(Instrumental Analysis)

(Code: SOU30270)

4th Stage Chemistry Department

Semester 7/Level UGIV

Lecturer: Dr. Vian S. Ismail

Email: vian.esmaeil@soran.edu.iq

Week 7/Lecture No. 7

Lecture time: Sunday: 11.30 -2.30

(20/ 11/2022 ) 1
Atomic emission

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Inductively Coupled Plasma
Inductively coupled plasma atomic emission spectroscopy(ICP-AES),
also referred to as inductively coupled plasma optical emission spectrometry (ICP-
OES) -is a type of emission spectroscopy that uses the inductively coupled plasma to
produce excited atoms and ions that emit electromagnetic radiation at wavelengths
characteristic of a particular element.

Plasma : It is a state of matter in which an

ionized gaseous substance becomes highly
electrically conductive to the point that long-
range electric and magnetic fields dominate
the behavior of the matter. The plasmastate
can be contrasted with the other states: solid,
liquid, and gas.
•ICP-use a high temperature plasma for
sample atomization/ excitation.
•In this technique higher fraction of atoms Figure 6.5. Illustration of an
exist in the excited state, giving rise to an inductively coupled plasma.
increase in emission signal and
allowing more types of atoms to be detected. 5
Plasma is a state of matter similar to a gas, except all of the particles carry an
electrical charge. Also, plasma tends to exist at very low pressure, so the particles
are even further apart than in a gas. Plasma can consist of ions, electrons, or
protons. Examples of plasma include lightning, the aurora, the Sun, and the inside
of a neon sign.
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General features of ICP
1.Very high temperature : This temperature is sufficient to convert all materials
into atoms, and excite a large proportion of them.
2. Also, due to high temperature, no refractory compounds are formed and thus:
a. Very low chemical interferences , even interference that may arise as a result
of the ionization of some atoms is very little, because ionization of argon gas in
plasma produces huge amounts of electrons that inhibit ionization of other
atoms.
b. Spectral interference is negligible.
3.The linear range curve is usually wide and exceeds the range which we obtain
from Flame photometry.
4. Argon gas is inert, so the analysis is done in an inert environment, that is free
from oxides.
5. Argon is characterized by a small number of emission lines of its own, and
therefore is considered an ideal gas to minimize the interferences.
6. Normally, the ICP does not need frequent maintenance.
7. More than one element can be analyzed.
8. It requires large quantity of argon gas about 17.0L/mint.

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ICP-AES-Application

-Clinical Analysis: metals in biological fluids (blood, urine).

-Environmental Analysis: trace metals and other elements in waters,
soils and plants.
-Pharmaceuticals: traces of catalysts used; traces of poison metals
(Cd, Pb etc).
-Industry: trace metal analysis in raw materials; noble metals
determination.
-Forensic science: gunshot powder residue analysis, toxicological
examination
( e.g., thallium (Tl) determination).

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Advantages
•Several elements can be recorded at once
•Higher temperatures means lower inter-element interference
•Several elements can be analyzed from a very small sample
•Nonmetals can be determined by plasma
•Low concentration refractory compounds can be determined
•High concentration range for plasma sources

Disadvantages
•Equipment is more expensive
•Procedure is more complicated
•Higher operating costs

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Direct calibration

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Instrumentation of Atomic absorption spectrometry

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Atomization Sources
There are a variety of strategies that can be used to create atoms from molecular
substances. The three main methods involve the use of a flame, a device known as
a graphite furnace or a plasma. These three atomization methods are commonly
used with liquid samples. Since many samples do not come in liquid form (e.g.,
soils, sludges, foods, plant matter), liquid samples suitable for introduction into
flames, furnace or plasma instruments are often obtained by digestion of the
sample. Digestion usually involves heating the sample in concentrated acids to
solubilize the metal species. In some cases it is desirable to measure a sample its
solid form. There are arc or spark sources that can be used for the analysis of solid
samples.

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1. Flames
Flames can be used as an atomization source for liquid samples. The sample is
introduced into the flame as an aerosol mist. The process of creating the aerosol is
referred to as nebulization. Common nebulizer designs include pneumatic and
ultrasonic devices. The most common flame atomization device, which is
illustrated in Figure 6.1, is known as a laminar flow or pre-mix burner. Often the
monochromator is placed after the flame and before the detector.

Figure 6.1. Illustration of a laminar flow or pre-mix burner. 23

In AAS, the flame functions as :
(i) sample holder,
(ii) Desolvation source, and
(iii) volatilization source.

