Spectroscopy –I

Atomic Absorption Spectroscopy

presented by
Reena V. Rathod
Contents…..

• Introduction
• Working Principle
• Instrumentation:
 Radiation sources
 Atomizers
 Wavelength selector
 Detectors
• Interferences
• Applications and Limitations
Atomic absorption spectroscopy and atomic emission
spectroscopy are used to determine the concentration of an
element in solution.
Introduction
• Invention: Introduced in 1955 by Alan Walsh in Australia and
Firstly used for mining, medical treatment & agriculture.

• Atomic Absorption Spectroscopy (AAS) is a quantitative method of

analysis which is applicable to many metals and a few non-metals,
almost every metallic element can be determined quantitatively by
using the spectral absorption characteristics of atoms.

• It can analyze over 62 elements.

Alan Walsh
(1916-1998)
Difference between molecular absorbance and atomic
absorbance spectrum

Applying Lambert-Beer’s law is difficult

Follow Lambert-Beer’s law due to
 Uniformity of concentration  variations in the atomization from the
path length of analyte sample matrix
molecules.  non-uniformity of concentration path
length of analyte atoms.
 Principle
• “When a beam of monochromatic radiation
is passed through the atoms of an element,
the rate of decrease of intensity of
radiation is proportional to the intensity of
incident radiation as well as the
concentration of the solution.”

• It is based on the same principle as the

flame test used in qualitative analysis.
 The high temperature of the flame excites a valence electron
to a higher-energy orbital

 The atom then emits energy in the form of light as the electron
falls back into the lower energy orbital (ground state)

 The intensity of the absorbed light is proportional to the

concentration of the element in the flame

 Each element has a characteristic spectrum

Example: Na gives a characteristic line at 589 nm

 Atomic spectra feature sharp bands

Instrumentation of AAS

Atomized
Sample

• Hollow Cathode
Lamp(HCL)
• Electrodeless Discharge
Lamp(EDL)
Hollow cathode lamp (HCL)
• An excellent, bright line source for most of the elements determinable by
atomic absorption.
• Each HCL will have a particular current for optimum performance.
• In general, higher currents will produce brighter emission and less baseline
noise. As the current continues to increase, lamp life may shorten and spectral
line broadening may occur, resulting in a reduction in sensitivity and linear
working range
 The anode and cathode are sealed in a glass cylinder normally filled
with either neon or argon at low pressure. At the end of the glass
cylinder is a window transparent to the emitted radiation.

 The cathode of the lamp frequently is a hollowed-out cylinder of the

metal whose spectrum is to be produced. Its constructed from a highly
pure metal resulting in a very pure emission spectrum.

 The ‘‘multi-element’’ lamp may provide superior performance for a

single element or, with some combinations, may be used as a source
for all of the elements contained in the cathode alloy.

 Anode is made up of tungesten

DISADVANTAGES OF HCL:

A finite lifetime – due to depletion of the analyte element from the cathode
Adsorption of fill gas atoms onto the inner surfaces of the lamp – the primary
cause for lamp failure

Some cathode materials can slowly evolve hydrogen when heated – a

background continuum emission contaminates the purity of the line spectrum
of the element, resulting in a reduction of atomic absorption sensitivity and
poor calibration linearity.
Electrodeless Discharge Lamp (EDL)
A small amount of the metal or salt of the element for which the source is to be used is
sealed inside a quartz bulb
This bulb is placed inside a small, self-contained RF generator or ‘‘driver’’. When power is
applied to the driver, an RF field is created.
The coupled energy will vaporize and excite the atoms inside the bulb, causing them to
emit their characteristic spectrum.
They are typically much more intense and, in some cases, more sensitive than comparable
hollow cathode lamps. Hence, better precision and lower detection limits where an analysis
is intensity limited.
EDL are available for a wide variety of elements, including Sb, As, Bi, Cd, Cs, Ge, Pb, Hg, P, K,
Rb, Se, Te, Th, Sn and Zn

CONSTRUCTION OF AN EDL
Atomization

Desolvation and vaporization of ions or atoms in a sample:

high-temperature source such as a flame or graphite
furnace

 Flame atomic absorption spectroscopy

 Graphite furnace atomic absorption spectroscopy

1- Flame atomic absorption spectroscopy:

