CHM260

CHAPTER 3
ATOMIC SPECTROSCOPY
BASED ON FLAME
ATOMIZATION: THEORY,
INSTRUMENTATION AND
APPLICATION

NOR AKMALAZURA JAN

 SUBTOPICS
1.Atomic absorption spectroscopy (AAS):
Introduction

Fundamental principles of Flame AAS

Instrumentation in FAAS

AAS spectrophotometer

Interferences in AAS

Atomic absorption analytical techniques

Quantitative analysis by 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

Comparison of AAS and AES

 INTRODUCTION
Spectroscopy of atoms:
- atoms are the simplest and purest form a matter and
cannot rotate or vibrate as a molecules does.
- atoms only undergoes electronic transitions when
energy is absorbed.
Because the electronic transitions are discrete
(quantized), line spectra are observed.
Applications of atomic spectroscopy:
i) analysis of heavy-metals contaminations in
environmental samples. Examples of heavy- metals
are the transition metals, some metalloids,
lanthanides and actinides.
ii) metal impurities in pharmaceutical samples
 INTRODUCTION
Three techniques (methods) included in atomic spectroscopy:

1) atomic absorption spectroscopy (AAS)

2) atomic emisssion spectroscopy (AES)
3) atomic fluorescene spectroscopy
 Atomic absorption spectroscopy and atomic emission
spectroscopy are used to determine the concentration of an
element in solution.
Atomic absorption spectroscopy:

Absorbance = -log(P/Po)
P = Power of transmitted radiation
Po = Power of incident radiation

Atomic emission spectroscopy:

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

AAS: Light is absorbed by atoms of an analyte.

The sample is aspirated in the form of aerosol into flame
using nebulizer.
In the flame, the liquid/solvent is evaporated while the
metal vaporized as atoms.
The flame contains atoms of the metal.

The flame is lined up in a beam of light of the appropriate

wavelength.
 The flame (thermal energy) causes the atom to undergo a
transition from ground state to the first excited state.
When the atoms make their transition, they absorb some of
the light from the beam i.e. radiation of a particular
wavelength that produced by a special source made from
that element (example HCL). Wavelengths of radiation
given off by the source are the same as those absorbed by
the atoms in the flame.
The more concentrated the solution, the more light energy
is absorbed.
 The lamp must be aligned perfectly to the hottest part of
the flame and travels to the detector (example
photomultiplier tube).
Detector measures the intensity of the beam of light.
- the intensity of beam will reduced when the light absorb
by the metal.
- the detector records the reduction as an absorption.

Absorbance = -log(P/Po)
P = transmitted radiation
Po = incident radiation

The absorption is shown on a read out by the data system.

 This absorption follows Beers law i.e. absorbance is
directly proportional to the pathlength in the flame and to
the concentration of atomic vapor in the flame.

Concentration of atomic vapor directly proportional to the

concentration of the analyte in the solution being
aspirated.

The concentration of analyte (metals) in a sample can be

determined by using calibration curve (Absorbance
versus concentration of standard solution).
 Processes occurring in flame
Ca *
AAS AES
Excitation h
energy, h (Emission)
Aspiration
CaCl2 CaCl2 (g) Dissociation Ca (g) + 2Cl (g)
solution energy

CaO* Excitation CaO Ionization

Flame
energy, h CaOH energy
CaOH* gases

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.

o Atomization: The process by which a sample is converted to

an atomic vapor or elementary ions.

o Device used to converted a sample to an atomic vapor is

called atomizer.

o Two common methods of sample atomization:

i) Flame atomization**
ii) Electrothermal atomization
 FLAME ATOMIZATION

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

Acetylene / air: most common

Acetylene / N2O flame is the best for refractory elements.
(refractory: elements that form stable compounds that are
not completely atomised at the temperature of the flame or
graphite furnace).
Selection of flame type depends on the volatilization of
interest.
Significant variations in flame temperatures can be obtained
by changing the composition of fuel and oxidant.
 Flames are only stable at certain flow rates:

