Atomic Absorption and Atomic Emission Spectrometry

The absorption of radiation by atoms in the sun’s atmosphere was first observed
in 1814. However, it was only in 1953 that an Australian physicist Alan Walsh,
demonstrated that atomic absorption could be used as a quantitative analytical tool in
the chemical laboratory. Today atomic absorption spectrometry (AAS) is one of the
most widely used methods in analytical chemistry.
► Basic principles of AAS and AES: Let us consider the simplified energy level
diagram shown in the following figure; where E0 represent the ground state in which
the electrons in the given atom are at their lowest energy level and E 1, E2, E3 etc.
represent higher or excited energy levels.
E3

E2

E1

E0
Figure 5: Transitions between different quantized energy levels.
Transition between two quantized energy levels, say from E 0 to E1, corresponds to the
absorption of radiant energy, and the amount of energy absorbed (ΔE) is determined by
Bohr’s equation: ΔE = E1 – E0 = hν = hc/λ
where c is the velocity of light, h is Planck’s constant, ν is the frequency and λ, the
wavelength of radiation absorbed. Clearly, the transition from E 1 to E0 corresponds to
the emission of radiation of frequency ν.
Since an atom of a given element gives rise to a definite, characteristic line
spectrum, it follows that there are different excited states associated with different
elements. The consequent emission spectra involve not only transitions from excited
states to the ground state, e.g. E3 to E0, E2 to E0 (indicated by bold lines in the figure), but
also transitions such as E3 to E2, E3 to E1 etc. (indicated by dotted lines). Thus it follows
that the emission spectrum of a given element may be quite complex. In theory it is also
possible for absorption of radiation by already excited states to occur, e.g. E 1 to E2, E2 to
E3 etc., but in practice the ratio of excited to ground state atoms is extremely small, and
thus the absorption spectrum of a given element is usually only associated with

Dr. Jishnunil Chakraborty – Assistant Professor – St. Paul’s C. M. College, Kolkata- 700 009 1
transitions from the ground state to higher energy states and is consequently much
simpler in character than the emission spectrum.
The relationship between the ground state and excited state populations is given
by the Boltzmann equation: N1/N0 = (g1/g0).e–ΔE/kT
where, N1 = number of atoms in the excited state, N0 = number of ground state atoms,
(g1/g0) = ratio of statistical weights for ground and excited states (g = 2J + 1), ΔE =
energy of excitation (hν), k = Boltzmann constant and T = temperature in kelvin.
Obviously, the ratio N1/N0 is dependent upon both the excitation energy ΔE and the
temperature T. An increase in temperature and a decrease in ΔE (i.e. when dealing with
transitions which occur at longer wavelengths) will both result in a higher value for the
ratio N1/N0 as will be evidenced from the following table.
Table 1: Variation of atomic excitation with wavelength and temperature.
Element Wavelength (nm) N1/N0
2000 K 4000 K
Na 589.0 9.86 × 10–6 4.44 × 10–3
Ca 422.7 1.21 × 10–7 6.03 × 10–4
Zn 213.9 7.31 × 10–15 1.48 × 10–7
It should be noted that in AAS, as with molecular absorption, the absorbance A is
given by the logarithmic ratio of the intensity of the incident light signal I 0 to that of the
transmitted light It, i.e.
A = log(I0/It) = KLN0
where N0 is the concentration of atoms in the flame (number of atoms/cc.), L is the path
length through the flame (cm.), K is a constant related to absorption coefficient. For
small values of A, this is a linear function.
With atomic emission spectrometry, the detector response E is given by the
expression:
E = k.α.C
where k is related to a variety of factors including the efficiency of atomization and of
self-absorption, α is the efficiency of atomic excitation and C is the concentration of the
test solution.
The AAS phenomenon can be divided into two major processes: (1) the
production of free atoms from the sample and (2) the absorption of radiation from an
external source by these atoms. The absorption of radiation by free atoms (those

