ATOMIC SPECTROSCOPY

BASED ON FLAME
ATOMIZATION (CHAPTER 3)
CHM 260
 Lesson Outcomes
2

 Explain the principles of Flame Atomic Spectroscopy

(absorption and emission)
 Draw and label the schematic diagram of AAS and
AES
 Able to explain the functions of each component in
AAS and AES
 Discuss the difference in terms of parts and functions
of AAS and AES
3.1 Fundamental Principle
Atomic Spectroscopy
 Atomic Spectroscopy
4

 A class of spectroscopic methods in which the species

examined in the spectrometer are in the form of ATOMS
(not molecules or ions)
 Spectral transitions are observed to occur between
electronic energy levels in the visible, UV and x-ray
regions
 The wavelengths of the observed absorption/emission
lines are characteristic of a particular ELEMENT
 The intensity of the spectral line is proportional to the
number of atoms undergoing the corresponding
transition
 En
Emission
Absorption

E1

E1

5
 Atomic Spectra
6

 Each element has a characteristic spectrum.

Example: Na gives a characteristic line at 589 nm
 Atomic spectra feature sharp bands
 Applications of Atomic Spectroscopy
7

 Wide application in industry & research

 High sensitivity for qualitative and quantitative
determination of metallic elements
eg:
- Clinical studies : Ca & Mg
- Environmental pollutants : Pb, Hg, Cu, Cd etc
- Forensic studies
- Toxicological studies : Heavy metals (As, Cr, Hg
etc)
 Elements detectable by atomic absorption

8
  Three techniques (methods) included in atomic
spectroscopy
1. Atomic absorption spectroscopy (AAS)
2. Atomic emission spectroscopy (AES)
3. Atomic fluorescence spectroscopy

(Focus on 1 & 2 only)

9
3.2 Flame AAS
Flame Atomic Absorption Spectroscopy
 AAS Principle
11

 AAS is based on the same principle as the flame test

used in qualitative analysis
 When an alkali metal salt or a calcium, strontium or
barium salt is heated strongly in the Bunsen flame, a
characteristic flame colour is observed:
Na →yellow
Li → crimson
Ca → brick red
Sr → crimson
Ba →green
  In the flame, the ions are reduced to gaseous metal
atoms
heat
compound atom
 The high temperature of the flame excites a valence
electron to a higher-energy orbital. The atom then
emits energy in the form of (visible) light as the
electron falls back into the lower energy orbital
(ground state)

12
  The ground state atom absorbs light of the same
characteristic wavelengths as it emits when returning
from the excited state to the ground state
 The intensity of the absorbed light is proportional to
the concentration of the element in the flame
(quantitative analysis)
 Absorbance or emission of atomic vapour is
measured (Oxidation states (e.g. Fe2+, Fe3+) cannot
be distinguished)

13
 3.2.1 Atomization Process (Sample
14
Introduction)
 In order to perform atomic spectroscopy, atoms of the
analyte must first be formed, usually in the form of an
atomic vapor
 Atomization is the process by which a sample is
converted to an atomic vapor
- Solution of the analyte is evaporated rapidly at an
elevated temperature to yield a finely divided solid
 Atomizer is a device used to convert a sample to an
atomic vapor
 Type of Atomizer Typical Atomization
Temp, °C
Flame 1700-3150
Electrothermal vaporization (ETV) 1200-3000
Inductively coupled argon plasma 4000-6000
(ICP)
Direct current argon plasma (DCP) 4000-6000
Microwave-induced argon plasma 2000-3000
(MIP)
Glow-discharge plasma (GD) Nonthermal
Electric arc 4000-5000
Electric spark 40 000 (?)
15
 3.2.2 Flame Atomization
16

Process occurring during atomization process:

1. Nebulization

Conversion of the liquid sample to a fine spray

2. Desolvation

Solid atoms are mixed with the gaseous fuel

3. Volatilization

Solid atoms are converted to a vapor in the flame

(molecules/atoms/ions.)
 What are the process involve to change the analyte
from one state to another?

