Errors in Quantitative Measurement In practice, there is error associated with any measurement - that is, the measured value differs from a theoretical true or actual value, Obviously, we seek to minimize error in measurement and obtain a value that is as close to the true value as practical or possible. When we report the result of a measurement, we also report an estimate of the error or uncertainty of the ‘measurement as a matter of good scientific practice ‘There are two types of error that we distinguish - random error and systematic error - and these can be related to the specific meanings for the terms accuracy and precision earlier discussed. Random errors are due to the precision of the equipment, and systematic errors are due to how well the equipment was used or how well the experiment was controlled, Systematic error Random error Determinate Errors Constant Error ‘These errors are the same for all measurement Systematie/Biased Error + Systematic errors are biases in measurement which lead to a situation wherein the mean of many separate measurements differs significantly from the actual value of the measured attribute in one direction, + Assystematic error makes the measured value alway's smaller or larger than the true value, but not both. An experiment may involve more than one systematic error and these errors may nullify one another, but each alters the true value in one way only. + Accuracy (or validity) is a measure of the systematic error. If an experiment is accurate or valid, then the systematic error is very small + Systematic errors include personal errors, instrumental errors, and method errors,Categories of System: Operational error Errors caused by humans are se methods or procedures. anscending and have nothing to do with experimental Exampl + Non-quantitative treatment from analysts while experimenting + Less precise quantitative sedimentation + Heating / sediment heating at temperatures that are less precise * Cooling the exchange rate is less sufficient before use weigh Error Instruments and Reagents ‘This occur when using instruments or choosing reagents. Exampl Instruments / tools used are not calibrated before use. +The fatty / dirty burette is not cleaned before use + The reagents used are not pure © Volumetric equipment, such as burets, pipets, and volumetric flasks, frequently deliver or contain volumes slightly different from those indicated by their graduations Method Error Exampl + Incorrect sampling + The reaction is not perfect + The presence of impurities on deposits when using Gravimetry + Selection of inappropriate indicators to determine the end point of the titration Additive and Comparable Errors (Proportional) The absolute value of the additive error does not depend on the quantity of the constituents of the substance set, whereas in proportional error itis very influential Example 1: + The loss of the weight of the exchange rate at the time of the annealing will not affect the quantity of constituent substances placed in the exchange rate later. 2Example 2: + The presence of impurities in the standard solution causes the increase in the quantity of constituents linearly or not, so that it can result in an error of normality (N) value of a standard solution. Indeterminate/Random/Chance Error Arrandom error makes the measured value both smaller and larger than the true value; they are errors of precision. © Random errors oceur by chance and cannot be avoided. ‘© Random error is due to factors which we do not, or cannot, control How to Minimize Errors in Quantitative Analysis, + Calibrate tools and make corrections The instrument is calibrated and corrected against standard measurements in order to determine whether the instrument used is in good condition (not damaged). In addition to calibration, itis also important to wash glass-sized appliances (eg biuret, volume pipette) to clean and impurities free + Setting the blanks Make separate assignments to blanks. The objective is to know the presence of impurities in the reagents and the correction of the standard solution to reach the end. point of the titration. Correction value should not be too big (not correct and not careful) + Conducting surveillance Under identical conditions, determination is made of samples and standards containing constituents of equal weight as contained in the sample + Using comparative analysis methods Analysis using different methods, e.g, determination of iron content (Fe) in the sample by Gravimetry in comparison with the Volumetric method. The methods used are correct if the results obtained do not differ significantly + Perform a parallel assignment Check the results obtained from the analysis and make repeated assignments, For example, titration is done 3 times not just once to get the right result. However, the titration volume obtained should not differ much or more than 0.05 (must be precision). Meaningful Numbers In addition to the above, to reduce errors in quantitative analysis is also very important to understand meaningful numbers using the principles of rounding off.Estimation of Errors Percent Error Percent error (sometimes referred to as fractional difference) measures the accuracy of a measurement by the difference between a measured or experimental value E and a true or accepted value A. The percent error is calculated from the following equation: 9 EAL % Estor = = ‘The reliability of a set of measurements, such as the sequence x1, X2, 3........Xn is specified by certain measures called errors Average deviation /Average error (d) ‘The average error or average deviation is the arithmetic mean of all individual errors (deviation ‘from the mean) without regard to