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ATOMIC ABSORPTION

SPECTROSCOPY (AAS)

SPEKTRUM GELOMBANG
ELEKTROMAGNETIK

Transisi
spin inti
atom

Transisi spin
elektron tak
berpasangan

Molekul
vibrasi

Eksitasi
elektron
valensi

Eksitasi
elektron
inti

Reaksi
Fisi
(Nuklir)

Elements detectable by atomic absorption are highlighted in pink in this


periodic table

AAS
- Atomic-absorption spectroscopy quantifies the absorption
of ground state atoms in the gaseous state .
- The atoms absorb ultraviolet or visible light and make
transitions to higher electronic energy levels. The analyte
concentration is determined from the amount of
absorption.
- Concentration measurements are usually determined
from a working curve after calibrating the instrument with
standards of known concentration.
- Atomic absorption is a very common technique for
detecting metals and metalloids in environmental
samples.

TEORI

TEORI
AAS : salah satu metode yang paling umum untuk
analisis logam dan beberapa semilogam (metalloids)
Logam : Fe, Pb, Cr, dll.
Metalloids : Sb, As, Se, dan Te

Metode analisis kuantitatif yang didasarkan pada


penyerapan/absorpsi radiasi oleh atom
Akibat absorpsi :
Transisi elektron dari ground state ke excited state

Transisi
Energi yang diserap sesuai dengan perbedaan energi
transisi dari GS ke ES

E = E1 E0 = hc /

+ e

A
hv

E
+

- excited state

E0 ground state

hv

h Plancks constant
c velocity of light
- wavelength

Atomic Absorption and Emission Lines


Resonance Lines
E3(Excited state)
E2(Excited state)
E1(Excited state)

E
Eo(Ground state)
Absorption

Emission

Most Intense Line


3 Absorption Lines
6 Emission lines

E = E1 - E0 = h = hc/

UV-Vis vs AAS
Both methods are used to determine the
concentration of an element in solution.
Both methods use a standard curve.
Difference between UV and IR spectroscopy is that
sample must be atomised.
Sample may be atomised by:
(1) A flame
(2) Electrically heated furnace
(3) A Plasma
9

Sensitivity
Atomic spectroscopy is very sensitive for most
elements.
Concentrations at the ppm level may be routinely
determined using flame atomisation.
Using electrothermal atomisation, concentrations
at the ppb may be determined.
1 ppm = 10-6g/g or 1g/g

10

INSTRUMENTASI

Atomic Absorption
Spectrophotometer

The Atomic Absorption


Spectrometer
Atomic absorption spectrometers have 4 principal
components
1 - A light source ( usually a hollow cathode lamp )
2 An atom cell ( atomizer )
3 - A monochromator
4 - A detector , and read out device .

Skema Kerja AAS

Lamp
detector

monochromator
Burner

slit

meter

Skema Cara Kerja AAS


Sample (Atoms in flame)
Chopper

Source

h
Io

HCL

Flame

h
h Detector
Monochromator
It

Burner

Fuel

Oxidant
(Air)

Amplifier
V

Cloud
Chamber

Output
e.g. PC/Printer

Nebuliser
Waste
Sample uptake

HCL = Hollow-cathode Lamp

Figure 1. Schematic Diagram of an Atomic Absorption Spectrophotometer

The Flame Atomization


Ia
Process
It
Light
Io
[M ]
0

with
specific

gas

atomizat
ion

[MX]gas

vaporizat
ion

[MX]soli

desolvati
on

[M+,X-] mis

nebuliza
tion

aq

[M+,X-] soluti
aq

on

How can we obtain the data?


The intensity of the light
coming through the cathode
lamp is measured

The higher the concentration


of the metal that is being
observe in the sample the
greater the absorbance.

The intensity of the light is


then again measured and
compared to the first result.
= absorbance

The light can then be absorbed


by the atoms from the sample
that has been vaporized in the
flame.
This wavelength can then
promote the electrons to a higher
energy level = excited state

Fungsi masing-masing
komponen alat
1. Light source
It is designed to emit the atomic spectrum of a
particular element.
Specific lamps are selected according to the
element to be determined.
The hollow cathode lamp (HCL) or electrode
Discharge Lamps (EDL) are widely used.

