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Atomic Spectroscopy

Ashraf M. Mahmoud, Associat

Atomic Spectroscopy Methods


1. Atomic Emission Spectroscopy (Flame Photometry)
2. Atomic Absorption Spectrometry (AAS)

Atomic Spectroscopy
To understand the relationship of these techniques to each other, It is
important to understand the atom itself and the atomic process
involved in each technique.

Ground state atom (stable or


normal orbital configuration)

Excited
states

Excited state atom

Excited
states

3
3
3

Spectral resonance line


(The strongest line)

Ground
state

Ground
state

Light energy

Atomic Spectroscopy
Practically, the ratio of the excited to ground state atoms is extremely small.
Therefore, The absorption spectrum is usually only associated with transitions
from the ground state to higher energy states

Energy

~0% population
Emission

Excited state atoms

Absorption

~100% population
Boltzmann equation explain the relatioship between

Ground state atoms

the ground and excited state atoms

N1/N = (g1/g)e-E/KT
N1: No. of excited atoms

N: No. of ground state atoms

K: Boltzmann constant

E: excitation energy

T: Temperature in kelvin

Atomic Spectroscopy
The process of excitation and decay to ground
state is involved in the two techniques of atomic
spectroscopy.
We measure the energy absorbed or emitted and
use it for quantification process

Atomic Emission Spectroscopy (AES)


(Flame Photometry)
Principle:

Flame photometry is based upon those particles


that are electronically excited in the medium.

Flame : is the source of excitation energy. (low energy source).


Uses:
Flame photometry is used mainly for the determination of alkali
metals and easily excited elements (Na, K, Li, Ca, etc.) particularly
in biological fluids and tissues

Flame Photometry
Events occur in FES
Solution of metal
salt (NaCl)

Ground state atoms


Na

Solvent evaporation

Emission and
return to G

Solid aerosol of
metal salt (NaCl)

Excited atoms
Na*

Volatilization or decomposition

Gaseous metal
salt (NaCl)

Atomization

Excitation

Free atoms
Na

Flame Photometry
Instrument
components

Monochromator

Flame

Detector

Flame Structure
Interzonal

Secondary
combustion zone

region

Primary
combustion zone
Fuel- oxidant mixture

Flame Photometry
Functions of Flame
1. To convert the constituents of liquid sample into the vapor state.
2. To decompose the constituents into atoms or simple molecules:
M+ + e- (from flame) M + h
3. To electronically excite a fraction of the resulting atomic or
molecular species
Oxidant - Fuel
Max. temp. (oC)
M M*

Air-

propane

1725

Air-

acetylene

2400

The flame is composed of : Oxygen- acetylene

3100

a fuel gas and oxidant gas

Nitrous oxide-acetylene

3000

Air-hydrogen

2000

Oxygen-hydrogen

2700

Air + argon -hydrogen

1577

Flame Photometry
Factors affecting intensity of flame emission :
1- The concentration of the analyte in solution
2- The rate at which excited atoms are formed in the flame.
3- The rate at which the sample is introduced into the flame.
4- Temperature of the flame.
5- Composition of the flame.
6- The ratio of fuel to oxidant in the flame.
7- Solvent used to dissolve the sample.
The flame temperature is the most important factor. Increase in
flame temperature causes an increase in emission intensity. This is
controlled by composition of the flame.
High temperature flames should not be used for elements that
ionized easily e.g. Na, K, Li or Ce. However, high temperature
flames are generally favored for transition elements and alkaline

Flame Photometry
Effect of the solvent used to dissolve the sample; if the solvent is
water the process is slow and if it is organic solvent the process
is fast and emission intensity is increased.
It is therefore very important that calibration curves be
prepared using the same solvent.
The stochiometric ratio of fuel to oxidant in the flame must be
used, in which both fuel to oxidant are totally consumed.

Flame Photometry
The nebulizer-burner system
To convert the test sample into gaseous atoms
Nebulizer produce an aerosol of the test solution
Burner in which the mixing between fuel and oxidant

Types of burner system

Flame

1. Pre-mix or laminar flow burner

Fuel in

Advantages
1. Homogenous flame
2. Suitable for AAS and AES as
the pathway could be increased

Disadvantages
Suffers from explosion hazards

Burner

Oxidant in

Sample
Aspirator
air

Drain

Mixing
baffles

Flame Photometry
2. Total consumption burner

Fuel

Advantages
1. Simple to manufacture
2. Allows a total representative sample
to reach the flame
3. Free from explosion hazards

Disadvantages
1.
2.

