Atomic Spectroscopy

Atoms are the simplest and purest form of matter and cannot
rotate or vibrate as a molecule does, only electronic transitions
within the atom takes place as energy absorbed. Atomic
spectroscopic methods can be divided into two groups: optical
atomic spectrometry and atomic mass spectrometry. Optical
atomic spectroscopy includes atomic absorption spectroscopy,
atomic emission spectroscopy and atomic fluorescence
spectroscopy.

1
Atomization Atomization Types of spectroscopy Common name and
Method temperature, abbreviation
0C

Flame 1700 - 3150 absorption Atomic absorption

spectroscopy, AAS
Emission Atomic Emission
spectroscopy, AES
Fluorescence Atomic Fluorescence
spectroscopy, AFS
Inductively 6000 - 8000 Emission Inductively coupled
coupled plasma atomic emission
plasma spectroscopy, ICP -AES
Mass Inductively coupled
plasma mass
spectroscopy, ICP - MS
2
 Atomic Absorption Spectrometry
Atomic absorption spectroscopy (often abbreviated FAAS) is the most
widely used method for trace metal analysis. It is particularly applicable
where the sample is in solution or readily solubilized. The absorption of
electromagnetic radiation by atoms allows both qualitative and
quantitative determination of a wide range of elements. Narrow band
sources of radiation specific to particular elements irradiate the atomic
vapor produced by flame, furnace or other methods and the absorption is
measured. The quantity of interest in atomic absorption measurements is
the amount of light at the resonant wavelength which is absorbed as the
light passes through a cloud of atoms. As the number of atoms in the
light path increases, the amount of light absorbed increases in a
predictable way. By measuring the amount of light absorbed, a
quantitative determination of the amount of analyte element present can
be made.

3
Principle
The principle states that “Atom absorbs light at the same wavelength at
which it emits light".
Basically this means that atoms in the ground state absorb the same
radiation as they emit in the excited state. An atom in the ground state
will absorb an amount of energy equal to the energy difference between
the energy level of the electron in the excited state and the energy level
that the electron occupies in the excited state. The amount of radiation
absorbed depends on the amount of the sample element present.

4
Absorption at a selected wavelength is measured by the change in light
intensity striking the detector and is directly related to the amount of the
element in the sample.
Ideally, the lines of an atomic spectrum should be very narrow, of the
order of 10-5nm. However, thermal movement causes Doppler shifts and
pressure broadening due to collisions among the atoms, and also
electrical and magnetic fields in the sample vapor all tend to broaden the
lines slightly to above 10-5nm. If a source emitting a broad band of
wavelengths were used, the fraction absorbed by a narrow line would be
small. It is therefore important to use a source producing a sharp
emission line characteristic of the element to be analyzed, for example, a
zinc source lamp to determine zinc. These are called resonance line
sources, and may be a hollow cathode lamp (HCL) or an electrodeless
discharge tube, both described below.

5
 Instrumentation
Atomic absorption spectroscopy instrumentation can
conveniently be considered under the following subheadings.

Detector and
Light source atomizer
monochromator readout device
(hollow cathode
Lamp )

6
Atomic Absorption Instrumentation
five basic components of an atomic absorption instrument:
1. The light source that emits the spectrum of the element of
interest
2. An "absorption cell" in which atoms of the sample are
produced (flame, graphite furnace)
3. A monochromator for light dispersion
4. A detector, which measures the light intensity and amplifies
the signal
5. A display that shows the reading after it has been processed
by the instrument electronics

7
Sources
A narrow line source is required for AAS. The most popular source is the hollow-
cathode lamp, although electrodeless discharge lamps are popular for some elements.
The Hollow-cathode Lamp - A light source which emits the sharp atomic lines of the
element to be determined
Hollow cathode lamp: Provide the analytical light line for the element of interest and
provide a constant yet intense beam of that analytical line. These lamps are designed to
emit the atomic spectrum of a particular element, and specific lamps are selected for use
depending on the element to be determined.
It is also required that the source radiation be modulated (switched on and off rapidly)
to provide a means of selectively amplifying light emitted from the source lamp and
ignoring emission from the sample cell. Source modulation can be accomplished with a
rotating chopper located between the source and the sample cell, or by pulsing the
power to the source.

