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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)
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
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
E
Eo(Ground state)
Absorption
Emission
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
Lamp
detector
monochromator
Burner
slit
meter
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
with
specific
gas
atomizat
ion
[MX]gas
vaporizat
ion
[MX]soli
desolvati
on
[M+,X-] mis
nebuliza
tion
aq
[M+,X-] soluti
aq
on
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.
23
Proses atomisasi
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
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
FLAMES
Rich in
free
atoms
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
Electrothermal Atomisation
Graphite Furnace
43
Tempat Sampel
46
Steps in GF atomization
Atomization
Ashing
Drying
Disadvantages
48
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.
ANALISIS KUANTITATIF
Hukum Lambert-Beer
Jika Io dilewatkan larutan setebal b maka
intensitas berkurang menjadi It yang sebanding
dengan b Io/It = k.b
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 :
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
Contoh
Lar.stand Ag
2
4
6
8
10
A
0,12
0,21
0,33
0,42
0,51
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
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
Examples
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
NaBH
As (V)
(sol)
[H+]
AsH3
hea
t
in
flame
As0(gas) + H2
(ng/mL)
Sensitivity and detection limit
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
Analyte atoms in solution are aspirated into the excitation region where they
are desolvated, vaporized, and atomised by a plasma
ICP AES
Plasma
Polychromator
Detector
Excitation
Excitation
Relaxation
Ground State
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
400nm
800nm
Spectral Region
Vacuum UV
160
Ultra-Violet
190
Visible
360
Wavelength = nm
Near IR
760
900
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.
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
Instrument Components
1. Sample
Introduction
ii.the Nebulizer
which converts the solution to
an aerosol that is sent to
Instrument Components
2. Energy
= plasma
Source
Instrument Components
2. Energy Source
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
Axial view
Instrument Components
3. Spectrometer
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)
Instrument Components
4. Detector
Full,
continuous
wavelength
coverage;
never miss an
analyte
Instrument Components
5. Electronics
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)
Absorption
Emission
- Atomic absorption
depends upon the
number of ground state
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.