ANALISIS FISIKOKIMIA

Prof. DR. Harrizul Rivai, M.S.

Guru Besar Kimia Farmasi
Fakultas Farmasi
Universitas Andalas
REFERENCE

Copyright © 1998
INSTRUMENTAL
ANALYSIS
Optical ATOMIC SPECTROSCOPY:

1- Atomic Absorption Spectroscopy (AAS)

2- Atomic Emission Spectroscopy (AES)

3- Atomic Fluorescence Spectroscopy (AFS)

Atomic Absorption Spectroscopy:

A= ε b C

Bear-Lambert Law
Types of Atomic Absorption Spectroscopy:

1- Flame Atomic Absorption

Spectreoscopy (FAAS)

2- Electrothermal ( Flame-less ) Atomic

Absorption Spectroscopy (EAAS)
Flame Atomic absorption spectrometer
• In this method, light from a source is directed
through the sample to a detector.

Light Path
Sources for AAS:
1- Hollow Cathode Lamps (HCL)
Multielement lamps are available.

2- Electrodeless Discharge Lamps

(EDL)
Hollow cathode lamp:
• The source of light is a lamp whose cathode is composed of the
element being measured.
• Each element requires a different lamp.
The lamp is housed inside the lamp
compartment of the instrument.
atomic line source (HCL)
Sample Introduction Methods:
1- Introduction of solution samples:
a) Pneumatic Nebulizers
b) Electrothermal (furnace) evaporator
c) Hydride generation (As, Sb, Sn, Se, Bi, Pb )
d) Cold vapor atomization ( Hg )
a )Pneumatic Nebulizers

1- Concentric tube
2- Cross flow
3- Fritted disk
4- Babington
Pneumatic Nebulizers :
Concentric Nebulizer
Flame pneumatic nebulizer
Adjustment of position of inner capillary

Typical uptake rate: ~5 mL/min

Typical delivery efficiency: ~5%
http://www.chemistry.nmsu.edu/Instrumentation
Electrothermal evaporator :

There is no nebulziation, etc. The sample is introduced as a drop

(usually 10-50 uL)

• The furnace goes through several steps:

a- Drying (usually just above 110 deg. C.)
b- Ashing (up to 1000 deg. C)
c- Atomization (Up to 2000-3000 C)
d- Cleanout (quick ramp up to 3500 C or so). Waste is blown out with a blast of
Ar.
Electrothermal atomic absorption (Graphite furnace)

Introduced sample
(solid, liquid, gas, slurry)

Pulse heat the ETV

Temp

Absorbance time
signal
A hydride generation and atomization system
2- Introduction of solid samples:
a) Electrothermal evaporators
b) Arc or spark ablation
c) Laser ablation
d) Glow discharge technique
Glow discharge atomization:
Free atom formation
(Atomization)
We need to be able to convert our sample to the atoms.
• Desolvation
• Volatilization
• Dissociation and ionization
SAMPLE INTRODUCTION AND ATOMIZATION
Sample atomization techniques:

1- Flame atomization
2- Electrothermal atomization
3- Glow discharge atomization
4- Hydride atomization
5- Cold – vapor atomization
Nebulizer / Burner system
Advantages of flame:
• Convenient
• Reproducible
• Easy to use
• inexpensive
Flame Characteristics

“Regions in a flame”
Flame characteristics:
Flame absorbance profile for three
elements
Optical elements of monochromators :

1- An entrance slit
2- A collimating lens or mirror
3- A prism or grating
4- A focusing element
5- An exit slit
Grating and Prism
A Prism function
Interference grating
The effect of the slit width
Photon transducers:
1- Vaccum phototubes

2- Photomultipliers tubes
Vaccum phototubes:
Photomultipliers tubes:
Single Beam Instrument
Double Beam Instrument
Chopper
Mechanical modulator or Choppers
Interferences in Atomic Absorption
spectroscopy:
1- Spectral interferences
a- overlapping of two lines(< 0.01 nm- 308.211 V ,
308.215 Al )
b- presence of combustion products (broad band
absorption- scatter the radiation by particulate
products)
C- absorption or scattering (CaOH in Ba absorption, Ti,
Zr and W refractory oxides or incomplete
combustion of organic solvents) by the matrix
components
2- Chemical interferences
a- formation of compounds of low volatile ( Ca-PO43-
or SO4 -2 )
b- Dissociation equilibria
c- Ionization equilibria