Hollow Cathode Lamp


Quartz window

The light source is usually a


hollow cathode lamp of the
element that is being measured.
Pyrex body
It contains a tungsten anode and
a hollow cylindrical cathode
made of the element to be
determined. These are sealed in
a glass tube filled with an inert
Anode
gas (neon or argon ). Each
element has its own unique lamp
Cathode
which must be used for that
analysis .

Hollow Cathode Lamp


The cathode of the hollow cathode lamp (HCL) contains the
element being analysed.
Therefore the atomic radiation emitted by the HCL has the
same frequency as that absorbed by the analyte atoms in the
flame or furnace.
The linewidth from the HCL is relatively narrow (compared to
linewidths of atoms in the flame or furnace) because of low
pressure in lamp and lower temperature in lamp.
Thus the linewidth from the HCL is nearly monochromatic (vs
sample).

Scheme of a hollow cathode lamp

Apply sufficiently high voltage between the cathode and


the anode:
(1) Ionization of the filler gas:
Ne + e- = Ne+ + 2e(2) Sputtering of the cathode element (M):
M(s) + Ne+ = M(g) + Ne
(3) Excitation of the cathode element (M)
M(g) + Ne+ = M*(g) + Ne
(4) Emission of radiation
M*(g) (M(g) + h

23

Electrodeless Discharge Lamps


(EDL)
Constructed from a sealed quartz tube containing a
few torr of an inert gas such as argon and a small
quantity of the metal of interest (or its salt).
The lamp does not contain an electrode but instead is
energized by an intense field of radio-frequency or
microwave radiation.
Radiant intensities usually one or two orders of
magnitude greater than the normal HCLs.
The main drawbacks: their performance does not
appear to be as reliable as that of the HCL lamps
(signal instability with time) and they are only
commercially available for some elements.

Electrodeless Discharge Lamps


(EDL)

Ar (g) ---------> Ar* (g) + M (s) -------> M* (g) + Ar (g)


h
Mo

Proses atomisasi

Sample cell- Tungku pembakar


2. Sample cell
Where an atomic sample vapor is generated in the
light beam from the source.

Nebulizer :
Suck up liquid sample at a controlled rate
Create a fine aerosol for introduction into the flame
Mix the aerosol and fuel and oxidant thoroughly for
introduction into the flame

Nebulasi

Nebulizer - burner

Nebuliser - burner
To convert the test solution to gaseous atoms
Nebuliser --- to produce a mist or aerosol of the
test solution
Vaporising chamber --Fine mist is mixed with the fuel gas and the carrier gas
Larger droplets of liquid fall out from the gas stream
and discharged to waste

Burner head --- The flame path is about 10 12 cm

Fuel Flow rate


Oxdnt. Flow rate
Burner height

Proses atomisasi : 2 cara


Dengan nyala : Flame api, Plasma
Tanpa nyala ( Flameless) :
Hidrida
Pembentukan uap dingin (Cold Vaporgeneration)
Tungku grafit

Atomisasi

Flame
Create atoms (the
elemental form) of the
element of interest
Fe0, Cu0, Zn0, etc.

Temperature nyala
Tergantung pada kombinasi oksidan dan
bahan bakar
Bahan bakar : asetilen, gas alam, hidrogen
Oksidan : udara, N2O

Destroy any analyte ions and breakdown


complexes

Types of Flames Used in Atomic


Spectroscopy

FLAMES
Rich in
free
atoms

Various flame atomization techniques

Electrothermal or Graphite Furnace


Atomizer

graphite
tube

Atomization
occurs in an
electrically
heated graphite
tube
The graphite
tube is flushed
with an inert
gas (Ar) to
prevent the
formation of
(non-absorbing)
metal oxides
39

Grafit furnace atau electro thermal atomizer (ETA) :


Penghantar panas listrik : batang grafit C atau Ta, yang
dialiri gas inert untuk mengusir udara yang
menyebabkan oksidasi/ pembakaran
Sampel dalam l diuapkan di atas permukaan furnace
Pemanasan furnace dimulai 100oC dengan cara
mengalirkan arus listrik : penguapan pelarut atau
pengeringan sampel padat
Suhu dinaikkan sampai 700-1000oC sehingga sampel
terbentuk abu. kemudian suhu dinaikkan menjadi 20003000 dengan menaikkan arus sampai 100mA terjadi
atomisasi. Sisa pembakaran dihembus dengan gas Ar

Electrothermal Atomisation
Graphite Furnace

Sample holder consists of a graphite tube.