sign. d =¥24 Where N= Number of measurement (or analysis) x + = deviation from the mean (individual error) Standard deviation (or root-mean-square error) This is the square root of the average of the squares of the deviations from the overall mean = For large value of N, ie, N 230, N-I=N in the above equation For Ns30 SIN x ix-z| lez? 1 72 12-795-0.7 -0.77= 0.49 2 16 3 18 4 80 5 82 6 83 1 82 583/7=79(i) Coefficient of variation (called the relative standard deviation ie RS.D) ‘This is the ratio of the standard deviationa9 or standard error) to the average of the set of data, RSD == Relative standard deviation can be expressed in percentage or in parts per thousand 1. Relative standard deviation (R.S.D)in percentage RSD (%) 2. Relative standard deviation in parts per thousand 7 (iii) Variance (9) (c) Probable error (r) A relationship has been established between the root-mean-square error(s), average deviation (@) and probable error by the formula; R=0.6745s= 0.78760 Question Analyses of a sample of iron ore gave the following percent value for the iron content; 7.08, 7.21, 7.12, 7.09, 7.16, 7.14, 7.07, 7.14, 7.18, 7.11. Calculate the mean, standard deviation, average deviation, coefficient of variation for the values Absolute Error ‘This is the difference between the true value and the measured value, with regards to sign. Absolute error (€ )= Observed value (x)- true value (T) ‘Thus, we have e= T. for single measurement -T for a set of replicate analyses Questions 1. The accepted value for the chloride content in a standard milk sample obtained from extensive previous analysis is 54.20%. The same sample was carried out by a new instrumental procedure and 54.05% was observed. Calculate the absolute error. 2. The accepted value for the chloride content in a standard milk sample obtained from extensive previous analysis is 54.20%. Five analysis of the same sample were carried out by a new instrumental procedure, The values obtained are $4.01, 554.24, $4.05, 54.27 and 54.11%. Calculate the standard deviation and the absolute error in this new analytical procedure © =(54.05 - 54.20) % = 0.15%, note that absolute error has regard for signs (b) Bx _ S40ses424es4osessa7e54tt 54 196 54 140p Means, # === : Standard deviation = SIN x ial ear T S401 S40-3414=0.13 [0018 o] 3424 010 0.0100 3 3405 0.09 0.0087 4 3427 013 0.0169 3 Sh O05 0.0005 Summation [270.68 0.0528 DE 0.0528 1150% Absolute error= Mean value - True value = 54,14 - 54,20 = 40.06% Relative error (R) Relative means: considered in relation or in proportion to something else Absolute error Relative error (R)= True value T From the above example, 0s _ % R= 255 =0.0011% Relative error can be expressed in percentage or in parts per thousand as follows 6(@) Percentage relative error R(%) (ii) Relative error in Parts Per Thousand R (ppt) =F xo TG Relative Accuracy (Ra) This is the measured value or mean (in case of a set of measurements) expressed as a percentage or in part per thousand of the true value, measured value (or mean) True value Relative Accuracy (Ra) From the above examples measured value (Ba) =a OR ey = Beara (i) RO TRY True value (a), Raexpressed in Percentage Ra(%)= (b), Ra expressed in Part Per Thousand x(or 8) 1000, TONG Ra (ppt) Rules for Combination of Errors Maximum errors or maximum deviations (E) combine according to different rules from standard errors or standard deviation, (i) For maximum error, the absolute (or relative errors in case of products, quotients and power) are added Eg. In Addition and Subtraction +B-C Maximum error in Z, ive. Ez Ez =Ea+ Eat Ec Where, Ea, Ex, Ecare maximum error in A, B and C respectively Multiplication and Division = the maximum error in Z, ie. Ezfa , Fe si =7 G4 +S sfs) Ex=Z C4 +B 4°8) Product, Quotient and Power ama” cH Zz Maximum error in Z, ie. Ez Se = Mia , Me jue Bea Z (et +e ey (ii) Standard error Addition and Subtraction Z=A+B-C Standard error in Z, .ie. AZ (Az)? = (AA)? +(AB)? +80)? Az = (Gay? + Gay + Cy Multiplication and Division Standard error in Z, ie. AZ r= 4 ee Cee 2 Te = +Qr+ & az=z({Ae+ C+ Product, Quotient and Power wwe? me tye + ne tye + wee az=Z( may? +p + weyExamples Given the summation below: y= 105 (£0.02) + 4.10 (4.0.03) ~ 1.97(0.05) where the values in the parenthesis are the limits estimate of standard errors. Calculate (i) absolute standard error in y (ii) percentage relative error in y. Recall; A+B-C Standard error in Z, ie. AZ (az)? = (aa)? +(aB)? #(aC)? AZ = (MA)? + (AB)? + (AC)? Thus; (Ay)? = (£0.02)? +(40.03)? +(+0.05)? (£0.02)? + (40.03)? + (40.05)? = JE(@.0004 + 0.0009 + 0.0025) = vE0.0038 = =+0.06 ay, 300, % relative error= ot y= 105 +410-1.97=3.18 % relative error = S22 x22, = 189% For more Examples; consult Fundamental Physical Chemistry, Series A , by Olajire Abbas Question Solve this question The unit of viscosity is called poise (7). Viscosity is determined experimentally by measuring the time (t) for certain volume (v) under a pressure (P) according to the Poiseeuille equation: _ per env Ifthere is an error of AP in P, At in t AR inR, AL in L and AV inV a. calculate the% error in poise b, What are the unit of poise in S. 1. units?References Abass A. Olajire 2008: Fundamental University Physical Chemistry, Series A hittps://courses.lumenlearning.com/boundless-statistics/chaptet/measurement-error/, Chapter 5 Errors in Chemical ‘Analyses hittp:// web iyte.edu tr/~serifevalcin/lectures/chem201/en_S.pdf ‘Theory of Errors in Quantitative Analysis. Ligeia _ “Experimental Methods. An Introduction to the Analysis and Presentation of Data,” Les Kirkup, Wiley, (1994) “Data Reduction and Error Analysis for the Physical Sciences.” Philip R. Bevington, MeGraw Hill (1969), * 10