionize the gas.
InitiaI ionization can be provided by a TesIa discharge and
the pIasma is sustained by ionized argon formed in the high
temperature pIasma.
17
The sampIe is directed into the pIasma through a capiIIary
tube mounted in the centre of the torch assembIy. An RF
generator of 1-5 kw at 3-100 MHz wiII sustain an argon
pIasma which produces 5000 - 10000 K depending upon
the power, gas fIow rate and composition and coupIing
efficiency. Optimum viewing heights vary with the anaIyte
and which is usuaIIy a compromise of 3 -10 mm range in
muIti-eIement anaIysis.
ICP is an extremeIy versatiIe source for AES. SampIe
soIutions are nebuIized into a chamber and the aerosoI
is directed into the pIasma using a carrier gas. Standard
caIibration curves for most eIements are Iinear over 5-6
orders of magnitude in concentration and detection Iimits
range from 0.1 to 200 ppb.
18
MICROWAVE INDUCED PLASMA
The pIasma source consists of a microwave resonator
or a cavity inductiveIy coupIed to a high frequency
generator by means of a coaxiaI waveguide. It provides
200-500 W of power at a frequency of 2 - 45 GHz. Power
is transferred to the microwave cavity by means of a
coupIing Ioop.
MIP is used to determine a wide variety of gases
such as C, H, N, O, F, CI, Br, S. Detection Iimits range
from 1 - 50 ppb and caIibration curves are Iinear over
3 - 4 orders of magnitude.
19
B. SEPARATION OF EM RADIATION
EIectromagnetic radiation can be separated into its
components by a variety of instruments and techniques.
Grating instruments are commonIy used. For high
resoIution spectroscopy the incident radiation can be
separated in two dimensions by an EcheIIe grating and
separating muItipIe orders with a prism. Fourier transform
spectroscopy has been deveIoped that extends the
waveIength range to uItravioIet region.
20
ECHELLE GRATING
21
CONCAVE GRATINGS
In RowIand mounting, the grating and the detector are
attached to a rigid bar that moves reIative to a fixed
entrance sIit. The angIe of diffraction remains constant
and the angIe of incidence varies. The detector is aIways
kept in a position normaI to the grating. Under these
conditions, the dispersion is Iinear over a broad waveIength
range.
In Abney mounting, grating and detector are fixed and
the sIit moves aIong the axis of the RowIand circIe. This is
sIightIy cumbersome because Iight source and externaI
optics aIso need to be repositioned when the angIe of
incidence is changed.
22
ROWLAND MOUNTING
23
In EagIe mounting, sIit and detector are mounted on the
same side of the grating normaI to aII components on
the RowIand circIe. This is a compact arrangement.
The Paschen - Runge mounting has sIit ,grating and
detector at fixed positions on the RowIand circIe. Most
of the commerciaI direct reading instruments are of
this type.
In Wadsworth mounting, a sphericaI mirror is used to
coIIimate the incident beam which iIIuminates the
grating with a paraIIeI Iight. When the waveIength
region is changed, the detector to grating distance must
be changed to maintain proper focus of the diffracted
Iight.
24
PLANE GRATINGS
The Ebert - Fastie and Czerny turner mountings utiIize a
pIane grating in combination with a sphericaI mirror to
coIIimate the incident beam and to focus the diffracted
Iight on the exit sIit or detector. The incident beam
passes over the grating and the diffracted Iight passes
under the grating. Since the detector is near normaI to the
grating pIane, the dispersion is approximateIy Iinear.
The Czerny -Turner mounting differs from the
Ebert - Fastie in that the spectrometer has two sphericaI
mirrors. These are used in combination with array
detectors which have repIaced photographic emuIsions
for the measurement of spectra.
25
Czerny - Turner mounting
26
C. DETECTION OF ELECTROMAGNETIC RADIATION
The PMT is the preferred mode of measurement. It
consists of a photo cathode, a series of dynodes and
an anode in an evacuated tube. The ampIification is
nearIy 1 miIIion. The Iine image is focused on the sIit
and directed to PMT by means of a refractor pIate.
27
PHOTOGRAPHIC DETECTOR
This is the most sensitive and versatiIe technique. A
densitometer is used for measuring and identifying
eIements. It consists of a photopIate or fiIm hoIder
assembIy and a Iight source and associated photo
detector to measure the quantity of Iight passing
through a photographic emuIsion. The photopIate is
moved in a direction normaI to the Iight beam and
can be positioned to measure any segment on the
photopIate. The image is magnified and dispIayed on a
screen. A reference spectrum with spectraI Iines of
known eIements is dispIayed adjacent to the sampIe
spectrum.