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What happens in the Flames
premix burner;
sample (1–2 mL) + oxidant + fuel :
A flame of Acetylene/air (giving a temperature of 2200 –2400 °C) or
Acetylene /dinitrogen oxide (2600 – 2800 °C) are often used.
Nebulization; aerosol (narrow size distribution and smallest sizes are
desirable)
A flexible capillary tube connects the solution to the nebuliser. At the
tip of the capillary, the solution is ‘nebulised’ – ie broken into small
drops. The larger drops fall out and drain off while smaller ones
vaporise in the flame.

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Remembering that the solution has molecules but we need atoms, there are
several steps required to complete this transformation. The first involves
evaporating the solvent (Eq 1). Many metal complexes form hydrates and the next
step involves dehydration (Eq. 2). The metal complexes must be volatilized (Eq 3)
and then decomposed (Eq. 4). Finally, the metal ions must be reduced to neutral
atoms (Eq. 5). Only now are we able to measure the absorbance by the neutral
atoms. If the measurement involves atomic emission, then a sixth step (Eq. 6)
involves the excitation of the atoms.

The problem with large aerosol droplets is that they will not make it through all of
the necessary steps during their lifetime in the flame. These drops will contribute
little to the signal, but their presence in the flame will create noise and instability in
the flame that will compromise the measurement. Hence, only the finest aerosol
droplets will lead to atomic species and only those are introduced into the flame.
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An important factor in the characteristics of a flame is the identity of the fuel and
oxidant. Standard Bunsen burner flames use methane as the fuel and air as the
oxidant and have a temperature in the range of 1,700-1,900oC. A flame with
acetylene as the fuel and air as the oxidant has a temperature in the range of
2,100-2,400oC. For most elements, the methane/air flame is too cool to provide
suitable atomization efficiencies for atomic absorbance or emission
measurements, and an acetylene/air flame must be used. For some elements, the
use of a flame with acetylene as the fuel and nitrous oxide (N2O) as the oxidant is
recommended. The acetylene/nitrous oxide flame has a temperature range of
about 2,600-2,800oC. It is also important to recognize that some elements do not
atomize well in flames. Flame and other atomization methods are most suitable for
the measurement of metals. Non-metallic elements rarely atomize with enough
efficiency to permit analysis of trace levels. Metalloids such as arsenic and
selenium have intermediate atomization efficiencies and may require specialized
atomization methods for certain samples with trace levels of the elements.
Mercury is another atom that does not atomize well and often requires the use of
a specialized atomization procedure. Flame methods are usually used for atomic
absorbance measurements because most elements do not produce high enough
concentrations of excited atoms to facilitate sensitive detection based on atomic
emission. Alkali metals can be measured in a flame by atomic emission. Alkaline
earth metals can possibly be measured by flame emission as well provided the
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concentration is high enough.
Atomic absorption spectrometry has many applications
Clinical analysis. Analysing metals in biological fluids such as blood and
urine.
Environmental analysis. Monitoring our environment – eg finding out
the levels of various elements in rivers, seawater, drinking water, air,
petrol and drinks such as wine, beer and fruit drinks.
Pharmaceuticals. In some pharmaceutical manufacturing processes,
minute quantities of a catalyst used in the process (usually a metal) are
sometimes present in the final product. By using AAS the amount of
catalyst present can be determined.
Industry. Many raw materials are examined and AAS is widely used to
check that the major elements are present and that toxic impurities
are lower than specified – eg in concrete, where calcium is a major
constituent, the lead level should be low because it is toxic.
Thus, the most important step is to produce free atoms of metals (M)
from sample solution (or Solid)
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TYPES OF INTERFERENCE
Spectral interference; overlapping signal from absorption or emission of
unwanted species (molecules or radicals)
Correction: choose another wavelength or use D2 lamp for flame signals

Ionization: Higher atomization temperature cause ionization of analytes like Na or

K;
Na → Na+ + e
Correction: add ionization suppresser, easily ionizable atoms like CsCl (to increase
electrons in the flame to reverse the direction of ionization reaction of the analyte
ionization, Le Châtelier’s principle.

Atomic emission spectroscopy is very sensitive to temperature fluctuations.

Atomic absorption spectroscopy is less sensitive to temperature fluctuations.

Chemical interference; Some metals cannot be determined in the presence of

other species due to the formation of thermally stable compounds and can not be
atomized.

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Example:
Ca can not be determined in the
presence of phosphate, because of the
formation of refractory calcium
phosphate and decreases the
atomization of Ca and the amount of
atoms produced are very low.
Correction: A releasing agents is added
like La3+ , salt solution LaCl3 to allow
chemical exchange
Ca3(PO4)2 + 2LaCl3 → 3CaCl2 + 2LaPO4
CaCl2 is easily atomized

EDTA may also be used for other metals.

Rich flame may also be used to give high
temperature able to atomize refractory
materials.
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Tutorial Section

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Elements analyzing using ICP

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