35 Atomic Emission

Course Code : PDA302T
Pharmaceutical Analysis
Session
Flame Photometry
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aculty of Engineering
Faculty of Pharmacy& Technology M. S. Ramaiah University of Applied Sciences
Atomic Emission Spectroscopy
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Session Objectives
By the end of this session, students will be able to:
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Detection Limits
Usually, atomic absorption based on electrotherma

l atomization has better sensitivities and detectio
n limits than methods based on flames. In genera
l, flame methods have detection limits in the rang
e from 1-20 ppm while electrothermal methods h
ave detection limits in the range from 1-20 ppb.
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This range can significantly change for specific eleme
nts where not all elements have the same detection
limits. For example, detection limits fro mercury an
d magnesium using electrothermal atomization are
100 and 0.02 ppb while the detection limits for the s
ame elements using flame methods are 500 and 0.1
ppm, respectively.
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Accuracy
Flame methods are superior to electrothermal methods in

terms of accuracy. The relative error in flame method ca
n be less than 1% while that for electrothermal method o
ccurs in the range from 5-10%. Also, electrothermal met
hods are more susceptible to molecular interferences fro
m the matrix components. Therefore, unless a good back
ground correction method is used, large errors can be en
countered in electrothermal methods depending on the
nature of sample analyzed.
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Flame Photometry Review
The technique referred to as flame photometry is a

flame emission technique. The basics of the techn
ique are extremely simple where a sample is neb
ulized into a flame. Atomization occurs due to hig
h flame temperatures and also excitation of easily
excitable atoms can occur.
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Emission of excited atoms is proportional to concentr
ation of analyte. Flame emission is good for such at
oms that do not require high temperatures for atom
ization and excitation, like Na, K, Li, Ca, and Mg. The
instrument is very simple and excludes the need for
a source lamp. The filter is exchangeable in order to
determine the analyte of interest and, in most cases
, a photomultiplier tube is used as the detector.
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Atomic Emission Spectr
oscopy
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Atomic Emission Spectroscopy
Atomic emission spectroscopy (AES), in contrast to AAS, us

es the very high temperatures of atomization sources to
excite atoms, thus excluding the need for lamp sources.
Emission sources, which are routinely used in AES, includ
e plasma, arcs and sparks, as well as flames. We will stud
y the different types of emission sources, their operation
al principles, features, and operational characteristics. Fi
nally, instrumental designs and applications of emission
methods will be discussed.
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Plasma Sources
The term plasma is defined as a homogeneous mi

xture of gaseous atoms, ions and electrons at ve
ry high temperatures. Two types of plasma atom
ic emission sources are frequently used:
1. Inductively coupled plasma
2. Direct current plasma
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Inductively Coupled Plasma (ICP)
A typical ICP consists of three concentric

quartz tubes through which streams
of argon gas flow at a rate in the range
from 5-20 L/min. The outer tube is
about 2.5 cm in diameter and the top
of this tube is surrounded by a
radiofrequency powered induction coil
producing a power of about 2 kW at a
frequency in the range from 27-41
MHz. This coil produces a strong
magnetic field as well.
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Ionization of flowing argon is achieved by a spark whe
re ionized argon interacts with the strong magnetic
field and is thus forced to move within the vicinity o
f the induction coil at a very high speed. A very high
temperature is obtained as a result of the very high
resistance experienced by circulating argon (ohmic
heating).
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The top of the quartz tube will exper
ience very high temperatures and
should, therefore, be isolated and
cooled.
This can be accomplished by passing

argon tangentially around the wall
s of the tube. A schematic of an IC
P (usually called a torch plasma) is
shown below:
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The torch is formed as a result of the argon emissio
n at the very high temperature of the plasma. The
temperature gradients in the ICP torch can be pict
ured in the following graphics:
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Plasma Appearance and Spectra
A plasma torch looks very much like a flame but with a ver
y intense nontransparent brilliant white color at the core
(less than 1 cm above the top). In the region from 1-3 cm
above the top of the tube, the plasma becomes transpar
ent. The temperatures used are at least two to three ord
ers of magnitude higher than that achieved by flames wh
ich may suggest efficient atomization and fewer chemical
interferences.
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The viewing region used in elemental analysis is usual
ly about 6000 oC, which is about 1.5-2.5 cm above th
e top of the tube. It should also be indicated that ar
gon consumption is relatively high which makes the
running cost of the ICP torch high as well. Argon is a
unique inert gas for plasma torches since it has few
emission lines. This decreases possibility of interfer
ences with other analyte lines.
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Ionization in plasma may be thought to be a problem
due to the very high temperatures, but fortunately t
he large electron flux from the ionization of argon w
ill suppress ionization of all species.
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The Direct Current Plasma (DCP)
The DCP is composed of three electrodes arranged in an in

verted Y configuration. A tungsten cathode resides at t
he top arm of the inverted Y while the lower two arms
are occupied by two graphite anodes. Argon flows from
the two anode blocks and plasma is obtained by mome
ntarily bringing the cathode in contact with the anodes.
Argon ionizes and a high current passes through the ca
thode and anodes.
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It is this current which ionizes more argon and sustains the c
urrent indefinitely. Samples are aspirated into the vicinity o
f the electrodes (at the center of the inverted Y) where the t
emperature is about 5000 oC. DCP sources usually have few
er lines than ICP sources, require less argon/hour, and hav
e lower sensitivities than ICP sources. In addition, the grap
hite electrodes tend to decay with continuous use and shou
ld thus be frequently exchanged. A schematic of a DCP sour
ce is shown below:
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A DCP has the advantage of less argon consumption, s
impler instrumental requirements, and less spectral
line interference. However, ICP sources are more co
nvenient to work with, free from frequent consuma
bles (like the anodes in DCPs which need to be freq
uently changed), and are more sensitive than DCP s
ources.
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SUMMARY
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SUMMARY: Contd---
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Thanks for your kind attention
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35 Atomic Emission

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35 Atomic Emission

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Copyright:

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Course Code : PDA302T

By the end of this session, students will be able to:

Usually, atomic absorption based on electrotherma

Flame methods are superior to electrothermal methods in

The technique referred to as flame photometry is a

Atomic emission spectroscopy (AES), in contrast to AAS, us

The term plasma is defined as a homogeneous mi

A typical ICP consists of three concentric

This can be accomplished by passing

The DCP is composed of three electrodes arranged in an in

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