IN THE NAME OF GOD

INSTRUMENTAL
ANALYSIS
Classification of Analytical
Methods:

1- Classical or Chemical
Methods

2- Instrumental Methods
 Classical Methods:
• Separating the Components of sample by
precipitation, Extraction or Distillation
• Qualitative Analysis by treating the
separated components with reagents that
yield products that can be recognized by
their colors, their solubilities in a series of
solvents, their melting or boiling points, their
oders, their optical activities or their
refractive indexes.
• Quantitative Analysis by Gravimetric or
Titrimetric measurements.
 Instrumental Methods:
Early in the 20th century, measurements
of Physical properties of analyts such
as conductivity, electrode potential,
light absorption or emission, mass to
charge ratio, fluorescence,… began to
be used for quantitative and qualitative
analysis of a variety of inorganic,
organic and biochemical analytes.
 Types of Instrumental Methods:
• Emission of radiation • Electrical potential
• Absorption of radiation • Electrical current
• Scattering of radiation • Electrical resistance
• Refraction of radiation • Mass
• Diffraction of the • Mass to charge ratio
radiation • Rate of reaction
• Rotation of the • Thermal charact.
radiation • radioactivity
 Atomic Spectrometric Methods
for Qualitative and Quantitative
determinations:

1- optical Spectrometry

2- Mass Spectrometry

3- X – Ray Spectrometry
 Atomic Absorption Spectroscopy

• Qualitative and Quantitative

determination of more than 70
elements.
• Sensitivities of Atomic methods lie in
the ppm, ppb and ppt range.
• Fast, High selective and moderate
instrument costs.
Atomic Spectrum of Hg
Molecular Spectrum:
Energy Level Diagram:
 ATOMIC LINE WIDTHS

Atomic line widths are caused by:

1. Doppler broadening
2. Pressure effects due to collisions
Doppler broadening :

No shift is seen for atoms perpendicular to the

path of the photon detector. Atoms moving
toward the photon detector are detected at a
higher frequencies and those moving away from
the detector at a lower frequencies.
 Pressure broadening:
Pressure or collisional broadening
results from the collisions of the emitting
or absorbing species with other atoms or
ions in the heated medium. These
collisions cause small changes in the
ground and Excited state energy levels
and lead to a range of absorbed And
emitted wavelengths.
 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.
 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
Atomic Absorption Analytical
methodes :

1- Calibration curves

2- Standard addition method

Calibration curve
A calibration curve and the equation for
the line can be used to determine an
unknown concentration based on its
absorbance.
Standard additions often used with GFAAS
Atomic Fluorescence Spectroscopy
(AFS)

This method has three steps:

1- Formation of free atoms

2- Absorption of radiation by these atoms
3- emission of energy as radiation
AFS instrument
Multielement AFS:
 Sources for AFS:
1- Hollow cathode lamps ( with short
pulses of current)
2- Electrode – less discharge lamps
3- Laser sources
4- continuum sources
 Atomizers for AFS
1- Flame
2- Electrothermal atomizer
3- Glow discharge
4- Inductively coupled plasma
 Types of AFS instruments:
1- Dispersive instruments is made up :
- A modulated source
- An atomizer
- A monochromator or an interference filter
- Detector and readout system

2- Nondispersive instruments :
no monochromator or filter should be
necessary when an EDL or HCL are used as
source
 Atomic Emission spectroscopy:
Atomic Emission sources:
1- Atomization
2- Excitation

Types of atomic emission sources:

a) Flame sources
b) Arc and spark sources
c) Glow discharge sources
d) Laser sources
e) Plasma sources
 Flame Emission Spectroscopy

Flame Emission Spectroscopy is based upon those particles that

are electronically excited in the medium.

The Functions of Flame:

1. To convert the constituents of liquid sample into the vapor
state.
2. To decompose the constituents into atoms or simple
molecules:
3. To excite a fraction of the resulting atomic or molecular
species
M -> M*
 Arc and Spark Sources
• An electrical arc or spark between a pair of electrodes provides sufficient
energy to atomize and excite analyte samples.
• Used primarily for the analysis of solids such as metals, alloys, soil,
minerals, and rocks.
• For conducting samples, the electrodes are constructed from the sample.

• For non-conducting samples, the

sample is powdered, mixed with a
conducting powder (often
graphite) and placed on/in a
graphite electrode.
• Performance Characteristics
- Quantitative analysis is poor.
- Qualitative analysis is good but tedious.
- Advantages: Easily handles solids (especially metals and alloys)
- Disadvantages: Only semi-quantitative and working with solutions is
difficult.
 Electrode material
• The most common is graphite some
times metallic samples

• The advantage of graphite

– Inexpensive
– Available in high purity
– Resistance to attack by most reagents
Arc and Spark

Li2CO3 as
spectroscopic
buffer
 ICP
Inductively Coupled Plasma

– much higher temperatures than AA

– thus higher number of atoms in
excited state
– thus stronger signal
 Inductively Coupled Plasma “torch”

atomic emission

plasma

load coil

sample solution
Ar
 Characteristic of the ICP:
• High temperature
• Long residence time
• High electron number densities (few
ionization interferences)
• Free atoms formed in nearly chemically inert
environment
• Molecular species absent or present in very
low levels
• No electrodes
• No explosive gases
 Advantages of plasma:
1- more complete atomization
2- fewer chemical interferences
3- low ionization interference effects
4- atomization occurs in a chemically
inert environment
5- temperature cross section of plasma is
relatively uniform
6- wider linear range
 Disadvantages of ICP:
• Expensive

• Spectral overlap

• Is not simple to operate

– Considerable training is required to become
an efficient and knowledgeable user of ICP
Atomic Emission Spectrometer
 Multichannel spectrometers:
1- Polychromators ( Rowland circle )

2- A charge - coupled instrument

(charge - coupled detector : CCD )
 Plasma Application:

1- Useful for both quantitative

and qualitative determination in
liquids ( organic or aqueous
solvent)
2- All metal elements can be
determined.
 Advantages of Plasma, Arc and
Spark emission spectrometry
(vs. to FAAS and EAAS):
1- Lower interelement interference
2- Obtaining good emission spectra for most
elements under a single set of excitation
conditions
3- Determination of low concentrations of
elements that form refractory compounds.
4- Determination of nonmetals such as F,Cl,I
and S by plasma based AES.
5- Methods based upon plasma sources have
concentration ranges of several decades
 Advantages of FAAS and EAAS
vs. to Plasma, Arc and Spark
emission spectrometry:
1- Simple
2- Less expensive equipment
requirements
3- Lower operating costs
4- Procedures that require less operator
skills
 Summary & Comparison of
Common Atomic Spectrocopies

FAAS ETA-AAS ICP-AES

Qualitative
Fair Fair Good
Abilities:
Quantitative
Very Good Excellent Excellent
Abilities:
$50 – 100
Expense: $15,000+ $30,000+
K+
Simultaneous
Multielement
Analysis: Difficult Very Difficult Easy

Detection Limits: ppb - ppm < ppb < ppb - ppt

 Flame Atomic Absorption
Spectrometer

Po P Signal Processor
Source Wavelength Selector Detector Readout

Chopper

Sample
 Fluorescence Spectrometer

Po P Signal Processor
Wavelength Selector Detector Readout

90o

Source

Sample
 Emission Flame Photometer

P Signal Processor
Source Wavelength Selector Detector Readout

Sample