28
THE ICP SOURCE
A typicaI ICP source is caIIed a torch. It consists of three
concentric quartz tubes through which streams of argon
fIow at a totaI rate of 5-20 L/min. the inner diameter of the
tube is about 2.5 cm. The top portion of this tube is an
induction coiI that is powered by a radio frequency
generator which radiates 0.5 - 2 kW of power at 27.12 MHz
or 40.68 MHz at this voItage a spark from the TesIa coiI
ionises the argon.
29
The resuIting ions and their associated eIectrons interact
with the fIuctuating magnetic fieId produced by the
induction coiI. This interaction causes the ions and
eIectrons within the coiI to fIow in the cIosed annuIar paths.
The resistance of the ions and eIectrons causes ohmic
heating of the pIasma.
The temperature of the pIasma reaches 4000-6000 K, which
requires thermaI isoIation of the outer quartz cyIinder. This
is achieved by argon fIowing tangentiaIIy around the waIIs
of the tube and entering the pIasma radiaIIy.
In most of the instruments the torch is positioned at 90
0
and aIigned axiaIIy with the spectrometer system. The
radiation emitted from the pIasma is used for anaIysis.
30
TYPICAL DESIGNS OF ICP TORCHES
31
SAMPLE INTRODUCTION
The most common means of sampIe introduction is through
the BernouIIi effect. High veIocity moving gas fIowing
around a capiIIary sucks the sampIe and deIivers it at the tip
where the Iiquid breaks up into fine dropIets before entering
the pIasma.
Another way of introducing the sampIe is to pump it through
the capiIIary using a peristaItic pump. At the tip, high
veIocity argon fIows across at right angIes causing the same
BernouIIi effect.
It is aIso possibIe to atomize the sampIe in a graphite tube
and introduce the vapour into the pIasma.
32
MEIN HARD NEBULIZER
33
A typicaI pIasma appears as very intense white fIame. It has
a non-transparent core topped by a fIame Iike taiI. The core
extends a few miIIimeters above the tube and produces the
atomic spectrum of argon superimposed on a continuum
spectrum. The continuum spectrum is typicaI of charged
ions and eIectrons interaction and known as
"bremstrahIung".
10-30 miIIimeters above the core the continuum fades and
the pIasma is opticaIIy transparent. Hence spectraI
observations are generaIIy made a 15-20 miIIimeters above
the induction coiI where temperature of 6000-6500 K prevaiI.
In this region the background radiation is remarkabIy free
from the argon Iines but those of Ca
+
, Cd
+
, Cr
+
, Mn
+
etc.,
remain.
34
TEMPERATURE VARIATION IN THE PLASMA
35
ADVANTAGES OF PLASMA SOURCE
High temperatures ensure compIete atomization. Hence
fewer interferences are found in ICP.
Atomization occurs in a chemicaIIy inert environment.
The temperature cross section is more uniform.
Therefore seIf absorption or seIf reversaI do not occur.
Therefore caIibration curves are Iinear over severaI
orders of magnitudes of concentration.
Since the pIasma produces significant ionization, it is
an exceIIent source for ICPMS.
36
PLASMA SOURCE SPECTROMETERS
High resoIution 0.01 nm or / > 100,000.
Rapid signaI acquisition and recovery.
Low stray Iight.
Wide dynamic range (> 10
6
).
Accurate and precise waveIength identification and
seIection.
Precise intensity readings (< 1% reIative standard devn).
High stabiIity with respect to environmentaI changes.
Computerized data handIing.
37
SEQUENTIAL ICP INSTRUMENTS
Such instruments use a hoIographic grating
monochromator of 2400 or 3600 grooves/mm. Scanning
is accompIished by rotating the grating with a digitaIIy
controIIed stepper motor so that precise waveIengths
are focused on the exit sIit.
In some designs the grating is fixed and the sIit and
photomuItipIier tubes are moved aIong the focaI pIane.
For uItravioIet and visibIe range, separate sets of sIits
and PMTs are used. The switch between the two is
effected by the movement of a pIane mirror Iocated
between the two transducers.
38
The scanning of spectra is controIIed by a computer in
a series of smaII steps of 0.01 to 0.001 nm. UsuaIIy
whenever there is no emission, the spectra is scanned
quickIy and sIows down near a peak. Such an
arrangement is known as sIew scan spectrometer.