- at low flow rates (less than the maximum burning

velocity) the flame propagates into the burner body
causing flashback and, in some cases, an explosion.
- when the flow rate is increased, the flame starts to rise
above the burner body.
- best flames are obtained when the flow rate of the gas
is equal to the maximum burning velocity. At this equity
ratio the flame is most stable.
- At higher ratios, flames will reach a point where they
will no longer form and blow off the burner.
2. Flame Structure

Interzonal region is the hottest

part of the flame and best for
atomic absorption.
Oxidation of the atoms occurs in
the secondary combustion zone
where the atoms will form
molecular oxides and are
dispersed into the surroundings.

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

Nebulizer and burner are combined into a single unit.

Sample solution is directly aspirated into the flame.
All desolvation, atomization, and excitation occurs in the
flame.
Sample is drawn up the capillary and nebulized.
Sample flow rate: 1 to 3 mL/min.
Advantage:
- introduce relatively large and representative sample into
the flame.
Disadvantages:
- A relatively short path length through flame.
- Problems with clogging of the tip.
- Burners noisy from electronic and auditory stand point.
Turbulent Flow Burner
 Laminar flow burner

Sample is nebulized by the flow of oxidant past a capillary

tip.

Resulting aerosol then mixed with fuel and flows past a

series of spoilers (baffles) that allow only the finest
droplets to reach the burner head.

The larger droplets of the resulting aerosol condense and

drain out of the chamber to a waste container (~90%).

Aerosol, oxidant and fuel are burned in a slotted burner

that provided a flame, 5 10 cm in length.
 Laminar Flow Burner
Fine
droplets
 Function of nebulizer:
i) Suck up liquid sample at a controlled rate.
ii) Create a fine aerosol (nebulization) for introduction
into the flame.
iii) Mix the aerosol and fuel and oxidant thoroughly for
introduction into the flame (desolvation).

Function of the flame:

i) Produce atoms (the elemental form) of the element of
interest.
 Advantages:
i. Provide quiet flame.
ii. Longer path length, enhance sensitivity and
reproducibility.

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:

Flame atomizers have good precision (<1% relative

precision).
Relatively low sensitivity compared to electrothermal
atomization.
There are two reasons for the low sampling efficiency
of flame atomizers:
i) Most of the sample is wasted due to the nebulization
process.
ii) Atoms have a short residence times in the flame
(~ 10-4 s).
INSTRUMENTATION FOR FLAME ATOMIC
ABSORPTION SPECTROSCOPY (AAS)
Contain same basic components as an instrument
designed for absorption analysis of solution.

(Atomizer cell that contains

the gaseous atomized
sample)
 AAS

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:

1) Hollow cathode lamp (HCL)

2) Electrodeless discharge lamp (EDL)
 1. Hollow Cathode Lamp (HCL)

Components in HCL:

i)A cylindrical hollow cathode made of the element to be determined or an

alloy of it.
ii)Tungsten anode.
iii)Enclosed in a glass tube usually with a quartz or pyrex window since
the lines of interest are often in UV region.
iv)Tube is under reduced pressure and filled with inert gas such as Ne or
Ar.
 How does the Hollow Cathode Lamp works?
When potentials of 300 volts are applied to the lamp, the Ne
or Ar in the lamp will ionize at the anode.
The noble gas ions (positive ions) then accelerate towards the
cathode with sufficient kinetic energy to dislodge excited
metal atoms and produce an atomic cloud of metal atoms. This
is known as sputtering. The metal will become vaporized.
The vaporized metal is excited to higher energy levels by
continued collision with the high-energy gas ions.
When the electrons return to the ground state, the
characteristic lines that metallic element are emitted.
The filler gas also emitted lines, but the lines are not close
enough to the element lines to interfere.
A close-up view of a typical HCL

Hollow cathode lamp element Na

 The HCL lines are passed through the flame and become absorbed
by the test element because they posses just the right energy (the
right wavelength) to the result in the discrete electronic transitions.

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.