Dr. Jishnunil Chakraborty – Assistant Professor – St. Paul’s C. M. College, Kolkata- 700 009 2
analyte atoms removed from their chemical environment but not ionized) in the flame
involves a transition of these atoms from the highly populated ground state to an
excited electronic state. Although other electronic transitions are possible, the atomic
absorption spectrum of an element consists of a series of resonance lines, all originating
with the ground electronic state and terminating in various excited states. Usually the
transition between the ground state and the first excited state, known as the first
resonance line, is the line with the strongest absorptivity. The absorptivity of a given
element decreases as the energy difference between the ground state and the excited
states increases. All other factors being equal, if an analysis requires high sensitivity, the
first resonance line of the analyte is used.
The wavelength of the first resonance line for all metals and many metalloids is
longer than 200 nm, the short wavelength limit for operation in the conventional UV
region. The first resonance line for most nonmetals falls into the vacuum UV region
below 185 nm and, therefore, cannot be measured with conventional spectrometers.
Thus AAS instrumentation finds wide application for analysis of metals and metalloids.
The optical systems of AAS instruments can be modified to detect resonance lines of
nonmetals (< 200 nm) but these modifications add a significant expense to the
instrument and are not commonly used.
For AAS to function as a quantitative method, the width of the line emitted by the
narrow-line source must be smaller than the width of the absorption line of the analyte
in the flame. The shape of the spectral line emitted by the source is a critical parameter
in AAS. The flame gases are considered as a sample cell that contains free, unexcited
analyte atoms capable of absorbing radiation at the wavelength of the resonance line
emitted by the external source. Unabsorbed radiation passes through a monochromator
that isolates the resonance line and then into a photodetector that measures the power
of the transmitted radiation. Absorbance is determined by the difference in radiant
power of the resonance line in the presence and absence of analyte atoms in the flame.
► Interferences: Three types of interference are encountered in atomic absorption
methods: chemical interference, spectral interference and physical interference.
Chemical interference:
Matrix interference: Such as any reaction that prevents the sample getting into the flame,
may reduce the sensitivity. It is always preferable to run the standards in the same
matrix, or to use standard addition procedures.

Dr. Jishnunil Chakraborty – Assistant Professor – St. Paul’s C. M. College, Kolkata- 700 009 3
Chemical interference: The most common type of chemical interference is by anions that
form compounds of low volatility (refractory compounds) with the analyte and thus
decrease the rate at which it is atomized. Low results are the consequence. An example
is the decrease in calcium absorbance observed with increasing concentrations of
phosphate ion, which forms the refractory compound calcium pyrophosphate, Ca 2P2O7,
with the calcium ion.
Interferences due to the formation of species of low volatility can often be
eliminated by use of higher temperatures. Alternatively, releasing agents, which are
cations that react preferentially with the interference and prevent its interaction with
the analyte, can be introduced. For example, the addition of excess strontium or
lanthanum ion minimizes interference by phosphate in the determination of calcium.
Here, the strontium or lanthanum ion replaces the analyte in the nonvolatile compound
formed with the interferent.
Protective agents prevent interference by preferentially forming stable but
volatile species with the analyte. A common reagent for this purpose is EDTA, the
presence of which has been shown to eliminate interference by silicon, phosphate and
sulfate in the determination of calcium.
Ionization interference: The production of ions is most troublesome with alkali and
alkaline earth metals because of their low ionization potentials. A significant
concentration of free electrons exists as a consequence of the equilibrium:
M  M + + e-
Considering the free electrons as one of the products, the degree of ionization of an
analyte atom is strongly influenced by the presence of other ionizable metals in the
flame. Thus, if the medium contains not only the species M but species B as well, and if B
ionizes according to the equation:
B  B + + e-
Then the degree of ionization of M is decreased by the mass-action effect of the
electrons formed from B. B is called the ionization suppressor which provides a
relatively high concentration of electrons to the flame. Potassium salts are frequently
used as ionization suppressors because of the low ionization energy of the element.
Spectral interference: It is rare because of the sharpness of the atomic elemental lines,
but is difficult to overcome. For example, a vanadium line at 308.211 nm interferes in an

