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    Least Square Methods

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    Muhammad Sajjad

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    © All Rights Reserved
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    of 3
    The test statistic can now be calculated as p= Fite U6 0123 _ yg SIWN ~ 0032/ From Table al-5, we find that the critical value of ¢ for 3 degrees of freedom and the 95% confidence level is 3.18, Because t = ~3.18, we conclude that there is a significant difference at the 95% confidence level and, thus, bias in the method, Note that if we were to carry out this test atthe 993% confidence level, ,,, = 5.84 (Table a1-5). Because ~5.84 < 4.375, we would accept the null hypothesis at the 99% con- dence level and conclude there is no dilference between the experimental and the accepted values, ‘Note that sn this example the outcome depends on the confi- dence evel that is used, The choice of confidence level depends ‘on our willingness to accept an error in the outcome.” The significance level (0.05, 0.01, 0.001, etc) is the probability of ‘making an error by rejecting the null hypothesis. Hypothesis testing is widely used in science and engineer ing Comparison of one or two samples is carried out as described here, The principles can, however, be extended to ‘comparisons among more than two population means. Multiple ‘comparisons fall under the general category of analysis of vari ‘ance (ANOVA). These methods use a single test to determine ‘whether thee is a ditference among the population means rath cer than pairwise comparisons as is done with the f test. After ANOVA indicates a potential ditference, multiple comparison procedures can be used to identify which specific population ‘means differ from the others. Experimental design methods take advantage of ANOVA in planning and performing experiments. a1D METHOD OF LEAST SQUARES Most analytical methods are based on a calibration curve in which @ measured quantity y is plotted as a function of the known concentration x of a series of standards. Figure al-6 shows a typical calibration curve, which was computed for the ‘chromatographic determination of isooctane in hydrocarbon samples. The ordinate (the dependent variable) is the area un. der the chromatographic peak for isooctane, and the abscissa (che independent variable) is the mole percent of isooctane. AS is typical, the plot approximates a straight line. Note, however, "hor discussion a ror fn hypothe tenting, ee. 1, Devore, Probably and tats for Engineering and he Seiences, hed, Chap, 8 Boston: Brooks Cle 2016 see. A, Skoog DM. West FJ. Hele and SR. Crouch, Purdament of “Anayial Chemistry, the, Chap 7 Belmont, CA: Brook Cale, 201: 5.8 (Crouch and ff Hele Applications of Mirza" Excel n Analytical Chemis "ora dssion of ANOVA methods, sD. A, Skoog .M. Wes FJ Hale and §, 8 Grouch, Fundamental of Analytical Chemistry, th eda Ses, 7 D Method of Least Squares 903, \ 20 Peak are, abiary S 05 10 15 20 + Concenation af soctan, mol % [FIGURE 21-6 Calibration curve for determining iseactane in hydrocarbon mixtures that not all the data fall exactly on the line because of the random errors in the measurement process. Thus, we must try o find the “best” straight line through the points. Regression analysis provides the means for objectively obtaining such a line and also for specifying the uncertainties associated with its subsequent use, We consider here only the basic method of least squares for two-dimensional data. a1D-1 Assumptions of the Least-Squares Method Two assumptions are made in using the method of least squares The fist is that there is actualy a linear relationship between the measited response y and the standard analyte concentration x. The mathematical relationship that describes this sumption is ealed the ragresion model, which may be represented as yrmetb where b is the y intercept (the value of y when x is 0) and m is the slope of the Tine, We also assume that any deviation of the individual points from the straight line arises from error in the measurement. That is, we assume there is no ertor in x values of the points (concentrations). Both ofthese assumptions are appropriate for many analytical methods, but bear in mind 906 Appendix 1 Evaluation of Analytical Data that whenever there i significant uncertainty in the data, ba sic linear least squares analysis may not give the best straight line. In such a case, a moze complex correlation analysis may be necessary, In addition, simple least squares analysis may not be appropriate when the uncertainties in the y values vary signifi ‘cantly with x. In this case, it may be necessary to apply diferent Weighting factors