There are three types of particles that exist in the flame:

1. Atoms 2. Molecules 3. Ions

17
 3.2.3 Properties of Flame
18

Types of flame:
Fuel Oxidant Temperature °C Max burning
velocity cms-1
Natural gas Air 1700-1900 39-43
Natural gas Oxygen 2700-2800 370-390
Hydrogen Air 2000-2100 300-400
Hydrogen Oxygen 2550-2700 900-1400
Acetylene Air 2100-2400 158-266
Acetylene Oxygen 3050-3150 1100-2480
Acetylene Nitrous oxide 2600-2800 285

*Selection of flame type depends on the volatilization

temperature of the atom of interest. Most common is
Acetylene/air.
 Flame Structure
19

 Primary combustion zone is

characterized by existence of some
non atomized species & presence of
fuel species that emit in the blue
region of the electromagnetic
spectrum
 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
 Temperature Profile
20

Temperature profile in
degrees Celsius for a
natural gas-air flame
 Nebulizer
21

 sucks up the liquid sample (=

aspiration)
 creates a fine aerosol (fine
spray) for introduction into
flame
 mixes aerosol, fuel and
oxidant thoroughly, creates a
heterogenous mixture
 the smaller the size of the
droplets produced, the higher
the element sensitivity
 a) Concentric tubes.
b) Cross flow.
c) Fritted disk.
d) Babington.

22
 Methods of sample introduction in AAS

Method Type of sample

Pneumatic nebulization Solution or slurry
Ultrasonic nebulization Solution
Electrothermal Solid, liquid or solution
vaporization
Hydride generation Solution of certain
elements
Direct insertion Solid, powder
Laser ablation Solid, metal
Spark or arc ablation Conducting solid
Glow-discharge sputtering Conducting solid
23
 Burners
24

 The burner head is where all of the chemical

reactions take place
 The burner head consists of an inlet tube; fuel and
air inlets; a nebulizer; mixing cell; and the flame (the
reaction and sample cell)
 There are 2 types of burners in flame spectroscopy:
i. Turbulent flow
(total consumption burner)
ii. Laminar flow
(premix burner)
25
 Turbulent Flow Burner
26

❑ Nebulizer & burner are combined into a single unit.

❑ Sample is drawn up the capillary & nebulized.
❑ Sample flow rate: 1 to 3 mL/min.
27

Advantage
1. introduce relatively large & representative sample
into the flame.

Disadvantages
1. A relatively short path length through flame.
2. Problems with clogging of the tip.
3. Burners noisy from electronic and auditory stand
point.
 Laminar Flow Burner
28

❑ Sample is nebulized by the flow of oxidant which flow

through a capillary tip.
❑ Resulting aerosol then mixed with fuel & flow through
a series of baffles.
❑ Only finest droplets went through the baffels.
❑ Bigger sample droplets is collected at the bottom of
mixing chamber then drained to a waste container.
❑ Aerosol, oxidant & fuel are burned in a slotted burner
that provides a flame of 5 – 10 cm in length
29
 Advantages
1. Provide quiet flame.
2. Provide longer path length that enhance the sensitivity
& reproducibility.
Disadvantages
1. Lower rate of sample introduction.
2. Possibility of selective evaporation of mixed solvents in
the mixing chamber could create analytical
uncertainties.
3. Mixing chamber contains a potentially explosive
mixture that can flash back if the flow rates are too
low.
30
3.3 Instrumentation for Flame AAS
 AAS Instrumentation
32

Single Beam AAS Instrument:

The modulated power source can be replaced by a chopper

 Double Beam AAS Instrument:

33
  Radiation from HCL is split into 2 beams;
1. One passes through the flame.
2. The other around the flame.
 A half-silvered mirror returns both beams to a single
path then pass through the monochromator then
detector
 Monochromator is placed between sample and
detector

34
 3.3.1 Line Sources
35

 Radiation source in AAS is a line source which

provide narrow emission bands
 Common radiation source used in AAS
1. Hollow cathode lamp (HCL)
2. Electrodeless discharge lamp (EDL)
 Hollow Cathode Lamps (HCL)
36

❑ Light from this lamp exactly light required for the analysis,
even no monochromator is used.
❑ Hollow cathode lamp MUST contain the element to be
determined.
 How does HCL works?
37