Signal 1 (Blocked Beam) = Pe

Signal 2 (Transmitted Beam) = P + Pe
Overall Difference Signal = (P + Pe) - Pe = P (Corrected Signal)
 MONOCHROMATOR
Isolation of the absorption line from background
light and from molecular emissions originating in
the flame, i.e. tuned to a specific wavelength.

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

HCL Emission spectrum

of HCL: line Amplifier
spectra

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

The two beams are recombined by a half-silvered

mirror to a single path and then pass into a Czerny-
Turner grating monochromator and then detector
(photomultiplier tube).
The ratio between the reference and sample signal is
then amplified and fed to readout (digital meter or
computer).
 INTERFERENCES IN AAS

** 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 .

Sources of spectral interference:

i) Overlapping AA or AE lines
This type of interference is rare.
The separation between the lines must be <0.01 nm for
this to be a problem.
ii) Background interference

Due to scattering of the source beam or molecular (broadband)

absorption.
1) Scattering phenomenon is most important when
concentrated solutions containing elements that form refractory
oxides (like Ti, Zr, and W) are present in sample matrix.
- Metal oxide particles with diameters larger than the
wavelength of light appear to be formed, and scattering of the
incident beam results.
2) Samples containing organic materials or organic solvents
(used to dissolve sample) can form carbonaceous (especially in
cases of incomplete combustion) particles that scatter
radiation.
3) Presence of combustion products that exhibit broadband
absorption or particulate products that scatter radiation.
4) Source of absorption or scattering can be originated in the sample matrix.
- Example: Determination of barium in alkaline earth mixture. The
wavelength of Ba line used for atomic absorption analysis appears in the
center of a broad absorption band for CaOH.
- The effect can be eliminated by substituting nitrous oxide for air as the
oxidant which yields a higher temperature that decomposed the CaOH and
eliminates the absorption band.
 Background correction method
1. Two-line correction method
An emission line from the source that is very close to the
absorbance line for the analyte is used as a reference beam.
There must not be any absorption by the analyte at the
reference wavelength.
Any absorbance at the reference line is assumed due to
background absorbance and/or scattering from the sample.
The absorbance at the reference beam is then subtracted from
the absorbance measured for the analyte.
Sources of the reference line:
a) impurity in the lamp
b) filler gas line
c) nonresonance line
This type of background correction is not commonly used
since it is often difficult to find a useful reference line.
2) Continuum-source correction
Utilizes a continuum source (e.g. deuterium lamp) and
a chopper.
The continuous source will give broadband absorption
assumed to be due to scattering or absorption by the
sample matrix.
The absorbance of the beam from the deuterium lamp
is then subtracted from the analyte beam (HCL) and
thus a background correction is obtained.
3) Source self-reversal (Smith-Heiftje Correction)
High current in a HCL induces self absorption by
the lamp which results in a broadening of the
emission line.
High current and low current on the lamp is
alternated. Any absorbance observed during the
high current period of the lamp is assumed due to
background absorbance and subtracted from the
analyte signal.
4) Zeeman background correction

o Zeeman effect: When an atomic vapor is exposed to a

strong magnetic field (~10 kG), a splitting of
electronic energy levels of the atoms takes place that
leads to formation of several absorption lines for
each electronic transition. These lines are separated
from one another by about 0.01 nm, with the sum of
the absorbance for the lines exactly equal to the
original line from which they were formed.

o Plane polarized light will allow the observation of

different bands of absorption.
Schematic of an electrothermal atomic absorption instrument
that provides a background correction based on the Zeeman
effect
 Use a high resolution spectrometer
Example: High-Resolution Continuum Source AAS.
Interference is minimized through optimum line
separation.

Choose another wavelength for analysis

Tune the monochromator to a different spectral line for
the element of interest so that there is no overlap.
Example: A vanadium line at 3082.11 interferes in an
analysis based upon the aluminum absorption line at
3082.15 . This type of interference can be avoid by
employing the aluminum line at 3092.7 instead.
 Chemical interferences

Result from various processes occurring during

atomization that alter the absorption characteristics of
the analyte.

