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CHAPTER 3
ATOMIC SPECTROSCOPY
BASED ON FLAME
ATOMIZATION: THEORY,
INSTRUMENTATION AND
APPLICATION
Instrumentation in FAAS
AAS spectrophotometer
Interferences in AAS
Applications in AAS
SUBTOPICS
2.Atomic emission spectroscopy (AES):
Introduction
Principles in AES
Plasma sources
Interferences in AES
Applications of ICP-AES
Advantages of ICP-AES
Absorbance = -log(P/Po)
P = Power of transmitted radiation
Po = Power of incident radiation
Transmission = -log(Po/P)
Po = Power of radiation that reaches the detector in the
absence of sample.
P = Power of radiation that reaches the detector in the
presence of sample.
PRINCIPLES OF FLAME AAS
Absorbance = -log(P/Po)
P = transmitted radiation
Po = incident radiation
Ca+
Excitation
energy, h
= ground state
* = excited state Ca +*
Aspiration = A process to suck ("uptake") sample solution up the tube and into
the nebulizer chamber.
AAS = measure Ca
FLAME TEST
FLAME ATOMIC ABSORPTION SPECTROSCOPY
(AAS)
A = -log(P/Po)
Po P
Nebulizer
Aspiration
Fine capillary
tube
SAMPLE ATOMIZATION
o Atomization is the TECHNIQUES
most critical step in atomic absorption
spectroscopy.
Nebulization The
transformation of a liquid into
a spray of small droplets or
aerosols.
Desolvation - Solid atoms
are mixed with the gaseous
fuel.
Volatilization Solid atoms
are converted to a vapor in
the flame.
There are three types of
Process particles that exist in the
occurring during flame:
atomization 1) Atoms
1. Types of Flames
Fuel Oxidant Temperature, oC Maximum Burning
Velocity (cm s-1)
Natural Gas Air 1700-1900 39-43
Natural Gas Oxygen 2700-2800 370-390
Hydrogen Air 2000-2100 300-440
Hydrogen Oxygen 2550-2700 900-1400
Acetylene Air 2100-2400 158-266
Acetylene Oxygen 3050-3150 1100-2480
Acetylene Nitrous Oxide 2600-2800 285
Regions in a flame
3. Temperature profile
It is important to focus the entrance slit of the
monochromator on the same part of the flame for all
calibration and sample measurements.
Temperature profile in
degrees Celsius for a
natural gas-air flame
4. Flame Absorption Profiles
Temperature of a flame depends on the position from its tip.
It is necessary to concentrate on one spot in a flame and
adjust the height of the flame to get best signal.
Each element has its own specific height above burner tip.
Examples:
i) Ag- slow to oxidize. Use higher distances from the tip so
that higher temperatures are achieved to analyze the silver.
ii) Cr- best results occur at lower heights (fuel rich flames)
since at higher heights oxygen from atmosphere will force
chromium to convert to the oxide which will not be atomized
at flame temperatures.
iii) Mg-increasing the height above tip will increase the
signal due to increased atomization at higher temperatures.
However, at higher distances the oxide starts to form leading
to a decrease in signal.
Flame absorption profiles for three elements
5. Flame Atomizers
Burners
Function: Acts as the atomizer or converts the sample
into gas-phase atoms or elementary ions.
Turbulent Flow Burner
Disadvantages:
i. Lower rate of sample introduction.
ii. Possibility of selective evaporation of mixed
solvents in the mixing chamber, create
analytical uncertainties.
iii. Mixing chamber contains a potentially
explosive mixture that can flash back if the flow
rates are too low.
Performance Characteristics of flame atomization:
Furnace
RADIATION SOURCES LINE SOURCES
Beers Law requires that the source bandwidth must be
narrow relative to the absorption bandwidth to obtain a
linear relationship between absorbance and analyte
concentration.
This is a problem for AAS because absorption bandwidths
are very narrow (0.002 - 0.005 nm) compared to
monochromator slit widths ( 0.1 nm), which results in
nonlinear calibration curves.
This problem is overcome by using line sources with
narrow emission bands.
Line sources used in AAS:
Components in HCL:
The lines from HCL are narrower than absorption line of the
element in the flame because broadening of the absorption line at
the higher temperature and pressure of the flame. So, the entire
source linewidth is absorbed.
2. Electrodeless Discharge Lamp (EDL)
Constructed of a metal or salt of interest sealed in a quartz tube
filled with a noble gas (Ne or Ar) at low pressure (1 5 torr).
The noble gas is ionized and accelerated by a strong radio-
frequency (RF) or microwave field.
Ionized argon will hit the metal causing excitation of the atoms
of the metal of interest.
Provide radiant intensities usually one to two orders of
magnitude greater than HCLs.
Emission in Flames
Emission produced in flames due to presence of flame
constituents (molecular combustible products) and sometimes
impurities in the burner head.