Tube is heated electrically
Beam of light passes through the tube.
Offers greater sensitivity than flames.
Uses smaller volume of sample
typically 5 - 50 l (0.005 - 0.05 ml).
All of sample is atomised in the graphite tube.

43

Schematic Diagram of a Graphite Furnace

Tempat Sampel

Stages in a Graphite Furnace


Typical conditions for Fe:
Drying stage: 125o for 20 sec
Ashing stage 1200o for 60 sec
Atomisation 2700o for 10 sec
Requires high level of operator skill.
Method development difficult.

46

Steps in GF atomization

Atomization
Ashing
Drying

Advantages and Disadvantages of


Flame AAS
Advantages

equipment relatively cheap


easy to use (training easy compared to furnace)
good precision
high sample throughput
relatively facile method development
cheap to run

Disadvantages

lack of sensitivity (compared to furnace)


problems with refractory elements
require large sample size
sample must be in solution

48

Advantages and Disadvantages of


Electrothermal Atomisation
Advantages
very sensitive for many elements
small sample size
Disadvantages
poor precision
long cycle times means a low sample throughput
expensive to purchase and run (argon, tubes)
requires background correction
method development lengthy and complicated
requires a high degree of operator skill (compared to
flame AAS)

3- Monochromators
This is a very important part in an AA spectrometer. It is used
to separate out all of the thousands of lines. Without a good
monochromator, detection limits are severely compromised.
A monochromator is used to select the specific wavelength
of light which is absorbed by the sample, and to exclude
other wavelengths. The selection of the specific light allows
the determination of the selected element in the presence of
others.

4 - Detector and Read out Device


The light selected by the monochromator is directed onto
a detector that is typically a photomultiplier tube , whose
function is to convert the light signal into an electrical
signal proportional to the light intensity.
The processing of electrical signal is fulfilled by a signal
amplifier . The signal could be displayed for readout , or
further fed into a data station for printout by the
requested format.

ANALISIS KUANTITATIF

Dasar Analisis Kuantitatif


Hukum Beer :
Jika Io dilewatkan larutan dengan konsentrasi
C maka intensitas berkurang menjadi It yang
sebanding dengan C
Io/It = k. C

Hukum Lambert-Beer
Jika Io dilewatkan larutan setebal b maka
intensitas berkurang menjadi It yang sebanding
dengan b Io/It = k.b

Hukum Lambert -Beer


Io/It = e k b C
ln Io/It = k.b.C
log Io/It = k/2,303 .b C = abC
It/Io x 100 % = T %
log Io/It = log I/T = A
jadi

A = abC = b. C

Validitas A = a b C
Untuk absorpsi
Untuk konsentrasi yang relatif rendah
Konsentrasi besar : terjadi interaksi antara analit
sehingga mengurangi absorpsi radiasi
penyimpangan
Kesalahan minimal :

A = 0,44 atau 0.2-0.8

C sangat kecil A terlalu kecil It dan Io hampir


sama kesalahan besar

Aplikasi hukum Lambert Beer


Membandingkan A standar dengan A sampel :
Standar tunggal
Deret standar Kurva standar
Adisi standar

Standar tunggal
1. Larutan standar Pt 5 ppm T = 65%. Sampel limbah 10
ml diencerkan menjadi 50 ml T = 45%
Tentukan kadar Pt dalam limbah cair = ? mg/L
2. Tanah galian yang mengandung logam emas, 2 gram
dilarutkan menjadi 100 ml. Absorbansi = 0,54
Larutan standar 10 ppm A =0,24
Tentukan berapa % Au dalam sampel ?

Kurva Standar

Intensitas

Konsentrasi lar. standar

Contoh
Lar.stand Ag
2
4
6
8
10

A
0,12
0,21
0,33
0,42
0,51

Jika 1 g sampel uang logam dilarutkan menjadi100ml.