Types of chemical interferences:

1. Formation of low volatility compounds
- Anions present in the flame or furnace can form
compounds of low volatility with analyte and reduce
the fraction of the analyte that is atomized.
- Outcome: Low results of analyte or the absorbance
of analyte is decreased.
 Anion interference:
Example 1 (anion interference - SO2-4 and PO3-4 ):
- The decrease in Ca absorbance with increasing concentrations of
sulfate or phosphate ions in sample.

Ca2+ + SO2-4 CaSO4 (s) (non-volatile salt)

Ca2+ + PO3-4 Ca2P2O7 (s) (non-volatile salt)

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.

Fe2+ + SO2-4 FeSO4 (s) (non-volatile salt)

- SO2-4 prevents the atomization of Fe ion by producing refractory

compound (non-volatile salts) that are difficult to volatilize and are
not atomized in flames or plasmas.
- When there are less Fe atoms, the absorbance recorded is lower.
 Cation interference:

Example (cation interference Al):

- The absorbance of Mg is low due to the present of
Al.
- Al forms a heat-stable Al-Mg compound that are
difficult to volatile.
- The Mg atoms will decreased caused the
absorbance become lower.
 METHODS TO OVERCOME
FORMATION OF VOLATILITY
a)
COMPOUNDS
Releasing Agent Cations that react preferentially with
the interferant and prevent its interaction with the analyte.
- Addition of an excess of strontium or lanthanum ions
minimizes the interference of phosphate in the determination
of Ca and determination of Mg in the presence of Al.
- Strontium or lanthanum replaces the analyte (Ca or Mg) in
the compound formed with the interfering species.
- Example: Addition of 1000 ppm LaCl3 in Ca analysis.
Ca3(PO4)2 + 2LaCl3 3CaCl2 + 2LaPO4
b) Protective Agent
Prevent interference by forming stable but volatile species with
analyte.
3 common reagents: ethylenediaminetetraacetic acid (EDTA), 8-
hydroxyquinoline and APCD (ammonium salt of 1-
pyrrolidinecarbodithioic acid).
The present of high concentration of EDTA is to eliminate the
interference of Al, Si, phosphate, and sulfate in the
determination of Ca.
- EDTA + Ca Calcium-EDTA chelate Ca vapor
Dissociated
in the flame
- 8-hydroxyquinoline-eliminate the interference of Al in the
determination of Ca and Mg.

c) Use higher-temperature flame

Example: nitrous oxide-acetylene flame
2. Dissociation equilibria

In the hot, gas environment of a flame or a furnace,

dissociation and association reactions lead to
conversion of the metallic constituents to the
elemental state. Some of the reaction is reversible.

Example: MO M+O M = analyte

M(OH)2 M + 2OH OH = hydroxyl radical

A shift in the equilibrium towards the metal oxide

will result in a reduction in absorption of radiation by
the metal analyte.
 Example: Refractory elements such as Al, Ti, Mo
and V will react with O and OH species in the flame
to produce thermally stable metal oxides and
hydroxides.

This process is highly dependent on flame

conditions (i.e. fuel rich, fuel lean, or flame
temperature).

Metal oxides and metal hydroxides can be

decomposed by using high-temperature flames
such as nitrous oxide-acetylene flame so that
atomic vapor of the metal can be produces.
3. Ionization equilibria
M M + + e- M = analyte
Sample (liquid/solid) must be vaporized and
atomized in a high temperature source such as
flame.
This high temperature environment lead to
ionization of the analyte atoms.
Problem in the analysis of alkali metal ions:
Alkali metals have lowest ionisation energies
and are therefore most easily ionized in flames.
Ionisation leads to reduced signal intensity, as
energy levels of ions are different from those of the
parent ions.
 Ionisation of the analyte element can be suppressed by
adding an element that is more easily ionised. Ionisation
of the added element results in a high concentration of
electrons in the flame which shifts the equilibrium of the
analyte from the ionic to the atomic form.
M M + + e-