8
Working principle of hollow cathode lamp (HCL)
An electrical potential is applied between the anode and
cathode and some of the fill gas atoms are ionized. The
positively charged ions collide with the negatively charged
cathode and dislodge metal atoms in a process called
"sputtering." Sputtered metal atoms are further excited to
emission through impact with the fill gas.
It is also required that the source radiation be modulated (switched on and off
rapidly) to provide a means of selectively amplifying light emitted from the
source lamp and ignoring emission from the sample cell. Source modulation can
be accomplished with a rotating chopper located between the source and the
sample cell, or by pulsing the power to the source.

10
Life time: Hollow cathode lamps have a finite lifetime. Adsorption of fill gas atoms
onto the inner surfaces of the lamp is the primary cause for lamp failure. As fill gas
pressure decreases, the efficiency of sputtering and the excitation of sputtered metal
atoms also decrease, reducing the intensity of the lamp emission.
The sputtering process may remove some of the metal atoms from the vicinity of the
cathode to be deposited elsewhere. Lamps for volatile metals such as arsenic, selenium,
and cadmium are more prone to rapid vaporization of the cathode during use. While the
loss of metal from the cathode at normal operating currents (typically 5-25
milliamperes) usually does not affect lamp performance, fill gas atoms can be entrapped
during the metal deposition process which does affect lamp life.
Lamps which are operated at highly elevated currents may suffer reduced lamp life due
to depletion of the analyte element from the cathode. Some cathode materials can
slowly evolve hydrogen when heated. As the concentration of hydrogen in the fill gas
increases, 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. To eliminate such problems, most modern hollow cathode
lamps have a tantalum „„getter‟‟ on the anode which irreversibly adsorbs evolved
hydrogen as the lamp is operated.
11
Multi element & single element lamp: The cathode of the hollow cathode
lamp is usually constructed from a highly pure metal resulting in a very pure
emission spectrum of the cathode material. It is sometimes possible, however,
to construct a cathode or cathode insert from several metals. The resulting
„„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. However, not all metals may be used in
combination with others because of metallurgical or spectral limitations.
Special consideration should be given before using a multielement lamp as
analytical complications may result. Often the intensity of emission for an
element in a multi-element lamp is not as great as that which is observed for the
element in a single-element lamp. This loss of intensity could be a disadvantage
in applications where high precision or low detection limits are required. The
increased spectral complexity of multi-element lamps may require that alternate
wavelengths or narrower slits be used, which may also adversely affect
sensitivity or baseline noise.
12
The Electrodeless Discharge Lamp
For most elements, the hollow cathode lamp is a completely satisfactory
source for atomic absorption. In a few cases, however, the quality of the
analysis is impaired by limitations of the hollow cathode lamp. The
primary cases involve the more volatile elements where low intensity and
short lamp life are a problem. The atomic absorption determination of
these elements can often be dramatically improved with the use of
brighter, more stable sources such as the „„electrode less discharge
lamp‟‟.
Construction: 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. An accessory power supply is required to
13
operate an EDL.
Advantage of EDL over HCL ,
- much more intense and
-more sensitive
-better precision and lower detection limits
-longer lifetime
Drawback: the optical image for the EDL is considerably larger than
that in a hollow cathode lamp. As a result, the performance benefits of
the EDL can only be observed in instruments with optical systems
designed to be compatible with the larger image.

14
Sample cell (NEBULIZER & FLAME) :
Nebulizer:
-Suck up liquid sample at a controlled rate,
-Create a fine aerosol for introduction into the flame,
-Mix the aerosol, fuel and oxidant thoroughly for introduction into the
flame.
The variables that control the size of droplets are the:-
1) Difference in the velocity of gas and the liquid,
2) The density of the liquid,
3) The viscosity of the liquid, and
4) The volume flow rates of both the gas and the liquid.