Diambil 5ml diencerkan menjadi 50ml, A = 0,35.
Tentukan kadar (%) Ag dalam sampel

Adisi standar
Untuk mengatasi kesalahan matriks menyamakan
keadaan larutan sampel dengan lar. Standar
Cara : mencampurkan sampel dengan standar
Volume
sampel (mL)

Volume larutan
standar
Cu 10 ppm (mL)

Absorbansi

10

0,201

10

10

0,291

10

20

0,378

10

30

0,467

10

40

0,554

Persiapan sampel
Harus berupa larutan jernih
Padat

Cair

Gas

Destruksi

Penyaringan/
pengasaman
Penyerapan
pelarutan

Larutan jernih

AAS

Gangguan dalam Analisis

Gangguan dalam AAS


Spektrum :
Spektra analit overlap dengan spektra pengganggu,
karena spektrum absorpsi pengganggu berdekatan
dengan spektrum absorpsi analit (<0,1 A)
untuk V = 3082,11 A
Al = 3082,15 A dan 3092,7 A (yang dipakai)
Hasil pembakaran memberikan spektrum yang lebar
radiasi terpencar intensitas berkurang dikorekasi
dengan blanko

Kimia
Adanya reaksi kimia :
pembentukan senyawa dengan volatilitas tinggi
atau rendah
Ionisasi dalam nyala
Asosiasi atau disosiasi

Matriks
Viskositas larutan standar tidak sama dengan
analit

Cara mengatasi Gangguan Kimia


Reaksi kimia :
Pembentukan senyawa yang tidak volatil
Menggunakan suhu nyala yang lebih tinggi
Dengan penambahan Masking agent /protective
chelation
Dengan penambahan Releasing agent

Examples

Determination of calcium in the presence of sulfate or phosphate (e.g.


in natural waters)
3Ca2+ + 2PO43- = Ca3(PO4)2
(stable compound)

Release agent
Add 1000 ppm of LaCl3
2LaCl3 + Ca3(PO4)2 = 3CaCl2 + 2La(PO4)
CaCl2 readily dissociates

Protective chelation
Ca3(PO4)2+3EDTA = 3Ca(EDTA) + 2PO43Ca(EDTA) dissociates readily.

66

Ionisation Interference
M(g) M+(g) + eA problem in the analysis of alkali metal ions at low flame
temperatures and other elements at higher temperatures.
Because alkali metals have the lowest ionisation potentials,
they are most extensively ionised in flames.
At 2450 K and a pressure of 0.1 Pa, sodium is 5% ionised.
Potassium is 33% ionised under the same conditions.
Ionised atoms have energy levels which are different to the
parent atoms
therefore the analytical signal is reduced.
67

Solution
Add an ionisation suppressor
[M ][e - ]
K
[M]
[M ][e - ]
[M]
K
Add an easily ionised element such as Cs.
Add 1000 ppm of CsCl when analysing Na or K.
Cs is more readily ionised than either Na or K.
This produces a high concentration of electrons in the flame.

Matrix effects
The amount of sample reaching the flame is dependent on
the physical properties of the solution:
viscosity
surface tension
density
solvent vapour pressure.
To avoid differences in the amount of sample and standard
reaching the flame, it is necessary that the physical
properties of both be matched as closely as possible.
Example:
Analysis of blood ----> Addition Standard

Non-Atomic Absorption
Non-atomic absorption is caused by molecular absorption
or light scattering by solid particles in the flame.
The absorption measurement obtained with a hollow cathode
lamp is the sum of the atomic absorption and the non-atomic
absorption.
The interference is corrected for by making a simultaneous
measurement of the non-atomic absorption using a
continuum source (usually deuterium)
This problem is overcome by increasing the flame
temperature
this is called background correction
70

Background Correction

Metode dalam AAS

Pembentukan uap dingin :


Khusus untuk Hg
Reduksi dengan SnCl2 :
Hg2+ + Sn2+ Hg0 atom (uap) +Sn4+
Hg0 + hv absorpsi

Sensitivitas tinggi (< 1ppb-ppt)


Uap Hg berbahaya

Cold vapour technique


Hg2+ + Sn2+ = Hg + Sn (IV)