Dr. Jishnunil Chakraborty – Assistant Professor – St. Paul’s C. M. College, Kolkata- 700 009 4
analysis based upon the aluminum absorption line at 308.215 nm. This interference is
readily avoided by selecting a different aluminum line (309.270 nm, for example).
If the source of spectral interference by matrix products is known, an excess of
the interferent can be added to both sample and standards; provided the excess is large
with respect to the concentration from the sample matrix, the contribution of the latter
will become insignificant. The added substance is sometimes called a radiation buffer.
Physical interference: Most parameters that affect the rate of sample uptake in the
burner and the atomization efficiency can be considered physical interferences. This
includes such things as variations in the gas flow rates, variation in sample viscosity due
to temperature or solvent variation, high solid content, and changes in the flame
temperature. These can generally be accounted for by frequent calibration.
► Instrumentation in AAS: A basic AAS instrument consists of the following key
components:
(i) Light source: A light source to generate characteristic radiation of the element to be
analyzed. This is most often a hollow cathode lamp (HCL).
(ii) Atomizer: this is a combination of a nebulizer and a source of free atom production-
the burner.
(a) Nebulizer: It is a device through which the analyte solution is aspirated at a fixed
rate and the solution is converted to a mist (aerosol). If the aerosol is not produced,
atomization of the element in question is not possible quantitatively. If the solution
reaches the burner directly or with bigger droplets, the temperature of the burner will
go down and atomization will be prevented. It must be remembered that the residency
period of the solution on the burner is about 10–2 to 10–4 second and within this time
both drying up of the solution and atomization are not possible. Hence formation of the
aerosol is a must.
(b) Burner: A 10 mm burner is generally used and is lighted with acetylene or nitrous
oxide gas. The temperature of the air-acetylene flame (2300°C) and that of acetylene-
nitrous oxide flame (2800°C) helps in atomization.
(iii) Optical system: It directs the light from the source to the monochromator and the
detector.
(iv) Monochromator: It is used to isolate the specific analytical wavelength
(characteristic radiation). This may be either a grating or a prism.

Dr. Jishnunil Chakraborty – Assistant Professor – St. Paul’s C. M. College, Kolkata- 700 009 5
 (v) Detector: It measures the light intensity. This is generally a photomultiplier tube
(PMT).
(vi) Electronic device: This measures the response of the detector and translates its
response into useful analytical measurements like absorbance, transmittance,
concentration etc.

Line source Flame Monochromator Detector

Nebulizer Read-out
Figure 6: Schematic diagram of an AAS instrument.
Hollow cathode lamp (HCL): HCL is a source of characteristic radiation of an element.
HCL emits stable, intense radiation of the element to be estimated. Usually the
resonance spectral lines which are interference free are used for analysis.
In HCl, the anode and cathodes are placed in a Pyrex glass envelop with a quartz
window. Through this window the characteristic radiation comes out and goes to the
flame. The anode is made of tungsten wire and the cathode is cylindrical and is made of
the element whose characteristic radiations are to be generated. The HCL is generally
filled with an inert gas (argon or neon) at a low pressure (1-4 torr). The envelop is made
airtight.

Figure 7: Schematic
diagram of a hollow cathode lamp.
When a DC voltage around 300-500 volts is put across the cathode and the
anode, the atoms of the filler gas argon undergo ionization at the anode and are rapidly
attracted by the cathode. The fast moving ions strike the cathode and excite the atoms of
the cathode. These excited electrons of the excited atom come to the ground state and

Dr. Jishnunil Chakraborty – Assistant Professor – St. Paul’s C. M. College, Kolkata- 700 009 6
emit radiation which comes out through the quartz window and is used for analysis.
Quartz window is used since glass absorbs UV radiation. If the pressure is high, then
strike rate of the argon gas ions will be less. If the gas pressure is too low, then
vaporization rate of the cathode will increase and the cathode will be damaged.
It is sometimes possible to use an alloy of several elements for the hollow
cathode, and with such lamps, the lines of all the elements are emitted. These are the so-
called multielement HCLs and can be used as a source for usually two or three elements.
They may exhibit shorter lifetimes than do single element lamps due to selective
volatilization (“distillation”) of one of the elements from the cathode with condensation
on the walls of the lamp.
► Estimation of sodium and potassium in water samples: The determination of
sodium and potassium in water samples is very straightforward. Use of an air-propane
flame reduces the chance of interferences. To determine sodium, a sodium HCL is placed
in the operating position, and the sodium line is selected at 589 nm using appropriate
slit-width. Samples of 0.15-0.60 μg/cc of Na can be estimated by this method. Potassium
can be detected by replacing the sodium HCL to potassium HCL and adjusting the
resonance line source to 766.5 nm. By this method, 0.5-2.0 μg/cc of K can be
determined.
A series of standards must be prepared by mixing the stock solutions of Na and K
and their absorbance values are measured. The concentrations of the unknown sodium
and potassium are individually determined from the calibration curve.

*****

Dr. Jishnunil Chakraborty – Assistant Professor – St. Paul’s C. M. College, Kolkata- 700 009 7