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FACULTY OF APPLIED SCIENCES

DEPARTMENT OF CHEMISTRY

BTECH: CHEMISTRY

ANALYTICAL CHEMISTRY 4

MODULE 1

PRACTICAL REPORT (Experiment 3)

ICP-OES

STUDENT NAME: MARCEL LEE KISTAN

STUDENT No.: 21402399

LECTURER: Mr K Ramluckan

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TITLE & AIM OF THE EXPERIMENT

To determine the concentrations of copper (Cu) and manganese (Mn) in a multi-element sample
using an Inductively Coupled Plasma Optical Emission Spectrometer.

THEORY

The ICP-OES employs the basic principle of spectroscopy which relates the amount of energy
emitted or absorbed by electrons to the relative wavelength per the equation
𝒉𝒄
∆𝑬 = 𝒉𝒗 =
𝝀
where h= Planck’s constant =6.63 x10-34Js
c= speed of light (3 x108 ms-1)
v= frequency (Hz)
λ= wavelength (nm)

and also Beer-Lambert’s law

𝑨 = 𝜺𝒍𝒄

Where A= Absorbance or emission intensity


𝜀= molar absorption co-efficient
l= path length
c= concentration of the analyte
Using this relationship, we find the molar absorption or emission to be directly proportional to
the concentration of the species under investigation. This is evident from the plots obtained
which are linear.

The ICP-OES is a preferred instrument as it allows multi-element analysis. The instrument uses
a polychromator which enables it take multiple emission readings at various wavelengths for
multiple elements simultaneously. This ability and the reproducibility of results make it
favourable over other emission techniques.

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REAGENTS

 AR/Spectroscopic grade Copper (II) Nitrate Cu(NO3)2·nH2O


 Manganese Standard 100ppm
 65% Concentrated Nitric Acid HNO3
 Deionized water – AAS quality

INSTUMENTATION

Instrument Name : Shimadzu


Model : ICPE-9000
RF Power (kW) : 1.20
Plasma Gas (L/min) : 10.0
Auxiliary Gas (L/min): 0.60
Carrier Gas (L/min) : 0.70
Plasma View direction : Axial
λCu : 327.396 nm
λMn : 257.610 nm

EXPERIMENTAL PROCEDURE

As per practical manual

PRE-EXPERIMENTAL DATA & CALCULATIONS

 Vol. HNO3 required to prepare 1L of 1% v/v HNO3:

C1V1 =C2V2
(65%)(𝑥𝑚𝐿) = (1%)(1000𝑚𝐿)
(1%)(1000𝑚𝐿)
𝑥𝑚𝐿 =
(65%)
𝑥𝑚𝐿 = 15,40𝑚𝐿

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Mass of Cu (NO3)2 2.5H2O required to prepare 100ppm copper stock solution:
RMM of Cu = 63.55g/mol
Assay of Cu :98 %
232.59g
100mg 𝑜𝑓 𝐶𝑢 (𝑁𝑂3)2 2.5𝐻2𝑂
mol
= 1000ml x 63.55g x 100ml
𝑜𝑓 𝐶𝑢
mol

1g
=36.60mg x 1000mg =0.0366g of Cu
100%
=0.0366g x = 0.03735g of Cu
98%

Actual mass weighed = 0.0374g

Volume of 100ppm Cu required to prepare 5ppm in 100mL:


C1V1 =C2V2
(100𝑝𝑝𝑚)(𝑥𝑚𝐿) = (5𝑝𝑝𝑚)(100𝑚𝐿)
(5𝑝𝑝𝑚)(100𝑚𝐿)
𝑥𝑚𝐿 =
(100𝑝𝑝𝑚)
𝑥𝑚𝐿 = 5𝑚𝐿

Volume of 100ppm Cu required to prepare 7ppm in 100mL:


C1V1 =C2V2
(100𝑝𝑝𝑚)(𝑥𝑚𝐿) = (7𝑝𝑝𝑚)(100𝑚𝐿)
(7𝑝𝑝𝑚)(100𝑚𝐿)
𝑥𝑚𝐿 =
(100𝑝𝑝𝑚)
𝑥𝑚𝐿 = 7𝑚𝐿

Volume of 100ppm Cu required to prepare 10ppm in 100mL:


