ATOMIC SPECTROSCOPY

BASED ON FLAME
ATOMIZATION (CHAPTER 3)
CHM 260

By,

NAZWA JON

3.1 Fundamental Principle

Atomic Spectroscopy

Atomic Spectroscopy
3

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

Atomic Spectra
5

Each element has a characteristic spectrum.

Example: Na gives a characteristic line at 589 nm
Atomic spectra feature sharp bands

Applications of Atomic Spectroscopy

6

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)

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)

3.2 Flame AAS

Flame Atomic Absorption Spectroscopy

AAS Principle
9

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

compound

10

heat

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)

11

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)

12

3.2.1 Atomization Process (Sample

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 (?)
13

3.2.2 Flame Atomization

14

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
15

2. Molecules

3. Ions

3.2.3 Properties of Flame

16

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
17

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
18

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

Nebulizer
19

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)
b)

c)
d)

20

Concentric tubes.
Cross flow.
Fritted disk.
Babington.

Methods of sample introduction in AAS

Method
Pneumatic nebulization
Ultrasonic nebulization
Electrothermal
vaporization
Hydride generation

21

Type of sample
Solution or slurry
Solution
Solid, liquid or solution

Solution of certain
elements
Direct insertion
Solid, powder
Laser ablation
Solid, metal
Spark or arc ablation
Conducting solid
Glow-discharge sputtering Conducting solid

Burners
22

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)

Turbulent Flow Burner

23

Nebulizer & burner are combined into a single unit.

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

24

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

25

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

26

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.
27

3.3 Instrumentation for Flame AAS

AAS Instrumentation
29

Single Beam AAS Instrument:

The modulated power source can be replaced by a chopper

Double Beam AAS Instrument:

30

31

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

3.3.1 Line Sources

32

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)

33

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?

34

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

35

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) + h
36

Electrodeless Discharge Lamp (EDL)

37

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 radiofrequency (RF) or microwave field and excite the metal or salt of
interest
EDL can provide radiant intensities usually one to two orders of
magnitude greater than HCL

3.3.2 Source Modulation

38

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)

39

40

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.

3.3.3 Interferences
41

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
42

Spectral interferences: any physical process that effects the

light intensity at the analytical wavelength
a) Scattering by combustion or particulate products
Arise from the combustion products or particulate matters
from the atomization scatters the radiation from the source
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

How to solve the problems?

43

Tune the monochromator to a different spectral line

for the element of interest so that there is no overlap
Use the secondary lines for the element of interest
(can be found in the literature)

Chemical interferences
44

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

45

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
- 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

Dissociation equilibrium:
- Formation of compounds between the metal and other
components in flame (O, Cl)
- eg:
MCl M + Cl
NaCl Na + Cl

46

Ionization interference
47

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

48

3.3.4 Sample preparation &

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
Hot plate
b) Dry ashing

a) Wet Digestion (microwave)

49

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)

50

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
51

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
52

The concentration of analyte can be determined by:

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

Calibration Curve
53

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 Beers law
is being followed

Standard calibration curve

54

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

55

Extensively used in AAS. This process is often called

spiking the sample
Standard elements are the same as the analyte
Used to overcome matrix effect (due to the presence
of a lot of impurities in the sample)
Also used when the concentration of analyte is low
Involves adding one or more increments of a standard
solution to sample aliquots of the same size
Each solution is then diluted to a fixed volume before
measurement

If Beers law is obeyed,

A = bVstdCstd + bVxCx
Vt
Vt
= kVstdCstd + kVxCx
A= (kCstd)Vstd + kCxVx
Plot a graph of A vs Vstd
A = (kCstd)Vstd + kCxVx
Y =
mX
+
C
where the slope m and intercept C are
m = kCstd
C = kCxVx
56

For single-point standard addition

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

57

A1 Cs Vs
(A2 A1 ) Vx

Example:
In the determination of Si, in jet-engine oils using AAS,
the standard addition method was used and the
following data was obtained
Solutions

Concentration of added
Si standard (ppb)

Absorbance

Blank

0.00

0.018

Addition 1

12.50

0.094

Addition 2

25.00

0.139

Addition 3

37.50

0.179

Plot the standard addition graph and determine the

amount of Si present in the oil sample.
58

Answer:

The concentration of Si in the oil sample: -11.6= 11.6 ppb

59

3.3.5 Detection Limits & Accuracy

60

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