Cesium and potassium are common ionization

suppressors that are added to analyte solutions. These
atoms (Cs and K) are easily ionized and produce a high
concentration of free electrons in the flame.
- Example: Addition of 1000 ppm CsCl when analysed Na
or K.
 ATOMIC ABSORPTION ANALYTICAL
TECHNIQUES
SAMPLE PREPARATION
Sample in the form of diluted and filtered (particulates)
solution.
Dilution with water will be required to prevent clogging
of the burner.
Chemical interferences can be overcome by simple
addition of (dilution with) a suitable reagent . For
example, serum is diluted 1:20 with a solution
containing EDTA for the determination of Ca in order to
prevent interference from phosphate. Na and K, in
concentrations equal to those in serum, are added to Ca
standards to prevent ionization interference.
 QUANTITATIVE ANALYSIS BY ATOMIC
ABSORPTION SPECTROSCOPY
Calibration Curve
In theory, atomic absorption should follow Beers Law
with absorbance being directly proportional to
concentration.
But, calibration curves are often nonlinear.
Applying Beers law in atomic absorption spectroscopy
is difficult due to variations in the atomization from the
sample matrix and non-uniformity of concentration and
path length of analyte atoms.
 Standard-Addition Method
Extensively used in AAS.
Used to overcome sample matrix effects (due to the
presence of a lot of impurities in the sample).
Compensate for variation caused by physical and
chemical interferences in the analyte solution.
The most common way involves adding one or
more increments of a standard solution to sample
aliquots of the same size.
This process is often called spiking the sample.
Each solution is then diluted to a fixed volume
before measurement.
Standard Addition:
- if Beers law is obeyed,

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

compared with equation 1

A = kCstd (Vstd) + kVxCx

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

1. Plot the standard addition graph.

2. Calculate the concentration of Cr in the sample.
 10.0 mL unknown 10.0 mL unknown 10.0 mL unknown 10.0 mL unknown
10.0 mL unknown
+ distilled water + 10 mL 12.2 + 20 mL 12.2 + 30 mL 12.2 + 40 mL 12.2
ppm Cr ppm Cr ppm Cr ppm Cr

Standard 1 Standard 2 Standard 3 Standard 4 Standard 5

50 mL volumetric flasks
1. Plot the standard addition graph (Absorbance versus volume of
standard solution).
Absorbance

Volume of standard solution, mL

2. Calculate the concentration of Cr in the sample (Cx).

Cx = bCstd
mVx
= (0.202 x 12.2 ppm) = 30.81 ppm
(0.008 mL-1 x 10 mL)
Example 2:
In the determination of silicon, Si in jet-engine oils using AAS,
the standard addition method was used and the following
data was obtained.
Solution Concentration of Absorbance
added Si standard
(ppb)
Blank 0.0 0.018
Addition 1 12.5 0.094
Addition 2 25.0 0.139
Addition 3 37.5 0.179

Plot the standard addition graph and determine the amount of

Si present in the oil sample.
Graph Absorbance versus concentration of standard solution
Absorbance

x- intercept = -7

Concentration of standard solution, ppb

Amount of Si in jet engine oils = x-intercept

x-intercept when y = 0
0.004x + 0.028 = 0
x = -7
= -7.0 = 7.00 ppb
 APPLICATIONS OF ATOMIC ABSORPTION
SPECTROSCOPY

Used for the determination of over sixty metals

and metalloids.
The resonance lines for the nonmetallic elements
are located at wavelengths shorter than 200 nm,
thus preventing their determination by convenient,
nonvacuum spectrophotometers.
Detection limits:
Flame atomic absorption spectroscopy (FAAS):
0.001 0.020 ppm or 1-20 ng/mL
Detection Limits (ng/mL) for selected elements

Element AAS Flame Element AAS Flame

Al 30 Cu 2
As 100 Fe 5
Ca 1 Hg 500
Cd 1 Pb 10
Cr 3 Zn 2

1 ng/mL = 10-3 g/mL = 10-3 ppm

 Accuracy

- Relative error associated with a flame absorption

analysis is the order of 1% to 2%.
- With special precautions, this figure can be
lowered to a few tenths of one percent.
 DISADVANTAGES OF FLAME ABSORPTION
SPECTROSCOPY:
only solutions can be analysed
relatively large sample quantities required (1 2 mL)
less sensitivity (compared to graphite furnace)
problems with refractory elements

