Neha S.Mahajan et al.

/ International Journal of Engineering Science and Technology (IJEST)

ANALYSIS OF UNCERTAINTY
MEASUREMENT IN ATOMIC
ABSORPTION
SPECTROPHOTOMETER
NEHA S.MAHAJAN1 *
1*
M.Tech Student
Department of Mechanical Engineering,
G. H. Raisoni College of Engineering
Nagpur, Maharashtra, India
nehamahajan51@rediffmail.com

NITIN K. MANDAVGADE2
2
Department of Mechanical Engineering,
G. H. Raisoni College of Engineering
Nagpur, Maharashtra, India
nitin_man@rediffmail.com

S.B. JAJU3
3
Department of Mechanical Engineering,
G. H. Raisoni College of Engineering
Nagpur, Maharashtra, India
sbjaju@gmail.com

Abstract :
A spectrophotometer is a photometer that can measure intensity as a function of the light source wavelength.
The important features of spectrophotometers are spectral bandwidth and linear range of absorption or
reflectance measurement. Atomic absorption spectroscopy (AAS) is a very common technique for detecting
chemical composition of elements in metal and its alloy. It is very reliable and simple to use.
Quality of result (accuracy) depends on the uncertainty of measurement value of the test. If uncertainty of
measurement is more there may be doubt of about the final result. The final result of Atomic Absorption
Spectrophotometer gets affected by the number of parameters; we should take in to account will calculating the
final result.
This paper deal with the methodology of evaluating the uncertainty of measurement of chemical composition
using AAS. The study is useful for quality of measurement equipment and testing process.

Keywords - Uncertainty, Chemical Testing, Atomic Absorption Spectrophotometer.

1. Introduction
The objective of a measurement is to assign a magnitude to the measurand, the quantity intended to be
measured. The assigned magnitude is considered to be the best estimate of the values of the measurand. For a
given result there is not one value, but an infinite number of values dispersed about the result within an interval.
Hence measurement of a parameter is meaningless unless the width of interval within which the reported value
of the measured is expected to disperse is specified.

Material used for army purpose is to be tested in proper way because the chemical composition of material is
most affecting factor in performance of final product. While testing chemical composition the final result get
affect by various factors so the composition result may not be so correct.

The uncertainty to be truly meaningful, it must address the entire measuring process, which may have
uncertainties associated with factors such as equipment calibration, operator skill, sample variation, and

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environmental factors [4]. Uncertainty sources are classified according to the evaluation method used. Type A
uncertainties are evaluated statistically [2-5].

2. Atomic Absorption Spectrophotometer

The instrument employs a double beam technique where the emitted radiation from the light source of hollow
cathode lamps of elements of interest is split into two beams, a reference beam and a sample beam. Sample
beam travels through the flame while reference beam travels around the flame. The atomic absorption
Spectrophotometer is as shown in Fig.1

The liquid sample is reduced to a vapour mist of atomic population by a nebulizer with support gas. Mixed
with proper fuel, it is sprayed over the flame. The reference beam going around the flame is not affected because
the energy of sample beam going through the flame is absorbed by the sample element present in the liquid
sample and amount of absorption being proportional to the element concentration. Both these beam are
combined together before entering the monochromatic region which selects the appropriate resonance line and
direct it to the wide range photo multiplier tube. The electronics there after separates reference and sample
signal in time reference single is used to compensate for drift in lamp intensities and sample signal is processed
for photometric computation of the result [3].

2.1 Principle of working

When a liquid sample containing a chemical constituent element of interest is reduced to a spray mist of atomic
vapour, mixed with proper fuel and burn over a burner head and if light radiation of the same element from a
emitting source is passed through the flame, as atoms of the element in the sample vapour are present in ground
state of unexcited condition they absorb amount of corresponding radiation passing through the flame. Amount
of absorption by the analyst depend on its concentration in the sample and are directly proportional to each
other. Hence measurement of absorption value forms the base for calculation of its concentration in sample [1].

2.2 Method of Analysis

Every time when a element is estimated, the system is calibrated by aspirating a set of different strength
standard solution of known concentration of the element and graphical representation of absorbance verses
concentration is made to get a liner graph for the standard solution .when a unknown sample is aspirated in the
same condition, with reference to its measured absorbance and the standard graph concentration of the element
in test sample is displayed in part per million (ppm).

Fig. 1.Atomic absorption spectrophotometer

3. Evaluation of Uncertainty
Uncertainty of measurement (UOM) does not imply doubt about the validity of a measurement; on the contrary,
knowledge of the uncertainty implies confidence in the validity of a measurement result. It defines a range that
could be reasonably being attributed to the measurement result at a given confidence.
The UOM in atomic absorption spectrophotometer may be affected by following factors

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Qualitative factors-
 Knowledge of operator.
 Experience of operator.
 Training of operator.
 Education of operator.
 Confidence of operator
If the operator is unskilled, untrained, less experience & not having knowledge of equipment may perform
the test with less confidence which may affect result of test.

Test on atomic absorption spectrophotometer for chemical composition are performed by me with the help
of Mr.Ravishankar having experience more than 20 year in this field. Hence effect of qualitative factor in our
case negligible.

Quantitative factor-
 Repeatability
 Mass for weight of sample
 Volume taken
 CRM sample
 Calibration CRM
 Volume made

3.1 Repeatability

It is included in Type-A uncertainty. It is an analytical method including the calculation of standard deviation
and type-A standard uncertainty. Standard deviation indicates the spread of values. Spread of values tells us
something about the uncertainty of measurement. Repeatability factor is concerned with the instrument.