C1V1 =C2V2
(100𝑝𝑝𝑚)(𝑥𝑚𝐿) = (10𝑝𝑝𝑚)(100𝑚𝐿)
(10𝑝𝑝𝑚)(100𝑚𝐿)
𝑥𝑚𝐿 =
(100𝑝𝑝𝑚)
𝑥𝑚𝐿 = 10𝑚𝐿

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Volume of 1000ppm Mn required to prepare 100 ppm in 100mL:
C1V1 =C2V2
(1000𝑝𝑝𝑚)(𝑥𝑚𝐿) = (100𝑝𝑝𝑚)(100𝑚𝐿)
(100𝑝𝑝𝑚)(100𝑚𝐿)
𝑥𝑚𝐿 =
(1000𝑝𝑝𝑚)
𝑥𝑚𝐿 = 10𝑚𝐿

Volume of 100ppm Mn required to prepare 10 ppm in 100mL:


C1V1 =C2V2
(100𝑝𝑝𝑚)(𝑥𝑚𝐿) = (10𝑝𝑝𝑚)(100𝑚𝐿)
(10𝑝𝑝𝑚)(100𝑚𝐿)
𝑥𝑚𝐿 =
(100 𝑝𝑝𝑚)
𝑥𝑚𝐿 = 10 𝑚𝐿

Volume of 100 ppm Mn required to prepare 5ppm in 100mL:


C1V1 =C2V2
(100𝑝𝑝𝑚)(𝑥𝑚𝐿) = (5𝑝𝑝𝑚)(100𝑚𝐿)
(5𝑝𝑝𝑚)(100𝑚𝐿)
𝑥𝑚𝐿 =
(100𝑝𝑝𝑚)
𝑥𝑚𝐿 = 5 𝑚𝐿

Volume of 10 ppm Mn required to prepare 2ppm in 100mL:


C1V1 =C2V2
(10𝑝𝑝𝑚)(𝑥𝑚𝐿) = (2𝑝𝑝𝑚)(100𝑚𝐿)
(2𝑝𝑝𝑚)(100𝑚𝐿)
𝑥𝑚𝐿 =
(10𝑝𝑝𝑚)
𝑥𝑚𝐿 = 20 𝑚𝐿

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RESULTS & TREATMENT OF EXPERIMENTAL DATA
Table 1: Analysis Results of Copper

Analysis of Cu using ICP at 327,396nm


Set concentration Instrument Intensity Corrected Intensity
Multi-standard
(mg/L) reading reading
Blank 0,00
222,56
9253,50 9030,95
Std 1 5,00
12141,29 11918,74
Std 2 7,00
16919,53 16696,98
Std 3 10,00
13886,7 13664,15
Unknown
Table 1. Showing the results at 327.396nm for analysis of Cu using ICP

Analysis of Cu using ICP at 327.396nm


18000.00

16000.00 y = 1537.9x + 1270.9


14000.00 R² = 0.9993

12000.00
INTENSITY

10000.00

8000.00

6000.00

4000.00

2000.00

0.00
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00

CONCENTRATION / mg/L

Figure 1. Showing the results at 327.396nm for analysis of Cu using ICP

Calculating the concentration of unknown copper


y = 1537,9x + 1270,9
13664,15 = 1537,9x + 1270,9
X = 8,06 ppm

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Analysis of Mn using ICP at 257,610 nm
Set concentration Instrument Corrected
Multi-standard
(mg/L) Intensity reading Intensity reading

Blank
0,00 123,55
Std 1 2,00 52408,83 52285,28

Std 2 5,00 73920,88 73797,33

Std 3 10,00 144266,40 144142,85

Unknown 91450,23 91326,68

Table 2. Showing the results at 257.610 nm for analysis of Mn using ICP

Analysis of Mn using ICP at 257,610 nm


160000.00
y = 11746x + 23514
140000.00
R² = 0.9763

120000.00

100000.00
INTENSITY

80000.00

60000.00

40000.00

20000.00

0.00
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

CONCENTRATION / mg/L

Figure 2. Showing the results at 257.610 nm for analysis of Mn using ICP

Calculating the concentration of unknown manganese


y = 11746x + 23514
91326,68 = 11746x + 23514
x = 5,77 ppm

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DISCUSSION

The calibration curves above were obtained to ensure that the instrument was optimized to
eliminate error and inconsistency in the analysis. Ideally the curves should have an R2=1,
during the practical a R2=0,993 and 0,9763 was shown for the cu and Mn calibration curve
The curve is a representation of Beer-Lambert’s law which correlates the intensity of emission
to the concentration of the analyte.