ADVANTAGES OF FLAME ABSORPTION

SPECTROSCOPY:
inexpensive (equipment, day-to-day running)
high sample throughput
easy to use
high precision
ATOMIC EMISSION
SPECTROSCOPY
(AES)
 INTRODUCTION
Basic Schematic AES:

Scanning instruments can detect multiple elements.

Many lines detected, so sometimes it is a quantitatively
difficult method.
Source can be flame, but more commonly plasma
because it is much hotter.
 PRINCIPLES OF AES
The sample is introduced into an atomization-excitation source
where it is converted into atomic vapours of the analyte in excited
state:
solution liquid transform into an aerosols (nebulization)
solid atoms + gaseous fuel (desolvation) solid atoms are
converted to a vapor in the flame (volatilization) atoms /ions/
molecules are excited
The excited atoms return back to the ground state after a very
short lifetime (typically 106 to 109 s).
This is accompanied by the emission of electromagnetic
radiation. Each element emits light at a characteristic wavelength,
which is dispersed by a grating or prism and detected by the
transducers such as photomultiplier tubes.
This radiation is characteristic of the analyte in the sample.
 PLASMA SOURCES
Advantages of plasma:
o Simultaneous multi-element
analysis saves sample amount.
o Some non-metal determination
(Cl, Br, I, and S).
o Concentration range of several
decades (105 106)

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.

There are three types of plasma sources:

A) Inductively coupled plasma (ICP)
B) Direct current plasma (DCP)
C) Microwave induced plasma (MIP)

ICP and DCP are the most common plasma source.

Inductively Coupled Plasma (ICP)

Constructed of three concentric quartz tube.

Radio frequencies (RF) current passes through the
water-cooled Cu coil, which induces a magnetic
field.
A spark generates argon ions which are held in the
magnetic field and collide with other argon atoms
to produce more ions.
Argon in outer tube swirls to keep plasma above
the tube.
The heat is produced due to the formation of
argon ions.
ICP
A SCHEMATIC LAYOUT OF DIFFERENT COMPONENTS
OF AN ICP-AES SPECTROMETER
1. Sample introduction in ICP:

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

Plasma consists of two regions:

i) Excitation region
- The bright, white, donut shaped region at the top of
the torch.
- Radiation from this region is a continuum with the
argon line spectrum superimposed.
- Temperature: 8000-10000K
ii) Observation region
- The flame shaped region above the torch with
temperatures ~1000-8000K.
- The spectrum consists of emission lines from the
analyte along with many lines from ions in the torch.
Temperatures in a typical ICP source
3. Analyte Atomization and Ionization
By the time the analyte reaches the observation zone it
has resided in the excitation zone for 2 ms.
Advantages of ICP over flame:
i) Temperature is two to three times higher than in a
flame or furnace, which results in higher atomization
and excitation efficiencies.
ii) There is little chemical interference.
iii) Atomization in the inert (argon) atmosphere
minimizes oxidation of the analyte.
iv) Short optical path length minimizes the probability
of self-absorption by argon atoms in the plasma.
v) Linear calibration curves can cover up to five
orders of magnitude.
** Flame emission analysis is sensitive to flame
temperature / the flame must stable during
the analysis:
- In emission spectroscopy, the analyte signal
is due to a small number of excited atoms.
Therefore, any change or fluctuations in
flame temperature will dramatically influence
the number of excited species. Therefore, the
analytical signal will also be inconsistent.
 INTERFERENCES IN AES
Spectral Interferences:

i) Overlap of a spectral line from another element.