15
16
Flame: Destroy any analyte ions and breakdown complexes,
Create atoms (the elemental form) of the element of interest.
In AAS, the flame is only required to produce ground-state atoms. Frequently,
an air-acetylene flame is sufficient to do this. For those elements which form
more refractory compounds, or where interferences are encountered a nitrous
oxide-acetylene flame is preferred. In either case, a slot burner is used (100
mm for air-acetylene, 50 mm for nitrous oxide-acetylene) to increase the path
length and to enable a specific portion of the flame to be viewed. Atoms are not
uniformly distributed throughout the flame and, by adjusting the burner up and
down with respect to the light beam, a region of optimum absorbance can be
found. Premixed gases are heated in the preheating zone, where their
temperature is raised exponentially until it reaches the ignition temperature.
Surrounding the preheating zone is the primary reaction zone, where the most
energetic reactions take place.

17
18
Pre-Mix Burner System
The sample cell, or atomizer, of the AAS must produce the ground state
Atoms necessary for atomic absorption to occur. This involves the
application of thermal energy to break the bonds that hold atoms together
as molecules. While there are several alternatives, the most routine and
widely applied sample atomizer is the flame.
The burner used for flame AA is a premix burner. It is called that because
all the components of the flame (fuel, oxidant, and sample solution) are
premixed, as they take a common path to the flame. The fuel and oxidant
originate from pressurized sources, such as compressed gas cylinders,
and their flow to the burner is controlled at an optimum rate by flow
control mechanisms that are part of the overall instrument unit.

19
20
The process in pre-mix system: In this „„premix‟‟ design, sample
solution is aspirated through a nebulizer and sprayed as a fine aerosol
into the mixing chamber. Here the sample aerosol is mixed with fuel and
oxidant gases and carried to the burner head, where combustion and
sample atomization occur.

21
1. Nebulization -A solution of the sample was sprayed as an aerosol
through a nebulizer into a flame
2. Desolvation (Drying) – the liquid solvent is evaporated, and the dry
sample remains
3. Vaporization – the solid sample vaporises to a gas
4. Atomization – the compounds making up the sample are broken into
free atoms

22
FLAME ATOMIZATION & BURNER HEIGHT
In a flame atomizer, a solution of the sample is nebulized by a flow of
gaseous oxidant, mixed with a gaseous fuel, and carried into a flame
where atomization occurs.

23
First, the solvent evaporates, leaving behind formula units of the formerly
dissolved salt. Next, dissociation of the formula units of salt into atoms occurs,
the metal ions atomize, or are transformed into atoms.
Then, if the atoms are easily raised to excited states by the thermal energy of
the flame, a resonance process occurs in which the atoms resonate back and
forth between the ground state and the excited states.
Actually, only a small percentage of the atoms (less than 0.1%, depending on
the temperature of the flame) are found in the excited state at any particular
moment. As these atoms drop back to the ground state (a natural process), the
emission spectrum is emitted. For those atoms that are easily excited under
these conditions, the emitted wavelengths are in the visible region of the
spectrum, and the entire flame takes on a color characteristic of the element that
is in the flame. It is a characteristic color because each element has its own
characteristic line spectrum, the atomic fingerprint, resulting from the particular
energy transitions that element has.

24
An alternative vaporization method is to use a graphite furnace, which
is an open-ended cylinder of graphite placed in an electrically heated
enclosure containing argon to prevent oxidation. Temperatures in the
region of 2500 K are achieved, and the heating program is designed to
heat the sample, deposited on a smaller tube, by radiation. The graphite
furnace produces a peak signal whose area is proportional to the total
amount of vaporized element in the sample.

25
The use of graphite furnace atomic absorption (GFAA) has a number of
advantages:
i. it avoids interactions between the sample components and the flame since
atomization takes place in an inert gas stream;
ii. it gives increased sensitivity because of the longer residence time of the
sample in the beam from the source;
iii. the sensitivity is further increased because a higher proportion of atoms are
produced;
iv. it has the ability to handle small volumes of samples, down to 0.5-10 ml,
such as clinical specimens;
v. the results are more reproducible than flame AAS.
One disadvantage is that it is rather slower than flame AAS.
Another approach is hydride generation, as certain elements, such as arsenic,
tin and selenium, have volatile hydrides. By removing all organic matter by
oxidation, and then reducing the sample with sodium borohydride, NaBH
volatile hydride is produced and can be swept out into the radiation path using
argon. 26
A Monochromator: It is used to disperse the various wavelengths of
light which are emitted from the source and to isolate the particular line
of interest. The selection of a specific source and a particular wavelength
in that source is what allows the determination of a selected element to
be made in the presence of others.
Job of the monochromator
Isolate analytical lines photons passing through the flame, and remove
scattered light of other wavelengths from the flame. In doing this, only a
narrow spectral line impinges on the PMT. The wavelength of light
which is isolated by the monochromator is directed onto the detector,
which serves as the „„eye‟‟ of the instrument.

