Neha S.Mahajan et al.

/ International Journal of Engineering Science and Technology (IJEST)

ANALYSIS OF UNCERTAINTY MEASUREMENT IN ATOMIC ABSORPTION SPECTROPHOTOMETER

NEHA S.MAHAJAN1 *
M.Tech Student Department of Mechanical Engineering, G. H. Raisoni College of Engineering Nagpur, Maharashtra, India nehamahajan51@rediffmail.com
1*

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 1 2 3 4 5 6 7

Parameter UC UA UB n

Nomenclature Combined uncertainty Type A standard uncertainty Type B standard uncertainty Standard deviation No. of readings Effective Degree of freedom

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. 1 2 3 4 5 6 7 8 9 10

Readings X i % 0.6903 0.6953 0.6953 0.6977 0.6958 0.6977 0.6938 0.6977 0.6903 0.6977 Mean=X=0.6951

Standard Deviation =

n 1

(1)

= 0.0028 Standard uncertainty =

(2)

= 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 U2 = Mass for Wt of sample Expanded uncertainty for 0.1g is 0.00028

Distribution Normal

DOF

U3 = standard uncertainty due to volume taken. Vol. =20ml Max.calibration error=0.03 U4= Uncertainty due sample CRM Reported uncertainty=0.006 U5 = Uncertainty due to calibration CRM Reported uncertainty=.2% for 1000 ppm U6 = Uncertainty due to volume made Max. calibration error for 100ml=0.1 ml 100ml made 2 time

Triangular6

Calculation Standard uncertainty=0.00028/2 =0.00014 U2 = 0.00014/0.1=0.0014 Expanded Uncertainty is divided by coverage factor K=2 at confidence level of 95.45% Standard uncertainty=0.03/ =0.012 U3 = 0.012/20 = 0.00006

Value 0.0014

0.00006

Rectangular 3

U4 = 0.006/ = 0.0003 0.2/100=0.002 0.002/(10003) U5 = 0.000001

0.0003

Rectangular 3

0.000001

Triangular6

Standard uncertainty=0.1/ =0.04 U6 = 20.04/100 = 0.0008

0.0008

(3)

= 0.0091 Effective Degree of freedom=

=
eff

U c 4 n U i 4

(4)

i 1

= 9.406 From Students t-distribution, for the confidence level of 95.45% and for eff =9.406, the coverage factor K = 2.32 (5) Expanded Uncertainty (U) =K UC 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 Uncertainty U1 U2 U3 U4 U5 U6

Estimated value 0.009 0.00028 0.03 0.006 0.2% 0.1 ml

Distribution division Normal Normal Triangular Rectangular Rectangular Triangular

Sensitivity coefficient 1 1 1 1 1 1

Std. uncertainty 0.009 0.0014 0.00006 0.0003 0.000001 0.0008

DOF

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] [2] [3] [4] [5] [6] Beaty Richard D. and Kerber Jack D.(1993) Concepts, Instrumentation and Techniques in Atomic Absorption Spectrophotometrey. Second Edition BIPM/IECIIFCC/ISO/OIML/IUPAC, ISBN 92 67 101889, 1993-95- Guide to the expression of uncertainty in measurement. Erxleben A (2009).ppt on Atomic Absorption Spectroscopy. EA-4/02 (1990) Expression of the uncertainty of measurement in calibration: European Cooperation for Accreditation. GUM (1993) Guide to the expression of uncertainty in measurement, International Organization for Standardization, Geneva, ISBN 9267-10188-9, First Edition. 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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