Atomic Absorption spectroscopy

• Introduced by Alan walsh in 1955

• It is a power full technique used for used for
quantitative determination of trace metals.
• It tells us total content of the sample and almost
independent of molecular form of metal.
• Used for almost 60-70 elements.
• Sample almost does not require any prior
separation .
• Almost not sample preparation is required.

•
• In AAS the electrons of atoms in the ground state is
promoted to higher orbit(excited state) for a short
period of time by absorption of define quantity of
energy.
• The basis of this method is the measure of light
absorbed at the wavelength of a resonance line
(characteristics) by unexcited atoms of the elements.
• Unexcited atoms of the flame are determine in this
technique.
• As almost 99% of atoms are in ground state there for it
is almost the measure of total numbers of atom of the
flame and hence the concentration of the element.
• Beer-lambert`s law is followed here.
A=abc
• Absorbance (A) is propotional to concentration
(c) and path length b.
• The important advantage of absorption
• method lies in the fact that it consist of
measuring the ratio of intensities of
monochromatic lines
a) in the presences of absorbing atoms and
b) In the Absence of absorbing atoms
 Atomic line width
10-5nm -10-2 Ao

The widths of atomic lines are quite important in

atomic spectroscopy. For example, narrow lines are
highly desirable for both absorption and emission
spectra because they reduce the possibility of
interference due to overlapping lines. Furthermore, as
will be shown later, line widths are extremely
important in the design of instruments for atomic
emission spectroscopy. For these reasons, we now
consider some of the variables that influence the
width of atomic spectral lines.
As shown in Figure 8-6, atomic absorption and
emission lines are generally found to be made up
of a symmetric distribution of wavelengths that
centers of a mean wavelength ʎ , which is the
wavelength of maximum absorption or maximum
intensity for emitted radiation. The energy
associated with ʎo is equal to the exact energy
difference between the two quantum states
responsible for absorption or emission.
• Energy level diagrams, such as that shown in Figure 8-
la, suggest that an atomic line contains only a single-
wavelength ʎ-that is, because a line results from a
transition of an electron between two discrete, single-
valued energy states, the line width will be zero.
Several phenomena, however. cause line broadening
so that all atomic lines have finite widths, as shown in
Figure 8-6. Note that the line width or effective line
width 1/2ʎo of an atomic absorption or emission line is
defined as its width in wavelength units when
measured at one half the maximum signal. This point
is chosen because the measurement can be made
more accurately at half-peak intensity than at the
base.
 Sources of line broadening
• There are four sources of line broadening:
• (1) the uncertainty effect,
• (2) the Doppler effect
• (3) pressure effects due to collisions between atoms
of the same kind and with foreign atoms, and
• (4) electric and magnetic field effects.
• We consider only the first three of these
phenomena here, The magnetic field effect will be
discussed later on in connection with the Zeeman
effect.
Line Broadening from the Uncertainty Effect
(natural broadening)
Spectral lines always have finite widths because the
lifetimes of one or both transition states are finite,
which leads to uncertainties in the transition times and
to line broadening as a consequence of the uncertainty
principle . In other words, the breadth of an atomic line
resulting from a transition between two states would
approach zero only if the lifetimes of two states
approached infinity. Although the lifetime of a ground-
state electron is long, the lifetimes of excited states are
generally short, typically 10-7 to 10-8 s. Example 8-1
illustrates how we can estimate the width of an atomic
emission line from its mean lifetime and the
uncertainty principle.
 Doppler Broadening
The wavelength of radiation emitted or absorbed by a
rapidly moving atom decreases if the motion is toward a
transducer and increases if the atom is receding from
the transducer (see Figure 8-7). This phenomenon is
known as the Doppler shift and is observed not only with
electromagnetic radiation but also sound waves, For
example, the Doppler shift occurs when an automobile
blows its horn while it passes a pedestrian. As the auto
approaches the observer, the horn emits each successive
sound vibration from a distance that is increasingly
closer to the observer. Thus, each sound wave reaches
the pedestrian slightly sooner than would be expected if
the auto were standing still.
The result is a higher frequency, or pitch, for the
horn. When the auto is even with the observer.
the waves come directly to the ear of the observer
along a line perpendicular to the path of the auto,
so there is no shift in the frequency.
When the car recedes from the pedestrian, each
wave leaves the source at a distance that is larger
than that for the previous wave; as a result, the
frequency is smaller, and this results in a lower
pitch.
The magnitude of the Doppler shift increases with
the velocity at which the emitting or absorbing species
approaches or recedes from the observer. For relatively
low velocities, the relationship between the Doppler
Shift ∆ʎ . and the velocity v of an approaching or receding
atom is where A" is the wavelength of an unshifted line of
a sample of an element at rest relative to the transducer,
and c is the velocity of light.
individual atoms exhibit a Maxwell-Boltzmann velocity
distribution, in which the average velocity of a particular atomic
species increases as the square root of the absolute
temperature.
The Doppler shifts of such an ensemble result in broadening of
the spectral lines.' The maximum Doppler shifts occur for atoms
moving with the highest velocities either directly toward or
away from the transducer. No shift is associated with atoms
moving perpendicular to the path to the transducer.
Intermediate shifts occur for the remaining atoms,
and these shifts are a function of their speed and direction.
Thus, the transducer encounters an approximately symmetrical
distribution of wavelengths. In flames, Doppler broadening
causes lines to be about two orders of magnitude wider than
the natural line width.
 n Should be 

Superposition of tw sinusoidal wave of different frequencies but identical

amplitudes.
•
 Pressure Broadening
Pressure, or collisional, broadening is caused by collisions of the
emitting or absorbing species with other atoms or ions in the
healed medium. These collisions produce small changes in
energy levels and hence a range of absorbed or emitted
wavelengths. In a flame, the collisions are largely between the
analyte atoms and the various combustion products of the fuel.
These collisions produce broadening that is two or three orders
of magnitude greater than the natural line widths. Broadening
in the hollow cathode lamps and
discharge lamps used as sources in atomic absorption
spectroscopy results mainly from collisions between the
emitting atoms and other atoms of the same kind.
In high-pressure mercury and xenon lamps, pressure broadening
of this type is so extensive that continuum radiation is produced
throughout the ultraviolet and visible region.