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Title of Experiment

Determination of Metals with ICP Atomic Emission Spectrometry

Objectives of Experiment

To determine dissolved analytes in aqueous samples after suitable filtration and acid
preservation.

Introduction
Inductively coupled plasma-atomic emission spectrometry (ICP-AES) is one of the most
intensive and technique which is widely used in the determination of trace elements. This
method uses high-frequency inductively-coupled plasma as the light source, and is
convenient for the analysis of aqueous sample solutions. The spontaneous emission of
photons from atoms and ions that have been excited in a RF discharge is the base of this
technique. The sample solution which is directly injected to the instrument is then converted to
an aerosol and directed into the central channel of the plasma. The aerosol is quickly vaporized
due to high temperature at the inductively coupled plasma (ICP). Analyte elements are
discharged as free atoms in the gaseous state. Further collisional excitation within the plasma
transmits additional energy to the atoms, raising them to excited states. Adequate amount of
energy is available to convert the atoms to ions and to promote the ions to excited states. The
emission of a photon is used to relax the atomic and ionic excited state species to the ground
state. The wavelength of the photons can be used to determine the elements from which they
came from. The total number of photons is directly proportional to the concentration of the
originating element in the sample. This method has become highly recommended due to
its speed and accuracy. It is widely used as the official analysis method according
to JIS and ISO standards and the Japanese Water Supply Act. This instrument
supports an extensive range of analysis from trace levels to high concentrations. It
also supports analysis for research and development, automated analysis for
production control, and water-quality monitoring analysis for environmental
management.

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Reagents and Apparatus

ICP stock solution containing 4 solutions with several concentrations (in ppm) of Cu and Mg
respectively, 4 unknown concentrations of samples for each magnesium and copper, blank
solution, centrifuge tubes, ICP-AES Spectrometer

Diagram

Nitrogen gas flow

Argon gas flow

Purifies air flow

Inductively coupled plasma-atomic emission spectrometry (ICP-AES) machine

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Results and Calculations

Figure 1.1 Graph of intensity versus concentration of magnesium

Intensity versus Concentration of Magnesium


3500000

3000000

2500000

2000000
Intensity

1500000

1000000

500000

0
0 1 2 3 4 5 6
-500000
Concentration (mg/L)

The equation obtained from calibration curve for Mg: = 642399 42524

Sample calculation for unknown concentration of Magnesium (UM1):

= 642399 42524

1312493.7 = 642399 42524

= 2.109 /

Table 1.1: The table of concentration of each unknown of magnesium sample

Unknown Intensity Concentration (mg/L)


UM1 1312493.7 2.109
UM2 2530633.3 4.006
UM3 4148926.9 6.525
UM4 5275925.7 8.279

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Figure 1.2 Graph of intensity versus concentration of copper

Intensity versus Concentration of Copper


4500000
4000000
3500000
Intensity

3000000
2500000
2000000
1500000
1000000
500000
0
-500000 0 1 2 3 4 5 6 7

Concentration (mg/L)

The equation obtained from calibration curve for Cu: = 644854 563

Sample calculation for unknown concentration of Copper (UC1):

= 644854 563

3217990.8 = 644854 563

= 4.991 /

Table 1.2: The table of concentration of each unknown of copper sample

Unknown Intensity Concentration (mg/L)


UC1 3217990.8 4.991
UC2 1937753.7 3.006
UC3 4612372.0 7.153
UC4 5989315.3 9.289

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Discussion

In this experiment, induced coupled plasma atomic emission spectrometry, (ICP-AES),


were used to determine the concentration of magnesium and copper in a sample. This inductively
coupled plasma (ICP) machine provides fast and precise methods for observing up to 50
elements simultaneously for minor and trace levels. It also has a superior detection capability,
especially for the rare-earth elements. When excited atoms from a sample are produced, they
emit electromagnetic radiation at wavelength characteristic of a particular element. On the other
hand, a spectrometer separates and settles these lines and measures their strength.

The ICP-AES consists of two parts, the ICP and the optical spectrometer. The ICP torch
contains 3 concentric quartz glass tubes. Argon gas is typically used to create the plasma. At the
point when the sample is brought into the spectrometer, it atomized into a fog like cloud. This
fog is conveyed into the argon plasma with a stream of argon gas. Argon gas flows into the
concentric channels of the ICP light. The radio frequency load coil is connected to its generator.
As power is switched on, oscillating electric and magnetic fields are set up at the end of light. As
the argon flows through the ICP light, electrons are peeled off, causing the argon atoms to form
argon ions.

Based on the ICP discharge, the ions formed are normally positive ions whereas elements
which form negative ions are hard to be determined via ICP-AES. These particles collide with
other argon atoms to produce further ionization, framing argon plasma and causing temperature
raise. The ionized argon produces temperatures near 6000-10000K, which thermally energizes
the external shell electrons of the components in the sample. In some designs, nitrogen or dry
compressed air is used to cut the plasma at a specific spot. A compressed nitrogen is utilized to
expel the plasma tail from the optical way in order to limit obstructions and extend the dynamic
range. The shear gas configuration offers an upkeep free and lower-cost way to deal with
expelling the cooler plasma zone.