Aspiration rate varies with different solvents


Suitable only for AES

Sample

Used mainly for FES (short bath)

Oxidant

3 concentric tubes, the sample, fuel and


oxidant only mix at the tip of burner

Oxidant
Fuel

Flame Photometry
Non Flame Atomizers
For example:

Heated Gravite Furnace

Sample evaporation time and temp. controlled drying and ashing


Advantages
1. small samples are analysed
2. 1000-fold more sensitive than flame
3. Oven is adaptable to determination of solid samples
Disadvantages
1. Low accuracy
2. Low precision
2. More ionic interferences due to very high temp.

Flame Photometry
As in UV

Monochromators

Films or photomultipliers

Detectors
Analytical technique
1. Choice of the wavelength:
2. Sample preparation:

of max. sensitivity and min. spectral interferences

a.

It is very important to obtain the sample in a form of solution, where the spectral
and chemical interferences are absent

b.

Demineralized dist. Water and very pure reagents are to be used because of the
high sensitivity of the technique

c.

Because of the instability of the very dil. Solution, it is advisable to dilute the
soln just before use.

d.

Several elements can be determined in blood, urine, cerebrospinal fluid and other
biological fluids by direct aspiration of the sample after dilution with water.

Flame Photometry
Chemical interferences: can often be overcome by simple
dilution with a suitable reagent solution e.g. serum is diluted by
EDTA solution for the determination of calcium in order to
prevent interference from phosphate.

Deviations from
linearity may occur

Absorbance,
Intensity

3. Standard curves

Concentration, c

Flame Photometry
3. Qualitative analysis
Flame photometry are useful mostly for the detection of elements in
group I and II of the periodic table. The presence of certain
elements can be detected by the use of a filter or monochromator.
Advantages and disadvantages
The method is not as reliable as other atomic emission spectroscopic
methods, but it is fast and simple.

4. Quantitative analysis
To perform quantitative analysis, the sample is introduced into the
flame and the intensity of radiation is measured. The concentration
of the emitting substance is then calculated from a calibration curve
or using standard addition method.

Flame Photometry
Application of flame photometry in pharmaceutical analysis
1. Metals are major constituents of several pharmaceuticals such as dialysis
solutions, lithium carbonate tablets, antacids and multivitamin - mineral
tablets.
2. The elements Na, K, Li, Mg, Ca, Al and Zn are among the most common
elements subjected to pharmaceutical analysis using flame emission
technique.
3.

Sodium and potassium levels in biological fluids are difficult to analyze by


titrimetric or colorimetric techniques. Their analysis is very important for
control of infusion and dialysis solutions which must be carefully monitored
to maintain proper electrolyte balance.

Advantages and disadvantages


1. Flame emission is the simplest and least expensive technique.
2. The analysis may be carried out without prior separation as other
components such as dextrose, do not interfere.

Atomic Absorption Spectroscopy

Atomic Absorption spectroscopy involves the study of the absorption


of radiant energy by neutral (ground state) atoms in the gaseous state.

Instrument components
P0

Monochromator

Detector

Source
Lamps
Hollow Cathod
lamp

Sample

low-pressure inert gas

Inert carrier gas


Ne or Ar

Atomic Absorption Spectroscopy


Electrodless Discharge Lamps, EDL
For easily evaporized elements as Hg or As
Used for AAS and AES
Give much greater radiation intensities than hollow cathod
There is no electrode, but instead , the inert carrier gas is
energized by an intense field of radiofrequency or microwave
radiation plasma formation which cause excitation of the
metal inside

Atomic Absorption Spectroscopy


Degree of absorption:
Total amount of light absorbed = (e2/mc2)Nf
Where:
e = electronic charge, m = mass of electron
c = speed of light,
N = total No. of atoms that can absorb light
f = Ability of each atom to absorb light
, e, m, and c are constants, therefore