39
OPTICAL SCHEMATIC DIAGRAM OF ICP
40
MULTICHANNEL INSTRUMENTS
In muItichanneI instruments the entrance sIit, exit sIits
and the grating surface are Iocated around the
circumference of a RowIand circIe which corresponds
to the focaI curve of the concave grating.
Radiation from each of the fixed sIits impinges on the
PMTs. The sIits are factory configured to transmit Iines
for seIected eIements. The signaIs are integrated , the
output is digitized and converted into concentrations.
For rapid anaIysis such instruments are quite usefuI.
41
MULTICHANNEL ARRANGEMENT 1
42
MULTICHANNEL ARRANGEMENT 2
43
APPLICATIONS OF PLASMA SOURCES
UsefuI for quaIitative and quantitative eIementaI
anaIysis. The sampIes must be dissoIved in aqueous
or organic soIvents.
In principIe aII metaIIic eIements can be determined
by ICP. For B, N, S and C, vacuum spectrometer is
necessary as their emission waveIengths are Iess
than 180 nm.
Li, K, Rb and Cs Iines are Iocated at near IR Iines
which Iead to detection probIems.
44
TYPICAL DETECTION LIMITS IN ICP
45
CHEMICAL ANALYSIS WITH ICP
TypicaI caIibration curves in ICP consist of eIectricaI
signaIs in the form of counts (intensity) versus anaIyte
concentration . More than 70 eIements have been
determined by ICP at various waveIengths and the
data is recorded to three decimaI pIaces with
appropriate intensity. The information is avaiIabIe in
severaI data bases and standard pubIications. Thus a
suitabIe waveIength for any eIement can be found
easiIy.
46
UsuaIIy the seIection of an anaIyticaI Iine depends
upon the intensity. However other concomitant
eIements present in the matrix shouId not be emitting
at the same waveIength. CaIibration pIots are usuaIIy
Iinear over severaI orders of magnitudes of concentration.
Therefore Iog-Iog pIots can aIso be used.
47
TYPICAL CALIBRATION CURVES IN ICP-AES
48
Departures from Iinearity often occur especiaIIy when
Iarge concentrations are covered.
SeIf absorption becomes evident onIy at high anaIyte
concentrations and causes the caIibration curves to
bend towards the horizontaI axis.
NonIinearity aIso arises from erroneous background
correction, from ionization and from nonIinear
detector responses.
49
INTERNAL STANDARD
In ICP work an internaI standard is often used. In
this case, the verticaI axis of the caIibration curve is the
ratio or the Iog ratio of the detector signaI for the anaIyte
and that of the internaI standard. Thus the intensity
improves to a considerabIe extent.
50
INTERNAL STANDARD CALIBRATION CURVES
IN ICP
yttrium 242.2 nm as internaI standard
51
INTERFERENCES
ChemicaI and matrix interferences are significantIy
Iower with pIasma sources compared to other atomizers.
However at Iow anaIyte concentrations the background
emission due to recombination of argon ions with
eIectrons is significant. For both singIe channeI and
doubIe channeI instruments, this correction is made by
taking an average of the background readings on either
side of the emission peak. Nowadays instrument
software accompIishes this task automaticaIIy or at the
discretion of the operator.
52
SpectraI interferences are aIways possibIe in ICP
anaIysis because emission spectra of many eIements
are rich in Iines. Therefore it is preferabIe to have a
knowIedge of the other matrix eIements in the sampIe
and their emission Iines to choose a noninterference
anaIyticaI Iine.
The software for ICP instruments has powerfuI routines
for waveIength seIection, caIibration, spectraI anaIysis
and deconvoIution of overIapping Iines. AdditionaIIy,
integrated data bases of spectraI Iines of other eIements
make spotting and correcting for interferences an
integraI part of the anaIyticaI process.
53
DETECTION LIMITS
In generaI, detection Iimits in ICP-AES are comparabIe to or better
than fIame AAS and eIectrothermaI AAS. The foIIowing tabIe is
iIIustrative.
54
DETECTION LIMITS OF ICP
55
TabIe 1. DETECTION LIMITS FOR AIR-ACETYLENE
FLAME
56
!"#$% ' (
57
!"#$% ' (
58
!"#$% ' (
59
!"#$% ' (
60
!"#$% '(
61
TabIe 2. DETECTION LIMITS FOR NITROUS OXIDE
ACETYLENE FLAME
62
!"#$% ' (
63
!"#$% ' (
64
!"#$% ' (
65
!"#$% ' (
66
!"#$% ' (