❑ When lamp is on, atoms are supplied with energy

that causes electrons of the atoms elevate to the
excited states.
❑ Upon electrons returning to ground state, wavelength
of the photon emitted are useful for the analysis.
❑ The photon emitted will supply the exact amount of
energy needed for the analyzed metal to undergoes
excitation.
 Excitation mechanism in HCL
38

❑ When lamp is on, atoms are supplied with energy that causes
electrons of the atoms elevate to the excited states
❑ Upon electrons returning to ground state, wavelength of the
photon emitted are useful for the analysis
❑ The photon emitted will supply the exact amount of energy
needed for the analyzed metal to undergoes excitation.
❑ When atoms return to ground state, line spectrum of that
specific atom emitted
❑ This light is directed at the flame where unexcited atoms of the
same element absorb the radiation and raised to the excited
state
❑ Absorbance is measured and related to the concentration
 Ar + e- → Ar+ + 2e-

Reactions in the HCL:

-ionization of filler gas: Ar + e- → Ar+ + 2 e-
-sputtering of cathode atoms: M(s) + Ar+ → M(g) + Ar
-excitation of metal atoms: M(g) + Ar+ → M*(g) + Ar
-light emission: M*(g) → M(g) + hν

39
 Cathode Lamp Process
40

Excited fill gas atoms sputter metal atoms from the cathode and
excite them via a kinetic energy transfer
 Electrodeless Discharge Lamp (EDL)
41

 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 and excite the metal or salt of

interest
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

EDL can provide radiant intensities usually one to two orders of
magnitude greater than HCL
42
 3.3.2 Source Modulation
43
 ❑ Why source modulation is employed in AAS?
1. To eliminate interference caused by emission of the
radiated flame from analyte atoms and flame gas
species.
2. To distinguish between the component of radiation
arising from the source and the component of
radiation arising from the flame background.
❑ Source modulator: Light chopper

(circular rotating metal disk)

44
 ❑ The function of light chopper is to eliminate the effects of
radiation from the flame.
❑ Light is “chopped” with a rotating half-mirror so that
detector could received two alternating signals. One from
the radiation source and one from the flame.
❑ At one moment (opaque), only light emitted by flame is
read by the detector since the light from the radiation
source is cut off.
❑ Next moment (transparent), light from both the flame
emission and radiation source is read. Transmission from the
source light is measured since the source light is allowed to
pass.
❑ Absorbance of the sample is determined by measuring the
difference in radiant power between flame emission signal
and signal from the radiation source.
45
 FAAS
46
 Process occurring
during
atomization

47
 3.3.3 Interferences
48

 Interference: when the presence of substance

changes the signal from the analyte of interest
when analytes concentration remain the same
 Interferences in AAS:
a) Spectral interference
b) Chemical interference
c) Ionization interference
 Spectral interferences
49

 Spectral interferences: any physical process that effects the

light intensity at the analytical wavelength
 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 3082.11Å interferes in an
analysis based upon the aluminum absorption line at 3082.15
Å.
  Sources:
a) Scattering by combustion or particulate products
- Arise from the combustion products or particulate
matters from the atomization scatters the radiation from
the source
- Presence of combustion products that exhibit broadband
absorption or particulate products that scatter radiation
b) Scattering by sample matrix interference
- Arise when the emission or absorption of an interfering
species overlaps or lies so close to the analyte absorption

50
 - 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

51
 ❑ How to solve the problems?
a) Tune the monochromator to a different spectral line for
the element of interest so that there is no overlap.
- Example: A vanadium line at 3082.11Å interferes in an
analysis based upon the aluminum absorption line at
3082.15 Å. This type of interference can be avoid by
employing the aluminum line at 3092.7 Å instead
b) 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.
52
 c) Zeeman background correction.
- 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
- Plane polarized light will allow the observation of
different bands of absorption