Total amount of light absorbed = constant x Nf


Since f is also constant for the same substance
A&C

Atomic Absorption Spectroscopy

Atomic Absorption Spectroscopy


Interferences
Spectral Interferences
1. They arise when the absorption line of an interfering species
either overlaps or lies so close to the analyte absorption line that
resolution by the monochromator becomes impossible. Ex. Mg in
presence of Ca.
2. They occur from band or continuous spectra which are due to
absorption of molecules or complex ions remaining in the flame
3. They arise from flame background spectrum.
Correction:
1. It may be useful to shift to another spectral line
2. Two line correction method: (Instrumental correction)
It employs a line from the source as a reference. The line should lie as close as
possible to the analyte line but must not be absorbed by the analyte. If the
conditions are met, any decrease in the reference line from that observed
during calibration arises from absorption by the matrix of the sample.

Atomic Absorption Spectroscopy


Chemical Interferences
occurrs during atomization that prevent the gaseous atoms
production of the analyte. They are more common than spectral
ones.
Types of chemical interferences
1.

Formation of stable compounds: incomplete dissociation of the sample in flame

2.

Formation of refractory oxides: which fail to dissociate into the constituent atoms

Examples 1. Detn. of Ca in presence of sulphate or phosphate


2.

Overcome

Formation of stable refractory oxides of TiO2, V2O5 or Al2O3 b


reaction with O2 and OH species in the flame

1. Increase in the flame temp. Formation of free gaseous atoms


e.g. Al2O3 is readily dissociated in acetylene-nitrous oxide flame

Atomic Absorption Spectroscopy


2. Use of releasing agents: M-X + R RX + M ex. Detn of Ca
in presence of phosphate
(Ca - phosphate + SrCl2 Sr-phosphate + Ca atoms) or
(Ca phosphate + EDTA Ca-EDTA easily dissociated complex ).
3. Solvent extraction of the sample or of the interferring elements

Ionization Interferences
Ionization of atoms in the flame decrease the absorption or emission

Overcome : 1. Use of lowest possible temp which is satisfactory for


the sample ex. Acetylene air must not be used for easily ionised
elements as Na, K, Ca, Ba
2. Addition of an ionisation supressant ( soln of cation has a lower
ionisation potential than that of the sample, e.g. addition of K-soln
to Ca or Ba soln. Ca Ca2+ + 2e K K+ + e

Atomic Absorption Spectroscopy


Physical Interferences
1.

Variation in gas flow rate

2.

Variation in sample viscosity

3.

Change in flame temp.

Overcome:

1. by continuous calibration
2. Use of internal standard

Advantages of AAS:

Very sensitive.
Fast.

Disadvantages of AAS: Hollow cathode lamp for each element.


Expensive element.

Relationship Between Atomic Absorption and Flame


Emission Spectroscopy
Atomic Absorption

Flame Emission

1. Measures the radiation


absorbed by the unexcited
atoms

1. Measures the radiation


emitted by the excited atoms

2. Depends only on the


number of unexcited atoms

2. Depends only on the


number of excited atoms

3. Absorption intensity is
NOT affected by the
temperature of the flame

3. Emission intensity is greatly


affected by the temperature
variation of the flame

Atomic Emission Spectroscopy


Using Non-Flame excitation sources
1. There is no single
elements

excitation source can excite all

2. The emitted radiation usually consists of sharp well


defined lines, which fall in UV or visible region
3. Identification of the of these lines permits qualitative
analysis of these elements, whereas measurements of
their intensities permits quantitative analysis
Advantages
1. Excellent method for trace element analysis at ppm level
2. Used nearly for all elements in periodic table

Atomic Emission Spectroscopy


3. Used for very small samples, even less than 1 mg
4. There is no need for prior separation
5. Relatively rapid technique

Disadvantages

1. Expensive
2. Low precision and accuracy
3. Destroying the sample
4. Used mainly for metals

High energy excitation sources


Plasma excitation sources
Laser
Arc and spark emission spectrometry (Spectrography)
Microwave and x-ray

Atomic Emission Spectroscopy


Plasma excitation sources
1.

A plasma is a cloud of highly ionized gas containing significant numbers of


positive and negative ions, free electrons and neutral particles.

2.

Plasma sources operate at high temperatures between 7000 and 15000 K.