In this experiment, the manipulated variable is the concentration of samples and the
responding variable is the intensity of light emitted. From the result of the experiment, a graph of
intensity of emitted light versus concentration is drawn for both magnesium and copper samples.

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Let y-axis to be the intensity and x-axis is the concentration. By using the three known
concentration of sample, a best fit graph can be obtained. The straight line graph show the
relationship of concentration of sample and intensity of light emitted to be proportional to each
other. From the graph, an equation is obtained for magnesium sample that is = 642399
42524 and another equation = 644854 563 for copper sample. By using the equation
obtained, the 4 unknown concentrations of samples for each magnesium and copper samples can
be calculated. The concentration of each unknown Cu and Mg is recorded in Table 1.1 and Table
1.2. Nevertheless, the concentration for the unknown sample for both Mg and Cu through
manual calculation is slightly different from the concentration obtained from the software. But
the concentration obtained through calculation is still acceptable as it falls in the range of
standard deviation.

There are some differences between ICP-AES and AAS. AES stands for 'Atomic
Emission Spectroscopy' whereas AAS stands for 'Atomic Absorption Spectroscopy'. Both of
these are spectro-analytical methods used in Chemistry to quantify the amount of a chemical
species; in other words, to measure the concentration of a specific chemical species. AAS and
AES differ in their operating principle where AAS employs the method of absorption of light by
the atoms and, in AES, the light emitted by the atoms is what is taken into consideration. In
AAS, a monochromatic light source is used to provide energy for the excitation of electrons. In
the case of AES, it is a flame that is often used. Another aspect that differentiates AES from
AAS is their operating principle. In AAS, there is a separate chamber for atomization of the
sample in AAS. When monochromatic light is bombarded through the sample the atoms absorb
energy, and the extent of absorption is recorded. However, in AES, atomization takes place step
by step upon the introduction of the sample to the flame. The sample which gets atomized in the
flame then absorbs the energy through the electrons which get excited. Later this energy is
released upon the relaxation of the atoms and is measured by the instrument as the emitted
energy.

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In aspect of detection limits, ICP-OES spectrometer has shown impressive detection
limits in the sub-ppb region for some elements using a high-resolution monochromator with
radially viewed plasma. Other spectrometers have been able to get improvements using an
axially viewed ICP, although this view has problematic matrix interferences. Flame AAS has
generally poorer detection limits than ICP-OES except for the alkalis metals for example sodium
and potassium. This is because AAS technique relies on ground state atoms and the absorption of
light that passes through the flame containing the atoms. But for ICP-OES requires different,
much higher temperatures for emission to take place for most of the elements. Because of the
high temperatures present in inductively coupled argon plasma not only atomic, but also ionic
emission takes place. This is an advantage since many metals have sensitive ionic emission lines.
This is the reason why ICP-OES, compared to the AAS technique, provides higher detection
sensitivity.

In aspect of analysis element, ICP-OES systems can analysis few elements in one time
but AAS only able to purely sequential which means element by element analysis. Although
AAS are fast, require only about 3 sec for one replicate measurement versus 30 sec which is ICP-
OES typically used. This means that when more than 10 elements need to be analyzed an ICP is
faster than an AAS.

In aspect of precision, the precision for ICP-OES up to 0.3%-1% and the precision for
AAS is up to 0.1% -1%.

Sample preparation is critical to the success of the method. The sample is dissolved in a
solvent, typically a dilute acid, but deionized water or an organic solvent may also be used.
Typically dilute nitric acid or hydrochloric acid is used to eliminate interference, but other acids
may be used if necessary. If the sample is not soluble or the solution clogs the nebulizer, an
alternate sample preparation method is required. Acid digestion may also be used; however
precaution must be taken to prevent loss of elements during the heating process. Precautions
must be taken when making mixed standard preparations to ensure all of the elements are
compatible in solution and no precipitation occurs. It is important to prepare standards and

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blanks in the same matrix as that of the sample to eliminate interference. During the experiment,
student should wear protective equipment such as laboratory coat and avoid staying near the
ICP-AES Spectrometer as it is operating at high temperature.

The calibration curve that we obtained in this experiment is when the concentration for
magnesium and copper increase the intensity we get from ICP for magnesium and copper will
also increase. This is due to the higher the concentration will having a high number of molecules
to absorb the light energy.

In overall by comparing between ICP-OES and AAS, the result obtain by ICP-OES is
more superior than AAS. This is because the detection limit for ICP-OES is better than AAS and
ICP-OES having high detection sensitivity than AAS.

Conclusion

References

Lajunen, L. H. J. and Peramaki, P. (2005). Spectrochemical analysis by atomic absorption and


emission. (1st ed.). Cambridge: Royal Society of Chemistry.

Velez, G. (2009). Inductively coupled plasma: the future of heavy metals testing. Retrieved from
http://www.sgs.co.ao/~/media/Global/Documents/Technical%20Documents/sgs- regulatory-
heavy%20metals-en-09.pdf