CHAPTER 4: ATOMIC

SPECTROSCOPY

General
3 major type of spectrometric method of
identifying elements in the samples
i. Optical spectrometry
ii. Mass spectrometry
iii. X-ray spectrometry
In Optical spectrometry, elements in the
sample are converted to gaseous atoms
or elementry ions by a process called
atomization. The absorption, emission, or
fluorescence of the atomic species in the
vapour is then measured.
Optical spectrophotometry
Common
i. Atomic absorption spectroscopy ,
Eg. AAS instrument
ii. Atomic emission spectroscopy, ICP-
OES
iii. Atomic fluorescence spectroscopy,
AFS

Note: Atomization is usually achieved
either by flames, electrically
heating or by plasmas.
Process Occurring in Flame (Gary D. Christian 6
th

ed, pg 522)
The solution is aspirated into the flame
as a fine spray
The solvent evaporates, leaving the
dehydrated salt
The salt is dissociated into free gaseous
atoms in the ground state
A certain fraction of these atoms
absorbed energy from the flame (some
of them are collided each other) and be
raised to the excited electronic state
The excited state have a short lifetime
and returned to the ground state by
emitting photon with characteristic
wavelength,

hc
E =
Continue.
Eg. characteristic wavelength of elements:






The intensity of emission/absorption is directly
proportional to the conc. of analyte in the solution,
therefore a calibration curve of emission/absorption
intensity vs conc. is prepared
However, side reactions in the flame may decrease the
population of free atom and hence reduced the
emission/absorption signal
Elements (nm)
Na 589
Ca 422
Zn 213
Continue.
Therearethreefundamentalprocessesthatcanoccurinthe
atomiclevel.
Eo
Ej
Atomic emission
Atomic absorption
(from ground state)
Ej
Ei
Ej
Ei
Atomic emission
(thermal excitiation)
Atomic flourescence
(light excitiation)
Processes
In
Flame
M*
excited
salt vapourised
*ATOMISED
*
Solution MX
Liquid aerosol
droplets
Salt mist of MX
Molecules of MX
M

M
+
ionised
MX
compound
formed
nebulisation
solvent evaporation
Dissociation
Thermal and chemical
Characteristic wavelength, transition
elements
Distribution between ground and excited states- Most
atoms are in the ground state
The relatives populations of ground-states N
0
and excited-
state N
e
at a given flame temperature via the Maxwell-
Boltzmann Equation


|
.
|

\
|
A

|
|
.
|

\
|
=
kT
E
o
e
o
e
e
g
g
N
N
g
e
and g
0
are the statistical weights of the excited and ground
state
AE is the difference in energy between the excited and lower
or ground state
k the Boltzmanns Constant 1.38062 x 10
-23
J K
-1

T is the temperature in K

Therefore, the more atoms in the excited state the higher
the intensity of the emission.


Representatives Detectin Limit by AAS and Flame
Emission Spectroscopy, FES/ICP
Element Wavelength (nm)
Detection Limit (ppm)
AAS FES (ICP)
Ag 328.1 0.001(A) 0.01
Al 309.3 0.1 (N)
Au
396.2 0.08
242.8 0.03 (N)
Ca
267.7 3
422.7 0.003 (A) 0.0003
Cu 324.8 0.006 (A) 0.01
Eu 459.4 0.06 (N) 0.0008
Hg 253.6 0.8 (A) 15
K 766.5 0.004 (A) 0.00008
Mg 285.2 0.004 (A) 0.1
Na 589 0.001 (A) 0.0008
Tl
276.8 0.03 (A)
535 0.03
Zn 213.9 0.001(A) 15
Detection Limit (ppm): The conc required to give a signal equal to three times the
standard deviation of base line (Blank)

< 300 nm: AAS shows superior detectability because high thermal energy required
to excite the atom for emission at these wavelength
300 < < 400 nm: either method exhibit comparable detectability


Energy level diagram illustrating energy changes associated with absorption of
electromagnetic radiation

A = pure rotational changer (far IR)
B = rotational + vibrational changes (near IR)
C = rotational + vibrational + electronic transition (Vis + UV)
E
o
= electronic ground state
E
1
= first electronic exited state