Furthermore, all dilutions made were within the allowed dilution limit of 20 times. The dilution
precaution is taken to reduce errors in dilution as the pipette used had a 5% graduation error.
Performing large dilutions, i.e. above 20 times increases the error in the dilution giving a false
representation of the sample analysed and the overall analysis.

The instrument has sample nebulizer located in the spray chamber where the sample is
aspirated, and then transported by the Argon (Ar) carrier gas into the plasma. The plasma itself
is sustained by a continuous flow of Argon gas. The RF generator powers the induction coil
and provides seed electrons to the plasma. Inside the plasma the sample is atomized, ionized
and excited. The spectral lines are isolated by the wavelength selector and the light then
converted into current by the detector. The signal is then processed by the computer into a
reading.

The torch during the analysis was orientated radially. The choice of configuration, particularly
between radially and axially-viewed plasma systems, is typically governed by the detection
limit requirements of the analysis, and by the complexity of the sample matrix.
Axially-viewed systems offer lower detection limits, whereas radially-viewed systems are
preferred for routine analysis of more complex sample matrices. For oils, metals and geological
samples, the detection limit of a radially-viewed system is usually sufficient, and the
application easier and more routine to run. Dual-view on the other hand is still horizontally
oriented plasma and although it offers a side-on (radial view), it does not offer the same benefits
as dedicated vertically oriented, radially viewed plasma.

The most common form of matrix interference observed within the plasma is ‘ionization
interference’, also known as ‘easily ionized element’ interference. Ionization interferences
result from the presence of high concentrations of easily ionized elements in samples,

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especially the common Group 1 elements, potassium and sodium, and to a lesser extent, the
Group 2 elements, calcium and magnesium. These elements have low energies of ionization
and are easily ionized by the high plasma temperatures. At sufficiently high concentrations, the
electron density within the plasma is increased to a level where the atomization-ionization
equilibrium of other elements is affected. This is one of many important reasons why matrix
matching of calibration and sample solutions is often recommended, although it is not always
possible.

Advantages of using an inductively Coupled Plasma Optical Emission Spectrometer (ICP-


OES)

The ICP over other excitation sources originate from its capability for efficient and
reproducible vaporization, atomization, excitation, and ionization for a wide range of elements
in various sample matrices. This is mainly due to the high temperature, 6000–7000 K, in the
observation zones of the ICP. This temperature is much higher than the maximum temperature
of flames or furnaces (3300 K). The high temperature of the ICP also makes it capable of
exciting refractory elements, and renders it less prone to matrix interferences.

Disadvantages of using an inductively Coupled Plasma Optical Emission Spectrometer (ICP-


OES)

One major drawback to ICP-AES is that it does not identify the oxidation state of the element
in its original matrix. For example, a sample may contain Fe+3 but when the iron is detected
in the plasma, it will be predominantly Fe with some Fe+.As well as refractory oxides affect
the partial ionized gas nebulizer by creating oxides particles that clog up the chamber,
making it less efficient and exposed to matrix effect.

CONCLUSION

The calibration of the instrument proved successful as the intensity readings obtained were
proportional to the concentration of the standard which conforms to the Beer-Lambert’s Law.
The unknown sample was found to have a concentration of 8,06 ppm Copper and 5,77 ppm

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Manganese, which falls within the range of the standards prepared. The experiment was
successful with all results obeying Beer-Lambert’s Law.

REFERENCES

1. ICP2012additional.pdf ( dutmoodle.dut.ac.za/moodle/)
2. Fundamentals of Analytical Chemistry 8th Ed. – Skoog, West, Holler & Crouch
3. www.perkinelmer.com
4. J. B. Ezell, Jr., At. Absorpt. Newsl. 6, 84 (1967).
5. W. Reichel and L. Acs, Anal. Chem. 41, 1886 (1969).
6. U. Westerlund-Helmerson, At. Absorpt. Newsl. 5, 97 (1966).

ANNEXTURES & ATTACHMENTS

1. Instrumental printout.

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