EMISSION
SPECROSCOPY
Inductively Coupled
Argon Plasma (ICP)
Excitation
Electrothermal
Flames
Sample
Solution Aerosols Atomisation
or Solid
Emission
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Skoog, Holler and Nieman, Ch. 10, 5th Edition
It is possible at extremely high
temperature (~7000K -14000K) to
produce strong atomic emissions of
all elements
However, ionisation problem is
endemic at high temperature
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What is a Plasma?
Ionised gas (highly charged cations,
electrons, neutral atoms & molecules)
good conductor of electricity
affected by magnetic field
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Instrumentation
Axial view of the plasma torch
Emission
region Radial view of the plasma torch
Magnetic f
field Induction coils powered by
Radio-frequency generator
Concentric
Quartz
tubes Sample flow Ar gas introduced tangentially
at flow rate of 5-20L/min
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Heat source - the ICP
Burner
A 27- or 41-MHz induction coil is wrapped
around the upper opening of the quartz
apparatus.
This inductor generates a rapidly oscillating
magnetic field.
A spark from the Tesla coil ionizes the Ar gas
and free electrons are accelerated by the RF
field.
The resulting ions and their associated
electrons from the Tesla coil interact with
the fluctuating magnetic field.
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The electrons in the magnetic field are accelerated and at
high speeds, cations and electrons known as the eddy current
collide with more Ar atoms producing further ionization .
Ionisation produces highly charged species such as Ar+, Ar*,
Ar, e- etc.
Within a few ms, a steady state results with high electron
density.
Thus, a plasma is created at the top of the torch with
temperatures at a significant rise (to 6,000 – 10,000 K).
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Plasma Characteristics
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Analyte atoms resides 2 seconds before
they reach 15-30mm height of the
plasma (temperature is 5000 to 8000K)
Complete atomisation compare to flame
Fewer chemical interference is
experienced…..Explain why?
No ionisation interference
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Desirable Properties of ICP
1. High resolution (0.01nm or / > 100,000)
2. Rapid signal acquisition and recovery
3. Low stray light
4. Wide dynamic range (>106)
5. Accurate and precise wavelength identification and
selection
6. Precision intensity readings (<1% relative standard
deviation at 500 x the detection limit)
7. High stability with respect to environmental changes
8. Easy background corrections
9. Computerized operation (readout, storage data
manipulations etc.)
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Plasma Spectrometers
Most spectrometers encompass
the entire UV-Visible spectrum
(170m to 800nm)
Equipped with vacuum
spectrometer which can extend
analysis to 150 to 160nm
(especially for P, Si, C etc.)
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Instrumentation
programmed to determine resonance line of one
element at a time
grating monochromator to disperse the emission
lines and a photomultiplier detector
much slower and therefore consume more sample
Simultaneous multichannel
simultaneous measurements of emission lines of up
to 60 elements at single excitation
expensive (US$80,000)
good reproducibility
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Advantages
Atomisation occurs in chemically inert environment
which results in lower inter-element intereference,
which is also a direct consequence of their higher
temperatures.
High and uniform temperature therefore greater
precision
They permit the determination of low concentrations
of elements that tend to form refractory compounds
(i.e., compounds such as the oxides of B,
Low noise & background
Multielement analysis
long linear dynamic range
ppb LODS
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Disadvantages
Complex spectra (sometimes)
need high resolution monochromator
high initial costs
high operating costs
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Sample Preparations
No difference to AAS
liquid samples can be
aspirated directly
through the nebulizer
solids may be dissolved
in suitable acids or
organic solvents
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DIRECT ANALYSIS OF SOLIDS
Electrothermal
vaporisation,
laser and spark
ablation, glow
discharge
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Contrast to Flame Emission
The temperature cross section of the plasma
is relatively uniform and a s a consequence
self absorption and self reversal effects are
not encountered. Thus, linear calibration
curves over several orders of magnitude of
concentration are usually observed.
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Calibration Curves
Plot of current versus analyte
concentration
Log-Log plot is necessary due
to wide concentration range
at which it is linear
Departure from linearity may
be encountered at high
concentration
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Non Linearity is due to:
self absorption
erroneous background correction
non linear responses of the detector
systems
Internal Standard is often used
plot of intensity ratio vs concentrations
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Interferences
Almost free of chemical and matrix interference
effects - Explain
Background correction is necessary at low
concentration of analyte - What is the problem?
Spectral overlap is very real - How can this problem
be overcome? e.g Lines for Fe and Co+, for example,
occur at 369.0730 and 369.0723 nm, respectively
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