53
 Chemical interferences
54

 Chemical interferences: alteration in analyte

absorbance caused by chemical processes during
atomization
 Sufficient energy must be available to dissociate
the molecular form of the analyte to free atoms.
 If the sample contains a component which forms a
thermally stable compound with the analyte that is
not completely decomposed by the energy
available in the flame, achemical interference will
exist resulting in low result
  Sources:
a) Formation of low volatility (refractory elements that
form stable compounds that are not completely
atomised):
- eg: a decrease in Ca absorbance is observed with the
increasing concentrations of phosphates,PO43- and
sulphate,SO42- due to formation of calcium phosphate
and calcium sulphate that lowers the absorbance
-Example:
Ca2+ + SO2-4 → CaSO4 (s) (non-volatile salt)
Ca2+ + PO3-4 → Ca2P2O7 (s) (non-volatile salt)

55
56

- Overcome by adding lanthanum chloride (LaCl3) to

samples, standards and blank. La3+ ions are a
releasing agent for Ca.
Ca3(PO4)2 + 2LaCl3 →3CaCl2 + 2LaPO4
- Overcome by adding protective agent such as EDTA
EDTA + Ca → Calcium-EDTA chelate→ Ca vapor
- Overcome by using higher-temperature flame:
- Example: nitrous oxide-acetylene flame
 b) Dissociation equilibrium:
- Formation of compounds between the metal and other
components in flame (O, Cl)
- eg: MCl ↔ M + Cl
NaCl ↔ Na + Cl

- A shift in the equilibrium towards the metal oxide will

result in a reduction in absorption of radiation by the
metal analyte.

57
 Ionization interference
58

 Some ions will be produced in hot flames (nitrous oxide –

acetylene flame)
 If additional energy is applied, the ground state atom can
be excited or an electron may be totally removede from
the atom, creating an ion which could reduce the number
of ground state atoms available for the light absorption
 Ions have a different spectrum from atoms
 Most serious for Mg, Ca, Na, Li, K, Sr
 Results in non-linear calibration curve
 Overcome by adding easily ionised element (Na, K, Cs),
creating a large number of free electrons in the flame &
suppressing of the analyte
 3.3.4 Sample preparation &
59
Quantitative analysis
Sample Preparation Methods:
 Some samples such as liquids and homogeneous

solids need no sample preparation

 Sometimes need to extract the analyte from the

sample solvent
Solid sample preparation:
Microwave
a) Wet digestion
b) Dry ashing Hot plate
 a) Wet Digestion (microwave)
60

 Microwave digestion is the best method converting liq. or

solid sample into solution
 The sample is digested with a combination of different
acids under high temperature and pressure
 The advantages include:
- sample contained within the digestion vessel
- highly efficient
- almost any sample can be digested
❑ Volatile element are retained in the reaction vessel
 a) Wet digestion (hot plate)
61

 Hot plate digestion uses glass or Teflon beakers for

the sample preparation. Usually re-dissolve steps
are needed
 Certain geological samples require tough
digestions. Use acids such as HF, HNO3 and HClO4
or Lithium metaborate fusion at 1200 °C. Uses
graphite crucible to heat the sample to molten state
 Organics can also be digested this way
 Problem: Loss of volatile elements
 b) Dry ashing
62

 For analysis of non-volatile elemnets

 Mainly used for organic samples
 Sample is dried and burnt at 500-600 °C to
remove carbonaceous matter
 Adv: Matrix effects are very much reduced
 Quantitative Analysis
63

 The concentration of analyte can be determined by:

a) Calibration curve
b) Standard addition method
 Quantitative analysis still follows Beer’s Lambert
Law and the concentration of unknown are
determined by the same way using the formula(
A = εbc)
 Width of the flame is consider as the beam
pathlength
 Calibration Curve
64

 A general method for determining the concentration

of a substance in an unknown sample by comparing
the unknown to a set of standard of known
concentration
 Plot is a linear of radiation absorbed vs concentration
of the analyte
 Analysis should never be based on the measurement
of a single standard with assumption that Beer’s law
is being followed
 Standard calibration curve
65

How to measure the

concentration of
unknown?
Practically, you have
measure the absorbance
of your unknown. Once
you know the absorbance
value, you can just read
the corresponding
concentration from the
graph .
 Standard Addition Method
66

 used to overcome matrix effect.