The detector will see the overall signal:
i) the power of the transmitted beam (P)
ii) the power of the emitted radiation from flame (Pe)
When measuring absorbance, the detector will measure as a
high transmittance signal (actually it is P + Pe)
SOURCE OF MODULATION
Interferences caused by emission of radiation by the flame must
be eliminated by modulating the output of the source.
Important of source modulation in AAS:
- To distinguish between the signal from the source (HCL) and the
flame (atomizer).
Device: circular metal disk or light chopper
Function chopper: It performs source modulation, which is to
discriminate between the signal emitted by the source (HCL) and
the signal emitted by the flame (atomizer).
Light chopper
Light is chopped with a rotating half-mirror so that detector
see alternating light intensities.
The incident beam hits the chopper at the solid surface, the
beam will be blocked and detector will only read the emitted
signal from the flame and the light from the source is cut off
(signal 1).
Next moment, light from both the flame emission and
transmission of the sources light is measured since the
sources light is allowed to pass (signal 2).
The elements of the detector is such that the emission signal is
subtracted from the total signal and this difference is what we
measured (corrected signal).
Correction method for background emission in flames is called
source modulation.
DETECTOR
A photomultiplier measures the intensity of the incident
light and generates an electrical signal proportional to the
intensity.
The detector records the reduction as an absorption.
Absorbance = -log(P/Po)
P = transmitted radiation
Po = incident radiation
The absorption of the lamps
emission spectrum by atoms
in the flame
Monochromator Detector
Laminar- Readout
flow burner
(consist of
nebulizer)
chopper
Sample
AAS SPECTROPHOTOMETER
1. Single Beam Instrument
** The modulated
detector power can be replaced
by a chopper
2. Double Beam Instrument
Double-Beam Instrument
Radiation from hollow cathode lamp is split into 2
beams by a mirrored chopper:
i) One passes through the flame
ii)The other around the flame
** AA = atomic absorption
** AE = atomic emission
Spectral interferences
An absorption or emission line that arises from an
interfering species that overlaps the analyte absorption
line or lies close enough to the analyte absorption line that
resolution by the monochromator is impossible.
Example: A vanadium line at 3082.11 interferes in an
analysis based upon the aluminum absorption line at
3082.15 .
Calcium
- SO2-4 and PO3-4 prevents pyrophosphate of Ca ion by producing
the atomization
refractory compound (non-volatile salts) that are difficult to
volatilize and are not atomized in flames or plasmas.
- When there are less Ca atoms, the absorbance recorded is lower.
Anion interference:
Example 2 (anion interference - SO 2-4 ):
- The decrease in Fe absorbance with increasing concentrations of
sulfate ions in sample.
A = bVstdCstd + bVxCx
Vt Vt
= kVstdCstd + kVxCx (equation 1)
k is a constant equal to b
Vt
Plot a graph: Absorbance versus Volume of
standard solution (should give a straight line).
A = m(Vstd ) + b
so,
slope; m = kCstd
intercept; b = kVxCx
Cx can be obtained from the ratio of these
two quantities: m and b
b = kVxCx
m kCstd
Cx = concentration of unknown
Cx = bCstd Vx = volume of the unknown
Vt = total volume
mVx Cstd = concentration of standard
Vs = volume of added standard
Example 1:
The chromium in an aqueous sample was determined by
pipetting 10.0 mL of the unknown into each of five 50.0 mL
volumetric flasks. Various volumes of a standard containing 12.2
ppm Cr were added to the flasks, followed by diluting with
distilled water.
Volume of Volume of Absorbance
unknown (mL) standard (mL)
10.0 0.0 0.201
10.0 10.0 0.292
10.0 20.0 0.378
10.0 30.0 0.467
10.0 40.0 0.554
50 mL volumetric flasks
1. Plot the standard addition graph (Absorbance versus volume of
standard solution).
Absorbance
x- intercept = -7
Disadvantages of plasma:
o very complex spectra - hundreds
to thousands of lines.
o High resolution and expensive
optical components.
o Expensive instruments, highly
trained personnel required.
Plasma Highly ionized, electrically neutral gaseous
mixture of cations and electrons that approaches
temperature 10,000 K.
a. Liquid Sample:
- Nebulizer similar to FAAS
- Sample nebulized in a
stream of argon with a flow
rate of 0.3 1.5 L/min.
- Sample aerosol enters the
plasma at the basethrough
the central tube.
b. Solid Samples
- Sample atomized by electrothermal atomization
and carried into the plasma by a flow of argon gas.
Device for
electrothermal
vaporization
2. Plasma Appearance
Atomic Absorption:
- it measures the radiation absorbed by the unexcited atoms
that are determined.
- depends only upon the number of unexcited atoms, the
absorption intensity is not directly affected by the
temperature of the flame.
2. Flames:
Flame Emission Spectroscopy:
- based upon those particles that are electronically
excited in the medium.
Instrumentation:
i)Sources of light Light source: HCL Does not use any light
source to excite the
electrons (just used the
flame).
ii)Detectors
The detector measures The detector measures
the energies from a light light emitted from excited
source which are species.
absorbed by unexcited
atoms/ions.