Thus, it produces a greater number of excited emitted atoms, especially in
the UV region, than that produced by flame.

3.

Using this technique, excitation operates through a plasma produced


electrically in a carrier gas such as nitrogen or argon.

3. The main types of argon plasma sources


a. Inductively coupled plasma; ICP
b. Direct current plasma; DCP
c. A microwave-induced plasmas is recently introduced to spectro-chemical
analysis methods.

Atomic Emission Spectroscopy

Plasma
Magnetic field

Induction coils

Quartz tubes
Argon
tangential flow
Sample flow

Atomic Emission Spectroscopy


Inductively coupled plasma; ICP
Argon gas flows upward through a quartz tube, around which is
wrapped with a copper or selenoid induction coil.
The coil is energized by a radio frequency AC generator creating a
changeable magnetic field on the flowing gas inside. This induces
a circulating current in the gas, which in turn heats it.
Argon is not a conductor at low temperatures, but becomes
electrically conducting by heating it. The induction is initiated by
arc or a heated graphite rod.
It is used for multi-element determination

Atomic Emission Spectroscopy


Direct current, DCP
It consists of a high-voltage discharge between two graphite
electrodes. The recent design employs a third electrode arranged
in an inverted Y-shaped which improves the stability of discharge.
The sample is nebulised at a flow rate of 1 ml/min. Argon is used
as carrier gas. The argon ionized by the high-voltage is able to
sustain a current.
DCP generally has lower detection limits than ICP. However, DCP
is less expensive than ICP.

Atomic Emission Spectroscopy


Advantages of plasma excitation source:
12-

The sample could be introduced in solution form through a


nebulizer (easy for quantitative analysis).
It is suitable for quantitative multielement determinations

3-

The high temperature of plasma eleminates many chemical


interferences present in a flame

4-

It is well suited for refractory (oxide forming) elements e.g.


P, Ur and tungeston and for difficult-to-excite elements
such as Zn and Cd.

5-

The emission intensity-versus-cencentration range is linear


over a very wide dynamic ranges of analytes.

Atomic Emission Spectroscopy


Laser excitation source
Laser beam is used to vaporize the sample, which is then excited
electrically.
The sample is loaded just beneath the two electrodes that will be
used to generate the electrical discharge.
A ruby laser is then focused through a microscope onto the
surface. The energy from the laser causes an intense local hot spot
which vaporizes a small quantity of sample.
The vapor circuits the electrodes and electrical discharge occurs
which excites the metals in vapor. The excited metals emit typical
emission spectra which are collected and measured as usual.

Atomic Emission Spectroscopy


Advantages of laser excitation source
1. Laser excitation produces a high density plasma and is used
for the spectrochemical analysis of solid materials.
2. The localization effect permits examination of areas as small
as 50 m in diameter, providing the biological researcher with
a tool capable of examining the insides of individual cells
without destruction of organic materials.
3. In laser excitation, the sample needs not to be electrically
conducting.

Quantitative analysis
Use of an inernal standard
If the composition of sample and matrix is unknown. The internal
standard is added to both unknown and calibration standards.
The internal standard should
1. resemble the element to be determined in rate of volatilization
and chemical reactivity.
2. have a measurable emission line in the same spectral vicinity as
the sample emission line.
3. It must not also present in the original sample.
Then, by plotting the ratio of intensities of the element to the
internal-standard element vs. concentration of the element, any
fluctuations should be compensated for.

Standard Addition Method


in order to partially or wholly counteract the chemical and
spectral interferences introduced by the sample matrix.

Applications of AES (using non-flame excitation sources)


AES is rapid method for qualitative and quantitative
determination of most metals.
It is superior than flame and atomic absorption methods. Flame
emission spectroscopy has the limitations of being only good for
few elements while atomic absorption techniques need a separate
source lamp for each element. AES methods; being very sensitive,
have numerious applications in analysis of biological samples.
For examples:
1. evaluation of platinum in body fluids and tissues after
administration of platinum containing anticancer drugs
2. determination of organic and inorganic Se compounds in
biological fluids and environmental samples
3. determination of trace elements such as Cd, Co, Cr, Cu, Fe,
Hg, Mn, Ni and Pb
4. Silicon is recogonized as an essential trace element
participating in normal body metabolism.