Sample introduction:
 Process in a Flame AA
M* M+ + e_ Ionization

Mo M* Excitation

MA Mo + A o Atomization

Solid Solution Vaporization

2- Graphite furnace atomic absorption spectroscopy

Sample holder: graphite tube

 Samples are placed directly in the

graphite furnace which is then
electrically heated.
 Beam of light passes through the
tube.
 Basic Graphite Furnace Program

transversely heated graphite atomizer

Three stages:
1. drying of sample
2. ashing of organic matter
3. vaporization of analyte atoms

To burn off organic

species that would
interfere with the
elemental analysis.
 Basic Graphite Furnace Program
THGA
Clean
Atomization
Temp

Pyrolysis

Dry 2
Dry 1

Time
 Graphite Flame
• Solutions, slurries and solid • Inexpensive (equipment, day-
samples can be analyzed. to-day running)

• Much more efficient atomization • High sample throughput

Advantages
• greater sensitivity • Easy to use

• Smaller quantities of sample • High precision

(typically 5 – 50 µL)

• Provides a reducing environment

for easily oxidized elements
• Expensive • Only solutions can be analyzed

Disadvanta • Low precision • Relatively large sample

-ges quantities required (1 – 2 mL)
• Low sample throughput
• Less sensitivity (compared to
• Requires high level of operator graphite furnace)
skill
 wavelength selector
– Also it is called wavelengh selector
– Select the specific wavelenght
– Polychromatic light →monochromatic light
– Simple one is enough for AAS
DETECTOR:

• The intensity of the light is fairly low, so a photomultiplier tube (PMT)

is used to boost the signal intensity

• A detector (a special type of transducer) is used to generate voltage

from the impingement of electrons generated by the photomultiplier
tube
Calıbratıon Technıques

Two main techniques

 Calibration curve method

 Standart addition method
Calıbration Technıques

Calıbratıon Curve Method:

• Draw a graph
• Have two or more variables
-One is set at known values
-One is measured response

• Most convenient for a large number of similar

samples analysis.
CALIBRATION TECHNIQUES

An example of calibration curve method

 CALIBRATION TECHNIQUES
STANDART ADDITION METHOD

• To measure the analyte concentration in a

complex matrix.

• Most convenient for small number of samples

analysis

• Prevent effect of chemical & spectral

interferences
 INTERFERENCES

• Causes higher or lower absorbance value

• Two major groups

Chemical Interferences

Spectral Interferences
 CHEMICAL INTERFERENCES

• The most common one in flame atomizer.

• Consequence of chemical reactions.

• Reduce amount of oxygen in flame to overcome

SPECTRAL INTERFERENCES

• Absorption or emission of the radiation at the

same wavelength

• Radiation which is absorbed→pozitive errors

• Radiation which is emmitted→negative errors

SPECTRAL CORRELATION METHODS

TWO-LINE CORRELATION METHOD

• Select two line

characteristic wavelength of analyte
very close to analyte line but not absorbed by
analyte

• Measure the difference between two lines

SPECTRAL CORRELATION METHODS

Contınuum Source Correlatıon Method:

• Select two lamps - Deuterium lamp & hollow cathode

lamp

• When hollow cathode lamp is used total absorbace is

measured

• When deuterium lamp is used only background

absorption is measured

• Measure the difference between two lines.

SPECTRAL CORRELATION METHODS

Zeeman Effect Correlatıon Method

• Presence of magnetic field
• Splitting of spectral lines
Advantages and Limitations
Advantages
• The most widely used method in analysis of elements
• Based on the absorption of radiation
• So sensitive (ppb)
• Quantitative analysis

Limitations
• There is little overlap between the spectral lines of different
elements.
Applications

 water analysis (e.g.Ca, Mg, Fe, Si, Al, Ba content)

 food analysis; analysis of animal feedstuffs ( e.g. Mn, Fe, Cu,
Cr, Se, Zn)
 Soil analysis
 Metal alloy analysis
 clinical analysis (blood samples: whole blood, plasma, serum;
Ca, Mg, Li, Na, K, Fe)
 analysis of additives in lubricating oils and greases (Ba,Ca,
Na, Li, Zn, Mg)