Calibration Curve
Standards containing known concentrations of the
analyte are introduced into the instrument
Response is recorded
Response is corrected for instrument output
obtained with a blank
Blank contains all of the components of the original sample
except for the analyte
Resulting data are then plotted to give a graph of
corrected instrument response vs. analyte
concentration
An equation is developed for the calibration curve
by a least-squares technique so that sample
concentrations can be computed directly

Atomic Absorption Spectrophotometer- Schematic Diagram For a
Double Beam Instrument
MONOCHROMATOR PHOTO
DETECTOR
AMPLIFIER
AND
READOUT
LIGHT
SOURCE
flame
Sampl
e
Chopper
Double beam instrument that measures the ratio P
0
/P (Beer Lambert
Law)
The source beam is alternately sent through the flame and around the
flame by the chopper
The detector measures these alternately and the logarithm of the
ratio is displayed
The detector amplifier is tuned to receive only radiation modulated at
the frequency of the chopper and the radiation emitted by the flame is
recorded (characteristic of individual element)

Major component:

Atomic Absorption Spectrophotometer- Major Componet
A. Sources: hollow-cathode lamp (HCL), used in
atomic absorbtion
Tube filled with inert gas (Ne or Ar)
Hollow cathode (negative) made with metal we
want to detect
Run a high voltage between anode and
cathode
This makes Ne or Ar ionize
Ne+ or Ar+ attracted to hollow metal cathode
As these ions hit the metal, atoms of metal are
ejected into the gas
As metal atom interact with energetic electrons
atoms are excited,
so generate light at that metals wavelength
since excitation is not by flame the linewidth is
extra sharp
Note: Flame used for atomization only not to
excited the electron of the free atom
Atomic Absorption Spectrophotometer- Major
Componet
B. Burner: pre-mix burner containing of nebulizer, chamber
and burner, desolvation/drying process
C. Flame: A flame provides a high-temperature source for
desolvating and vaporizing a sample to obtain free atoms
for spectroscopic analysis. In atomic absorption
spectroscopy ground state atoms are desired. For atomic
emission spectroscopy the flame must also excite the
atoms to higher energy levels. The table lists temperatures
that can be achieved in some commonly used flames.

Temperatures of some common flames
Fuel Oxidant Temperature (K)
H
2
Air 2000-2100
C
2
H
2
Air 2100-2400
H
2
O
2
2600-2700
C
2
H
2
N
2
O 2600-2800
Sample Preparation
The sample must be in the diluted form
and filtered for particulates
Type of sample: blood, urine, tissues,
cerebral spinal fluid and other biological
fluids by direct aspiration of the sample,
usually dilution with water is required to
prevent clogging of the burner
In the preparation of standards, the
matrix of the analyte must always be
matched, Eg. Analysing Zn in waste
water, standard solution is made up from
ZnCl
2

Case study: determination of heavy metals (Pb,
Cr, As and K) in Selom plant

Raw Materials : Selom plant
Chemicals: nitric acid and hydrochloric acid with ratio of
3:1 and distilled water
Procedure: dry the fresh Selom in the oven before
ashing process to avoid unnecessary explosion
Burn the dry selom in the furnace at 500C for one hour
About 5 g of Selom ash is required before acid
digestion process
The solution is then filtered and diluted to the required
concentration for AAS and/or ICP-OES analysis
Prepared the standard solution for each metal and
obtained their calibration curve
From the regresion equation the concentration of each
element can be calculated
Ashing method
placingthe sample in an open inert
vessel and destroying the combustible
(organic) portion of the sample by
thermal decomposition using a muffle
furnace. Typical ashing temperatures
are 450 to 550 C. Magnesium nitrate is
commonly used as an ashing aid.
Charring the sample prior to muffling is
preferred. Charring is accomplished
using an open flame.

Acid digestion/pressure
digestion/microwave digestion
Acid digestion process are employed
for the determination of elements in
solid subsequent to sampling and
mechanical sample preparation in
order to completely transfer the
analytes into solution so that it can be
introduced to analysis instrument-
ICP-OES, AAS and ICP-MS
Common acid used, mineral acids
(HCl, HNO
3
, HF, H
2
SO
4
etc)