Atomic spectroscopy

Chapter 20
2
Absorption of sharp lines
from hollow cathode lamp
Fluorescence following
absorption of laser radiation
Emission from thermally
populated excited state
Atomic techniques
ICP torch
3
Atomic absorption experiment
Gaseous atomic spectra consists of sharp line
sharp lines
little overlap between spectra of different elements
allow determination of many elements simultaneously
4
Sample introduction: Flame
Use of premix burners: fuel, oxidant and sample are mixed before
introduction
Nebulization: convert sample solutions into fine aerosol.

Premix burner
Flame Flame
atom particles solid aerosols Solution
ion volatlizat n evaporatio solvent on nebulizati

5
Flame temperatures
6
Effect of temperature
Higher temperatures increase the total
amount of atom population in the flame
(Absorption/emission)
Higher temperatures can also increase the
rate of ionization (Absorption/emission)
Ba Ba
+
+ e | at T > 3000 K 50% of Ba
is present as Ba
+
Flame temperature also determines the
relative number of excited atoms in the
flame (emission).
Analytical signal depends on the
Number of excited atoms
7
High boiling elements Refractory elements
require hotter flames e.g. Ca, Mg (Form MOH and MO
species in the flame).
Rich flames rich in fuel excess carbon reduces MOH
and MO
Increases sensitivity for refractory elements.
Lean flame with excess oxidant (hotter)
Elements requirements for rich or lean flame
Type of element
Flow rate
Oxidant and flame type

Effect of temperature
8
Experimental corner
Flame photometry
Determination of Na and potassium in cement
Analysis of water for Na, K, Li and Ca.
Analysis of Ca in food samples e.g. in cereals
Atomic absorption
Analysis of Fe and Zinc in food samples and in
drugs.
Analysis of Ca in food and water
Analysis of metal ions in water, sediments and soil
samples.
One of the most important analytical techniques for
the analysis of metal ions in various matrixes.

9
Graphite furnaces Electrothermal atomization
Advantages
Higher sensitivity than
flames
Residence time for atoms in
the optical light path is longer
Require less sample volumes
(1-100L).
Disadvantage
Require more operator skill

10

Example: analysis of Fe

Drying (125, 20s)
Charring or pyrolysis
(1400 , 60 s) to remove
organic matter
Atomization( 2100 , 10 s)
Purging with N
2
or Ar(
2100 , 3s)
Iron in blood samples
11
Furnace temperature
Furnaces can be heated
Transversely (from side to side)
Uniform furnace temperature
Longitudinal (from end to end)
Center of furnace is hotter than
ends
Memory effect interference
Memory effect
Interference from previous runs
Reduced by coating furnace by
pyrolytic graphite
12
Interference
A phenomenon in which the presence of one
substance in the analytical sample changes the
magnitude of the signal measured for the analyte.
Selectivity of techniques is related to its freedom
from interference effects.
Types of interference in atomic absorption
Memory effect
Matrix effect
Spectral interference
Chemical interference
Ionization interference.

13
Matrix modifiers for furnaces
A substance added to the sample to reduce loss of
analyte during the charring
By making the matrix more volatile or
The analyte less volatile
Examples:
Mg(NO
3
)
2
is added to retard the evaporation of Al.
Mg(NO
3
)
2
MgO(g)
Al(analyte) Al
2
O
3
(s)
3MgO(g) + 2Al(s) 3Mg(g) + Al
2
O
3
(s)
A
A
A
14
Analysis of Mn in sea water
NH
4
NO
3
is used as matrix modifier (matrix more volatile)
NH
4
NO
3
+ NaCl NH
4
Cl + NaNO
3
Smoke created by heating NaCl
NH
4
Cl +NaNO
3
evaporates
cleanly without making smoke
15
Inductively coupled plasma (ICP)
Plasma mixture of ionized Ar and electrons
Characteristics of the plasma
High temperature (6000 - 1000C)
Stable and chemically inert
Less interference compared to the flame
techniques