- For example, Cu emission at 515.323 nm is likely to show an
overlapping with the emission from Ar at 515.139 nm.
- Method to overcome the interferences: Can minimised either
by using a high resolution dispersion system or by using more
than one analytical line for the detection of a single element.
ii) Unresolved overlap of molecular band spectra.
iii) Recombination phenomena.
iv) Background emission from the source.
v) Stray light from the line emission of high concentration
elements.
 Physical Interferences:
o Processes of sample nebulisation and transport.
- The differences in the physical properties of the
sample and calibration solutions lead to variations in the
aerosol droplet size.
- Influence the efficiency of the nebuliser and the sample
introduction.
- The changes in viscosity and surface tension of the
solutions can also cause significant inaccuracies.
- Samples containing high amounts of dissolved solids
or high acid concentrations.
o Method to overcome the physical interferences:
i) Can be reduced by diluting the sample.
ii) Use an internal standard.
 Chemical Interferences:
i) Include molecular compound formation, ionisation
effects, and solute vaporisation effects.
These effects are generally not very significant in ICP-
AES.
Can be minimised by carefully controlling the operating
conditions such as incident power, observation
position, matrix matching, etc.

ii) Memory effects resulting from the presence of the

analytes in a previous sample and contributing to the
signals measured in a new sample are also an area of
concern.
Can be minimised by purging the system with a blank in
between samples.
 APPLICATIONS OF ICP-AES
Agricultural science: Analysis of agricultural products and foods
besides soil analysis.
Health sciences: i) Determination of Al in blood, Cu in brain tissue, Se
in liver, Na in breast milk.
ii) Direct determination of Ca, Fe, Cu, Mg, Na and K in serum samples.
Geological sciences: Presence of lanthanides and other elements in
rock samples.
Forensic Sciences: Crime scene soil analysis.
Metallurgy: Analysis of trace elements in stainless steel.
Environmental science: Waste water analysis, determination of
pollutant metals in variety of matrices.
Industry: i) Presence of metals like Cu, Fe, Ni, and Si in lubricating oils
or gasoline at tracer concentration.
ii) Traces of metals like Ca, Cu, Fe, Mn, Mg, P, K and Zn in beer or wine;
determination of trace elements in polymers and evaluation of
catalysts.
 ADVANTAGES OF ICP-AES
Rapid and simultaneous multi-element analysis.
Lack of chemical interferences.
High temperature of the excitation source : 5000 to 10000K.
Low sample requirements.
Absence of self absorption, the cause of non-linear
calibration plots in FES.
Validity of calibration curves over 4 to 6 orders of
magnitude.
Low detection limits: 1 to 100 ng/g or g/l (part per billion).
Good accuracy and precision: relative standard deviation of
about 1 per cent.
Applicability to elements that are difficult to be determined
by AAS: B, C, Ce, La, Nb, Pr, S, P, Ti, Ta, V and Zr can also be
measured.
 COMPARISON AAS AND
1. Principle of operations: AES
Flame Emission:
- it measures the radiation emitted by the excited atoms that
is related to concentration.
- depends upon the number of excited atoms and influenced
by temperature variations.

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.

The Function of Flame:

a. To convert the constituents of liquid sample
into the vapor state.

b. To decompose the constituents into atoms or

simple molecules:
M+ + e- (from flame) M + hv

c. To electronically excite a fraction of the

resulting atomic or molecular species:
M M*
3. Data obtained:
Both methods use atomization of a sample and
therefore determine the concentrations of elements.
AAS:
- Absorption of radiation of a defined wavelength is
passed through a sample and the absorption of the
radiation is determined. The absorption is defined by the
electronic transition for a given element and is specific
for a given element. The concentration is proportional to
the absorbed radiation.
AES:
- The element is excited. A rapid relaxation is
accompanied by emission of UV or visible radiation is
used to identify the element. The intensity of the emitted
photon is proportional to element concentration.
 AAS AES
Principle of Absorption of light by Emission of light by
operation unexcited atoms. excited atoms.
Use of flame Flame is used to Flame is used to atomize
atomize the sample. and excite the electrons.

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.

Beers Law Applicable Not applicable

Data obtained Absorbance versus Intensity versus
concentration concentration