27
Photomultiplier tube (PMT) which produces an electrical current
dependent on the light intensity. The electrical current from the
photomultiplier is then amplified and processed by the instrument
electronics to produce a signal which is a measure of the light attenuation
occurring in the sample cell. This signal can be further processed to
produce instrument readout directly in concentration units.
ELECTRONICS & READOUT: The electrical current from the
Photomultiplier tube is then amplified and processed by the instrument
electronics to produce signal which is a measure of the light attenuation
occurring in the sample cell. The signal can be further processed to
produce an instrument readout directly in concentration units or any
desired for (Absorbance or transmmitance).

28
Interferences may be troublesome in AAS. Background absorption by smoke
particles or solvent droplets may be removed as detailed above.
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.
Chemical interference due to the production of thermally stable compounds,
such as involatile phosphates of calcium, may sometimes be dealt with by
adding a releasing agent such as EDTA, or by using a hotter flame or a reagent
that preferentially forms stable, volatile compounds.
Ionization interference due to the production of ions is most troublesome with
alkali metals because of their low ionization potentials. Occasionally, ionization
suppressors such as lithium or lanthanum salts, which are easily ionized, are
added.
Spectral interference is rare because of the sharpness of the atomic elemental
lines, but is difficult to overcome. For example, the zinc line at 213.856 nm is
too close to the iron line at 213.859 nm, but the iron line at 271.903 nm could
be used to determine iron instead. 29
Applications
The spectrometer should be calibrated by using standard solutions of
the element to be determined, prepared in the same way as the sample
solution. Usually, acidic aqueous solutions are used; for example, many
elements are commercially available as 1000 ppm certified standards in
dilute perchloric acid.
Organic solvents, such as white spirit (~C10 alkanes) or methyl isobutyl
ketone, may be used if the sample is insoluble in water (e.g., a
lubricating oil). Standards can then be made of metal complexes soluble
in the organic solvent. The standard solutions should be chosen to
„bracket‟ the concentration to be determined and, ideally, the calibration
curve should be linear in that region. Multi-element standard stock
solutions are useful and permit more rapid determination of several
elements of interest.

30
The techniques are used for many industrial and research purposes,
especially:
i. agricultural samples, particularly the analysis of soils - metal
pollutants in soil and water samples are often determined by AAS;
ii. clinical and biochemical determinations, e.g., the measurement of
sodium, potassium, lithium and calcium in plasma and serum, and of iron
and lead in whole blood;
iii. metallurgical samples may be assayed to measure impurities;
iv. oils and petrochemical samples can be analyzed for metals in
feedstocks and to detect metals in used oils due to corrosion and wear.
v. water samples are extremely important, since pollution may be a
health hazard. Nickel, zinc, mercury and lead are among the metals
determined

31
•

32
Atomic Absorption Spectrophotometer

33
Flame Photometry (Flame Atomic Emission Spectrometry)
Flame photometry (flame atomic emission spectrometry) is a branch of
atomic spectroscopy in which the species examined in the spectrometer
are in the form of atoms.
AES was founded by Bunsen in the 1920. Lundegardh (1929-34)
developed an apparatus in which cations in solution were sprayed into an
air acetylene flame, and the spectra produced photographed and
compared with similar spectra from standard solutions.
Flame photometry is designed for the routine determination of the
concentrations of certain metals ( sodium (Na) ,potassium (K). lithium
(Li) and calcium (Ca ) ) in solution by measuring the intensity of the light
emitted by them when the solution is sprayed under controlled conditions
into a non-luminous flame.
The other branch of atomic emission spectrophotometry (AES) is
inductively coupled plasma-atomic emission spectrometry (ICP-AES), a
relatively new and very expensive technique. 34
Principle
Flame photometry relies upon the fact that the compounds of the alkali
and alkaline earth metals can be thermally dissociated in a flame and that
some of the atoms produced will be further excited to a higher energy
level. When these atoms return to the ground state they emit radiation
which lies mainly in the visible region of the spectrum. Each element
will emit radiation at a wavelength specific for that element.