11-17 L/min
16
Sample introduction
Ultrasonic nebulizers
17
Effect of temperature
kT E
e
g
g
N
N
on distributi Boltzmann
/
0 0
* *

A
=
N*/N
0
relative population of any states
T is temperature in K, k is Boltzmann constant
18
Effect of temperature
Flame temperature variation is very critical for
emission techniques compared to absorption
techniques
N*/N
0
for Na at 2600 K = 1.67 10
-4
N*/N
0
for Na at 2610 K = 1.74 10
-4
The fraction of atoms in the excited sate is <
0.02%
The fraction of atoms increased by 4% by an
increase of 10 K in T.

19
~ 700,000 times increase in
population of excited state
20
Instrumentation
To select one line from
the hollow cathode lamp!
To reject as much
emission from the flame
or furnace.

21
Hollow cathode lamp
Tungsten
Fabricated from
metal analyte
Inert gas (Ar)
at P = 1 5
torr
300 V
Ar (300 V) Ar
+
+ e
Ar
+
anode
e cathode causes sputtering of toms
Some of the sputtered metal atoms are in the excited state.
22
Atomic line broadening
23
Atomic line width
Line broadening
Natural broadening (quantum mechanical
effect)


Doppler effect
An atom moving toward the detector
appears at a lower wavelength than an
atom moving away from the detector.

Pressure broadening
Collision between excited atoms shorten
the lifetime of the excited sate

o o
t
o o v = > > A A
E
E h
t E t

|
4
|
M
T
7
10 7

~ o
24
Multielement detection with ICP
Up to 70 elements simultaneously
Uses CCD and CID detectors.
Multi photomultiplier systems
More sensitive

ICP torch
25
26
Background signals
Emission, absorption, and scattering from matrix, flame,
plasma or the white hot furnace
Must be minimized! better detection limits
Background absorbance
Mean baseline signal = average of
signal of pixels 1, 2, 14, and 15
Mean peak signal = average of pixel 7
and 8.
27
Background correction
Beam chopping
(modulation)
Distinguish signal of the
flame from that of the
desired atomic line at the
same
Corrects for emissions
from the flame but not
for scattering.



28
Deuterium lamp background correction
Deuterium lamp

Rotating chopper
To monochromator
Analyte hollow
cathode lamp
A
analyte
= A
hollow cathode lamp
A
deuterium lamp
deuterium_lamp
.ppt
29
Zeeman effect
Applying a magnetic field parallel to the light path
Analytical atomic lines split into three components
Two are slightly shifted one unshifted
t component absorbs plane polarized
o component absorbs radiation polarized at 90 C to the
fild.

30
Detection limits
The concentration of an element that gives a signal
that is 2 the peak-to-peak noise level of the baseline
The baseline noise should be measured for a blank
sample.
31
32
Interference
Spectral interference
Unwanted signals overlapping
with the analyte signals
Minimized by
D
2
or Zeeman correction for
flame emissions
Choose another wavelength for
analysis
Use high resolution
spectrometers


33
Chemical interference
Chemical reactions that decreases the
concentration of the analyte
SO
4
2-
and PO
4
3-
prevents the atomization of
Ca
2+
(forming nonvolatile compounds)
Minimized by adding releasing or masking
agents
Substance added to sample to decrease
chemical interference
8-hydroxyquinoline(masking), La
3+

(releasing) protects Ca
2+
from chemical
interference

34
Ionization interference
Ionization of an analyte decreases the
concentration of neutral atoms
M(g) M
+
(g) + e(g)
K = [M
+
][e]/[M]
Ionized atoms have different
absorption and emission
wavelengths
Minimized by addition of ionization
suppressor
An element added to sample to
decrease the extend of ionization
CsCl added at 1000 ppm during
analysis of K
35
Standard addition method
compensates for any type of interference
36