 involves adding one or more increments of a
standard solution to sample aliquots of the
same size.
 each solution is diluted to a fixed volume before
measuring its absorbance.
 How to produce standard addition
curve?
67

1. Add same quantity of unknown sample (spike) to a

series of volumetric flasks.
2. Add gradual amounts of standard solution to each
volumetric flask. For example 0 mL, 5 mL , 10mL , 15mL.
3. Dilute each flask to calibration mark, mix and measure the
absorbance.
68

Standard Addition Methods

Single-point standard Multiple additions

addition method method
 For single-point standard addition,
69

Absorbance A1 = εbVxCx
of diluted Eq. 1
sample Vt

Absorbance
of diluted
A2 = εbVxCx + εbVsCs Eq. 2
sample + std Vt Vt
70

For single-point standard addition,

Dividing the 2nd equation by the first & then rearrange it
will give.

Cx = A1 Cs Vs
(A2 – A1 ) Vx
 Example (Standard Addition)
71

A 2.00-mL urine specimen was treated with reagent

to generate a color with phosphate which then was
diluted to 100mL. Second 2.00mL sample was added
exactly 5.00mL of a phosphate solution containing
0.03 mg/mL phosphate then was treated in the same
way as the original sample. The absorbance of the
first solution was 0.428, while the second one was
0.538. Calculate the concentration of phosphate in
milligrams per millimeter of the specimen.
 Solution:
Cx = A 1 Cs Vs
(A2 – A1 ) Vx

Cx = (0.428) (0.03 mg PO43-/mL) (5.00mL)

(0.538 – 0.428)(2.00mL sample)

= 0.292 mg PO43- / mL sample

72
 • The difference between the volume of the standard
added at the origin and the value of the volume at
the intersection of the straight line with the x-axis or x-
intercept (Vs)0 is the volume of standard reagent
equivalent to the amount of analyte in the sample.
• Since,
kVscs kVxcx
A= +
Vt Vt
by solving the equation for cx,

(Vs ) 0cs
cx = −
Vx
73
 If Beer’s law is obeyed,
A = εbVstdCstd + εbVxCx
Vt Vt
= kVstdCstd + kVxCx
A = (kCstd)Vstd + kCxVx

k is a constant equal to εb/Vt

74
 Cx can be obtained from the ratio of these two
quantities m and b

b = kVxCx
m kCstd

Cx = bCstd
mVx

75
 Example 1 (Plotting Standard Addition
Graph)
76

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.

1. Plot the standard addition graph.

2. Calculate the concentration of Cr in the sample.
 Solution:
1. Plot the standard addition graph (Absorbance versus volume of standard
solution).
Absorbance
0.6

0.5
y = 0.0088x + 0.2022
R² = 0.9999
0.4

0.3

0.2

0.1

0
-40 -30 -20 -10 0 10 20 30 40 50

-0.1 Volume of standard solution, mL

77
 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)

78
 Example 2 (Plotting Standard Addition
79
Graph)
In the determination of silicon, Si in jet-engine oils using
AAS, the standard addition method was used and the
following data was obtained.

Plot the standard addition graph and determine the

amount of Si present in the oil sample.
 Solution:
Graph Absorbance versus concentration of standard solution
Absorbance
0.2
y = 0.0042x + 0.0283
R² = 0.975
0.15

0.1

0.05
x- intercept = -7

0
-20 -10 0 10 20 30 40
Concentration of standard solution, ppb
-0.05

Amount of Si in jet engine oils =  x-intercept 

x-intercept  when y = 0
0.004x + 0.028 = 0
80 x = -7
= -7.0 = 7.00 ppb
 3.3.5 Detection Limits & Accuracy
81

 Detection limits for FAAS vary enormously: from 1-5

ppb (eg: Ca, Cd, Cr, Cu) to more than 1000 ppb
(eg: P). Some elements (B, C, Br) cannot be
measured at all

 Accuracy of AAS:
- high sensitivity for most elements
- flame atomisation: concentrations at the ppm level
3.4 Flame Emission Spectroscopy
 Atomic Emission
83

 Electromagnetic radiation emitted when an excited

atom relaxes to lower levels by giving up the excess
energy in the form of photons