Hydride generation methods


For arsenic (As), antimony (Te) and selenium (Se)

NaBH
As (V)

(sol)

[H+]

AsH3

hea
t
in
flame

As0(gas) + H2

Pembentukan senyawa hidrida


Untuk unsur yang suhu atomisasinya tinggi maupun
yang sangat rendah : As, Bi, Sb, Se, Te dan Ge.
Unsur diubah menjadi senyawa hidrida yang volatil :
Reduksi unsur dengan NaBH4 dalam asam atau
basa uap AsH3, BiH3, dst
Uap logam hidrida dibawa oleh gas inert menuju sel
atomisasi (nyala api atau filamen listrik) atomisasi
AsH3 Aso
Aso + hv absorpsi

(ng/mL)
Sensitivity and detection limit

Advantages and disadvantages

High sensitivity
[10-10g (flame), 10-14g (non-flame)]
Good accuracy
(Relative error 0.1 ~ 0.5 % )
High selectivity
Widely used
A resonance line source is required for each
element to be determined

Contoh-contoh

Atomic Emission Spectroscopy

Inductively Coupled Plasma


Atomic Emission Spectroscopy

Atomic Emission Theory

Atomic emission spectroscopy (AES or OES) uses quantitative


measurement of the optical emission from excited atoms to determine
analyte concentration

Analyte atoms in solution are aspirated into the excitation region where they
are desolvated, vaporized, and atomised by a plasma

ICP AES

Electrons of an atom absorb energy and jump to


higher energy levels

When they return to normal states, they emit


characteristic photons of energy

By isolating these photon wavelengths, we can


determine the types and concentrations of the
elements present.

Atomic Emission Theory


Inductively Coupled Plasma Atomic Emission Spectrometer

Plasma

Polychromator

Detector

Excitation

Excitation
Relaxation

Ground State

Excited State

Electrons can be in their ground state (unexcited) or


enter one of the upper level orbitals when energy is
applied to them. This is the excited state

Atomic Emission
A photon of light is emitted when an electron falls from
its excited state to its ground state

+ hv

Excited State

Ground State

Photon

Element Wavelengths
Each element has a unique set of wavelengths that it
can emit
<-- uv -->

180nm

<-- visible -->

400nm

800nm

Atomic Emission explained


Atomic Emission the wavelength regions

Spectral Region
Vacuum UV

160

Ultra-Violet

190

Visible

360
Wavelength = nm

Near IR

760

900

Lower wavelengths are shorter and have more energy,


higher wavelengths e.g. in the Visible region, are longer
and have less energy

Effect of Temperature on
Emission
Wavelength increasing ->
200300400600800

5000 k
As Pb

Mn Mg Cu

Ca

Ba

Na

Li

Mg Cu

Ca

Ba

Na

Li

Na

Li

3000 k

2000 k
Ca

Emission sources
Flames
Direct Current Plasmas (DCP)
Inductively Coupled Plasmas (ICP)

PLASMA
A plasma is
an electrical conducting gaseous mixture containing
a significant concentration of cations and electrons.
(The concentrations of the two are such that the net
charge approaches zero).
In the argon plasma frequently employed for
emission analyses, argon ions and electrons are
the principle conducting species, although cations
from the sample will also be present in lesser
amounts.

Plasma has 2 characteristics:

i- can conduct electricity


II- affected by magnetic fields
Plasma is highly energetic ionized gases usually
inert, recently reactive oxygen is used.
Other plasmas include direct current plasma
(DCP) and microwave induced plasma (MIP)

Plasmas

ICP-AES
Inductively coupled plasmas are at least 2X as hot
as flames or furnaces.
The Ar plasma is the result of the flow of Ar ions in
a very strong, localized radio field.
6000-10000 K are common plasma temperatures.
Hot enough to excite most elements so they emit
light.
Hot enough to prevent the formation of most
interferences, break down oxides (REEs) and
eliminate most molecular spectral interferences.

Plasma Advantages
High Temperature allows for full
dissociation of sample components
Argon is Inert non reactive with
sample
Linearity analysis of samples
from ppb to ppm range in the same
method
Matrix tolerance robust and
flexible design with Duo and Radial
options

Instrument Components
1.