3.2 Mass for weight of sample

As the input and output estimates are not co-related, this component is evaluated as relative standard uncertainty
(RSU) sample wt for AAS analysis may range from 0.1 to 10 gram. The expanded uncertainties (K=2) for both
from the certificate are close together as 0.00028 and 0.00034.Considering the fact that smaller sample wt is
more frequently used in AAS analysis the RSU of smaller wt. is general may be consider.

3.3 CRM sample

As the uncertainty state in the certificate of CRM without confidence level and K factor their standard
uncertainty for rectangular distribution are given by stated U/√3 (for 1000 ppm).The highest calibration standard
is considered for this aspect as a maximum possible contribution toward this component. Therefore if 1000 ppm
solution has U ± 0.2 % ppm.

All Nomenclature for the parameters is shown on Table 1.

Table1. Nomenclature for the parameters

Sr. no Parameter Nomenclature

1 UC Combined uncertainty

2 UA Type A standard uncertainty

3 UB Type B standard uncertainty

4 σ Standard deviation

5 n No. of readings

6 Effective Degree of freedom

7 K Coverage factor

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After performing the observations on AAS for measured values of Mn ten times, readings are as shown in
Table-2.
Table2. Observations

Sr. no.
X X
2
Readings X i %
i

1 0.6903
2 0.6953
3 0.6953
4 0.6977
5 0.6958
6 0.6977
7 0.6938
8 0.6977
9 0.6903
10 0.6977

Mean=X=0.6951

 X 
2
 X
Standard Deviation =   i
(1)
 n  1
σ= 0.0028


Standard uncertainty = (2)
n

=
Repeatability (UA) = 0.009

Degree of freedom = n-1 = 10-1= 9

Type B Contribution

Sources of uncertainty and its calculations are as shown in Table 3.

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Table 3. Sources of uncertainty

Source Distribution DOF Calculation Value

U2 = Mass for Wt of Normal ∞ Standard uncertainty=0.00028/2 0.0014
sample =0.00014
Expanded uncertainty U2 = 0.00014/0.1=0.0014
for 0.1g is 0.00028 Expanded Uncertainty is divided
by coverage factor K=2 at
confidence level of 95.45%
U3 = standard Triangular√6 ∞ Standard uncertainty=0.03/ 0.00006
uncertainty due to =0.012
volume taken. U3 = 0.012/20
Vol. =20ml = 0.00006
Max.calibration
error=0.03
U4= Uncertainty due Rectangular ∞ U4 = 0.006/ 0.0003
sample CRM √3 = 0.0003
Reported
uncertainty=0.006
U5 = Uncertainty due to Rectangular ∞ 0.2/100=0.002 0.000001
calibration CRM √3 0.002/(1000×√3)
Reported U5 = 0.000001
uncertainty=.2% for
1000 ppm
U6 = Uncertainty due to Triangular√6 ∞ Standard uncertainty=0.1/ 0.0008
volume made =0.04
Max. calibration error U6 = 2×0.04/100
for 100ml=0.1 ml = 0.0008
100ml made 2 time

(3)

= 0.0091

Effective Degree of freedom=  = U c 4

U i 4
eff
n (4)
i 1  i

= 9.406

From Student’s t-distribution, for the confidence level of 95.45% and for  eff =9.406, the coverage factor
K = 2.32
Expanded Uncertainty (U) =K× UC (5)
U = 2.32 ×0.0091
U = 0.0211

Final result =0 .6951± 0.0211

Final uncertainty budget is as shown in Table 4.

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Table4. Uncertainty budget

Source of Estimated Distribution Sensitivity Std. DOF

Uncertainty value division coefficient uncertainty

U1 0.009 Normal 1 0.009 9

U2 0.00028 Normal 1 0.0014 ∞

U3 0.03 Triangular 1 0.00006 ∞

U4 0.006 Rectangular 1 0.0003 ∞
U5 0.2% Rectangular 1 0.000001 ∞
U6 0.1 ml Triangular 1 0.0008 ∞

Fig. 2 .Effect of various factors of uncertainty of AAS

Conclusion

Even if the result of the measurement is not perfect, it is possible to obtain reliable information, since the result
of the measurement is associated with its respective uncertainty. The success in estimating uncertainty of
measurement depends on correct analysis of the whole measuring process. Estimation of measurement
uncertainty is very important for reliability of measurement data. In case of Atomic Absorption
Spectrophotometer, uncertainty gets affected by different factors such as qualitative and quantitative. This
paper shows the effects of individual factors and its importance on final result. Evaluation of uncertainty gives
idea about various factors affecting the test results. Accordingly proper actions can be taken to reduce the effect
of factor which is affecting more. This helps to improve the quality of testing and calibration lab. In case of
AAS repeatability is affecting more, so while performing the test standard procedure should be followed which
help to minimize the uncertainty of measurement

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References:

[1] Beaty Richard D. and Kerber Jack D.(1993) Concepts, Instrumentation and Techniques in Atomic Absorption Spectrophotometrey.
Second Edition
[2] BIPM/IECIIFCC/ISO/OIML/IUPAC, ISBN 92 67 101889, 1993-95- Guide to the expression of uncertainty in measurement.
[3] Erxleben A (2009).–ppt on Atomic Absorption Spectroscopy.
[4] EA-4/02 (1990) Expression of the uncertainty of measurement in calibration: European Cooperation for Accreditation.
[5] GUM (1993) Guide to the expression of uncertainty in measurement, International Organization for Standardization, Geneva, ISBN
9267-10188-9, First Edition.
[6] Mandavgade N.K.(2011) Mathematical modeling of effects of various factors on uncertainty of measurement in material testing,
Proceedings of 2011 International Conference on Mechanical Engineering and Technology ICMET 2011, November 2011, London,
UK, DOI-http://dx.doi.org/10.1115/1.859896.paper43

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