35
The intensity(I) of the light emitted could be described by the
ScheibeLomakin Equation:
I = k cn
where:
c = the concentration of the element
k = constant of proportionality
n ~1 (at the linear part of the calibration curve), therefore the intensity of
emitted light is directly proportional to the concentration of the sample.
Over certain ranges of concentration the intensity of the emission is
directly proportional to the number of atoms returning to the ground
state. This is in turn proportional to the absolute quantity of the species
volatized in the flame, i.e. light emitted is proportional to sample
concentration.

36
Instrumentation
When metal is dissolved in solutions it exists as ions. When aspirated
(sprayed) into a butane-air or propane-air flame, the solvent in the
aerosol quickly evaporates leaving a solid residue, which is then broken
down to form an atomic species. The energy of the flame is able to excite
the atoms and move their electrons to a higher energy state. As these
individual atoms “cool” they fall back into their original unexcited or
ground state and emit their absorbed energy by radiation of specific
wavelengths. This discrete emission is isolated by an optical filter
(absorption or interference) and the intensity of that light measured by a
photo-detector (PT or PMT), then an electrical signal can be obtained
proportional to sample concentration. Such an electrical signal can be
processed and the readout obtained in an analogue or digital form.

37
38
The processes that occur in FAES may be summarized as follows:
i.Production of aerosol from solution (nebulization)
ii.Removal of solvent(drying)
iii.Vaporization of sample
iv.Atomization
v.Excitation
vi.Emission
Ionization may also occur to form metal ions
These stages each depend on the experimental parameters used in the
instrument.
For example: the viscosity of the solvent, which affects the aerosol
production; the nature of the solvent, which may affect the vaporization;
the rate of fuel flow, which can change the nebulization and the time the
atoms spend in the flame; the flame temperature, which controls the
evaporation, the atomization and the extent of ionization; and the nature
of the flame. 39
Application: Flame atomic emission spectrometry (FAES) and flame
photometry are used widely for the determination of alkali and alkaline
earth metals. The rapid determination of Na, K and Ca in biological and
clinical samples is one of the most important applications; for example,
calcium in beer, milk or biological fluids. The usual solvent is water, but
organic solvents may be used to enhance the intensity, since they produce
smaller droplets, and have a smaller cooling effect on the flame.

40
The instrument is calibrated with standard solutions of the elements to be
determined and the intensity of the emission recorded at each
characteristic wavelength. A calibration graph is constructed after
correcting for background (blank) emission. Flame photometry is an
empirical method of analysis, that is, you must calibrate the method
carefully. Many different experimental variables affect the intensity of
light emitted from the flame: Fuel and oxidant flow rates and purity,
aspiration rates, solution viscosity. Therefore, careful and frequent
calibration is necessary for good results and it is very important to
measure the emission from the standard and unknown solutions under
conditions that are as nearly identical as possible.

41
The signal intensity from a flame is dependent on
•the flame temperature,
•The rate of flow of liquid into the flame,
•The pressure and rate of flow of fuel gases,
•And any of many other variables which affect the character of the flame or atomizing
of the sample.
Interferences may affect the linearity of the calibration and are chiefly due to the
emission lines produced by other species close to those of the analyte. They may be
minimized by selecting a different spectral line for the analysis, or by altering the
spectral resolution or filter. The presence of anions that form very stable compounds
with the metal ions, such as sulfate and phosphate may interfere with some
determinations. At high analyte concentrations, the concentration of atoms in the flame
may be high enough to cause self-absorption. That is, the emission is reabsorbed by the
ground state atoms in the cooler outer layers of the flame. This sometimes causes a loss
in sensitivity at higher concentrations.
The advantages of FAES and flame photometry are that the instrumentation is
relatively simple and measurements can be made quickly.

42