Sample
Introduction

2.

Energy
Source

3.

6.

Computer and
Software

5.

Spectrometer

Electronics
4.

Detector

Instrument Components
1. Sample
Introduction

The sample solution


cannot be put into the
energy source
directly. The solution
must first be
converted to an
aerosol.
The function of the
sample introduction
system is to produce
a steady aerosol of
very fine droplets.

Instrument Components
1. Sample
Introduction

There are three basic


parts to the sample
introduction system.
i. the Peristaltic pump
draws up sample
solution and delivers it to

ii.the Nebulizer
which converts the solution to
an aerosol that is sent to

iii. the Spray chamber


which filters out the large,
uneven droplets from the
aerosol.

Instrument Components
2. Energy
= plasma
Source

The sample aerosol


is directed into the
center of the plasma.
The energy of the
plasma is transferred
to the aerosol.
The main function of
the energy source is
to get atoms
sufficiently energized
such that they emit
light.

Instrument Components
2. Energy Source

There are three basic parts to the


energy source.
i. the Radio frequency generator
which generates an oscillating electomagnetic field at a frequency of 27.12
million cycles per second. This radiation is
directed to

ii.the Load coil


which delivers the radiation to

iii. the Torch


which has argon flowing through it which
will form a plasma in the RF field.

Radial or Axial Configuration


Radial design Robust, fewer interferences
Petrochemical
Metallurgy

Axial design best sensitivity,


lowest detection limits
Environmental
Chemical

Duo viewing
Axial view plasma looks down the central channel of the plasma,
this provides the best sensitivity and detection limits
DUO this is an axially configured plasma that also allows for
radial view through a hole in the side of the axial torch

Dual View Optics


Radial view

Axial view

Instrument Components
3. Spectrometer

Once the atoms in a


sample have been
energized by the
plasma, they will emit
light at specific
wavelengths. No two
elements will emit
light at the same
wavelengths.
The function of the
spectrometer is to
diffract the white light
from the plasma into
wavelengths.

Simultaneous Optics Echelle


Spectrometer
Detector

Prism

Grating

ICP-Source

Instrument Components
There are several
types of
spectrometers
used for ICP.
Regardless of type,
all of them use a
diffraction grating.

3. Spectrometer
CID Detector

Focusing
Mirror
Echelle
grating
Prism
Shutter
Collimating
Mirror

Slit
(dual)

For the iCAP, an


echelle
spectrometer is
used. The
components in this
spectrometer are
shown at left.

Instrument Components
4. Detector

Now that there are


individual wavelengths,
their intensities can be
measured using a
detector. The intensity
of a given wavelength
is proportional to the
concentration of the
element.
The function of the
detector is to measure
the intensity of the
wavelengths.

What you get

Full,
continuous
wavelength
coverage;
never miss an
analyte

Power and flexibility


Rapid qualitative
analysis
Ability to analyze
for elements in the
future without
rerunning samples
Fingerprinting
Matrix or spectral
subtraction

Instrument Components
5. Electronics

The output from the


detector is processed by
a set of electronics. The
electronics control the
detector as well as
collect the readings from
the pixels
The function of the
electronics is to measure
and process the output
of the detector.

ICP Basics
ICP Performance
Typical analysis time for ICP is ~2-3 minutes.
This includes flush time, multiple repeats, printing,
etc. (Analysis time is independent of the number of
elements being determined)

Typical precision, amongst repeats within an


analysis, is ~0.5%
Typical detection limits are ~ 1-10 parts per billion

Atomic Absorption VS Emission Spectroscopy

Absorption

Emission

- Measure trace metal


concentrations in
complex matrices .

- Measure trace metal


concentrations in
complex matrices .

- Atomic absorption
depends upon the
number of ground state
atoms .

- Atomic emission depends


upon the number of
excited atoms .

- It measures the
radiation absorbed by
the ground state atoms.
- Presence of a light
source ( HCL ) .

- It measures the
radiation emitted by
the excited atoms .
- Absence of the light
source .

- The temperature in
the atomizer is adjusted
to atomize the analyte
atoms in the ground
state only.

- The temperature in the


atomizer is big enough
to atomize the analyte
atoms and excite them
to a higher energy level.

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