to the points and perform a weighted least squares analysis. a1D-2 Finding the Least-Squares Line Asillustrated in Figureal-6,the vertical deviation ofeach point from the straight in is called a residual, Te line generated by the least-squares method is the one that minimizes the sum ofthe squares ofthe residuals forall the points. In addition to roving the bed ft between the experimental pointe and the Straight line, the method gives the standard deviations for m and “he leastquares method finds the sum ofthe squares ofthe resale SS, and minimizes these according othe minim zation technigue of calculus! Theva of SS, found from Db. - (0+ mad? ‘where N ie the number of points used. The calculation of the slope and intercept is simplified by defining three quantities S,, Syp and S,, 28 follows Gs Sa = Di - FP = Yd - (al-31) Sy = YO. - FF = Sy (al-32) $= Dl w=) = Ya - SE aay where x, and y, are individual pairs of data for x and y, Nis the number of pairs, and ¥ and Yar the average values for xand y, thats, = Syx/N andy ~ Sy tN. Note that ,, and S,, are the sums ofthe squares of the de vations from the mesh for individual values of x and y. ‘The ‘expressions shown on the fa right in Equations a-31 through 41-33 are more convenient when a calculator without a built-in regression function is being used "or an Bice approach to weighted linear FU Hole, Applications f Micros elm Analy rons CA. Cengage Learning, 2017 pp. 31-397 reason, see SR. Crouch and I Chemistry. 3rd, Bel "the procedure lavolvesdierentting SS. with sespect test and then B sand rtng the derivatives equa 00. Tie ls two equions, called oral “suationsin the two unknowns and These are then ole the eae Six useful quantities can be derived from S,,.$,, and S,, as se Syp and Sy follows: 41. The slope of the tine, m: e139 2 135) 3 @1369) 44. The standard deviation of the slop, s, Ve @rs7) 5, The standard deviation of the intercept 4 (al-38) Vi-Sa De The standard deviation for results obtained from the calibration curve, 5: = 5 139) Equation 1-39 allows us to calculate the standard deviation from the mean J. ofa set of M replicate analyses of unknowns when a calibration curve that contains N points is used; recall that Fis the mean value of y for the N calibration points, This equation is only approximate and assumes that the slope and Intercept are independent parameters, which isnot strictly true, “The standard deviation about regression s, (Equation al-36) is the standard deviation for y when the deviations are mea sured not from the mean of y (as isthe usual case), but from the straight line that results from the least-squares prediction, The value of sis related to 85, by S.-co + made N=2 VN=2 In this equation, the number of degrees of freedom is N- 2 because one degree of freedom is lst in calculating m and one in determining b. The standard deviation about regression is often called the standard error of the estimate, It roughly responds to the size ofa typical deviation from the estimated regression line. Examples al-I1 and al-12 illustrate how these quantities are calculated and used. fee Complete a least-squares analysis of the experimental data provided in the fist two columns of Table al-7 and plotted in Figureal-6. Solution Columns 3,4, and 5 of the table contain computed values for 2S, yfvand xy, with their sums appearing asthe lst entry in ‘each column. Note thatthe number of digits carried in the ‘computed values should be the maximum allowed by the cal- culatoror computer, tat is, rounding should not be performed tun the calculation is complete ‘We now substitute into Equations al-31, a1-32, and 21-33 and obtain yy - (228i = 363775 - = 5.07748 5.365 12.51 = 1ssiss2 ~ SE * 39669 Substitution of these quantities into Equations al-34 and al-35 yields 2.39669 14537 = 20925 = 209 ‘TABLE al-7 Calibration Data for the Chromato- graphic Determination of Isooctane in a Hydrocarbon Mixture co ot res a rn 012390 1.1881 3.1684 6.7600 9.1809 16.0801 36.3775 0.38368 142934 2.80800 4.18140 7.01750 15.8192 0.64481 1.16640 1.90440 3.06250 690201 > anD Method of Least Squares 905 “Thus, the equation for the least-squares ine is y= 209x + 026 Substitution into Equation al-36 yields the standard deviation about regression (= BT 5-2 and substitution into Equation al-37 gives the standard deviation of the slope Sa Ne = 01442 = 014 2 _ feiway Sa V104537 Finally, we find the standard deviation of the intercept from Equation al-38: ‘The calibration curve found in Example al-11 was used for the chromatographic determination of isooctane in a hydro- carbon mixture. A peak area of 2.65 was obtained. Calculate the mole percent of isooctane in the mixture and the standard

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