En
hv
hv

hv
E1
 Introduction
84

 Basic Schematic
Atomizer

Detector

 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
85

 Each element emit its own characteristics line spectrum

 Quantitative analysis can be performed here by
observing what  are emitted & comparing these
with various standard
 Detector permits qualitative as well as quantitative
analysis
 Wavelength of emitted radiation indicates what
element is present and the radiation intensity indicates
how much of the element is present
86

 Intensity of the emitted light increase with concentration

 Relationship between intensity and concentration is
usually linear

I
I = kc
Unknown concentration can be
detected by comparison with one
or a series of standards in the
same manner for the molecular
techniques
c
 Principles common to AES & AAS
87

 AES- it measures the radiation emitted by the excited

atoms that is related to concentration
 AAS- it measures the radiation absorbed by the
unexcited atoms that are determined
 AES - depends upon the number of excited atoms, &
greatly influenced by temperature variations
 AAS - depends upon the number of unexcited atoms,
the absorption intensity is not directly affected by the
temperature of the flame
88
 Relationship between AAS & AES
89

 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
 Excitation sources
90

 Flame (3000 K)
 Plasma (5000-10000 K)
 Electric arc and spark (5000 K)
 Lasers (10000 K)
 Excitation source - Flame
91

 AES using flame as excitation source is only suitable

for light elements, eg: NA, K and Ca
 Normal flames are not hot enough to excite heavy
metals and emit light
 3.4.1 Instruments
92

1. Nebulizer
2. Burner
3. Monochromator
4. Detector
5. Readout device / computer
P Wavelength Signal Processor
Source Selector Detector
Readout

Sample
 Flame AES
93

Slit Slit

Emitted
Detector

Lens
Flame Filterer
 ❑ Sample is sprayed by the nebulizer into the burner
Carried into the flame
❑ Atomized & excited
❑ The emission from the excited atoms passes into the
monochromator where the selected wavelength is
passed through for measurement
❑ Intensity of the emitted wavelength is measured by
the detection system & indicated on the
readout/computer

94
 Disadvantages of FAES
95

 Spectral & chemical interferences as in AAS

 Limited linear range due to self absorption (photons
emitted by excited atoms partly absorbed by
ground state atoms in flame)
 Flame instability
 High emission background
 3.4.2 Interferences
96

INTERFERENCES

Chemical
Spectral
interference
interference

NOTE: same interference which occur in AAS

 3.4.3 FAAS vs FAES (comparison)
97

Flame Atomic Flame Atomic

Absorption Emission
Process measured Absorption (light Emission (light
absorbed by unexcited emitted by excited
atoms in flame) atoms in a flame)
Use of flame Atomization Atomization &
excitation
Instrumentation Light source No light source
Beer’s Law Applicable Not applicable
Data obtained A vs c I vs c
 Excitation source - Plasma
98

 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 is the most common plasma source
 Inductively coupled plasma (ICP)
99

 Constructed of three concentric quartz tube

 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
 Plasma Appearance:
a) Excitation region
 The bright, white, donut shaped region at the
top of the torch. Excites & ionises atoms
 Temp: 8000-10 000 K

b) Observation region
❑ The flame shaped region above the torch

with temperatures  1000 – 8000 K

❑ The spectrum consists of emission lines from
the analyte along with many lines from ions in
the torch

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 Sample introduction:
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 base through the
central tube
b) Solid sample
❑ Sample atomized by electrothermal atomization and
carried into the plasma by a flow of argon gas

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 Advantages of ICP-AES over FAES
102

 Temperature is two to three times higher than in a

flame or furnace, which results in higher atomization
and excitation efficiencies
 There is little chemical interference
 Atomization in the inert (argon) atmosphere minimizes
oxidation of the analyte
 Short optical path length minimizes the probability of
self-absorption by argon atoms in the plasma
 Linear calibration curves can cover up to five orders
of magnitude
  Much lower detection limit because:
- Higher temperature with the plasma will increase
the population of excited state atoms
- The plasma environment is relatively chemically inert
due to the higher population of electrons which will
minimize the interference of ionization

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