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                        2   is the lower  α /2 percentile point of the χ 2
                       χ ν,α/2                                 distribution, where ν  =  n  − 2 degrees of freedom
                                                     2
                       associated with the variance estimate (s ).
                        This interval for y and the Working–Hotelling confidence band for the calibration line are used to
                       estimate a confidence interval about   for the true concentration ξ. This typically is done graphically.x ˆ
                       Hunter (1981) provides a full derivation and explanation of the procedure.



                       Case Study: Solution
                       The fitted model calibration line is:

                                                 y =  b 0 +  b 1 x =  0.556 +  139.759x

                                               2
                       The estimate of the variance is s  = 1.194, which has ν = 15 − 2 = 13 degrees of freedom. The estimated
                       variances of the parameters are Var (b 0 ) = 0.2237 and Var (b 1 ) = 8.346. The appropriate value of the t
                       statistic for estimation of the 95% confidence intervals of the parameters is t 13,0.025  = 2.16, giving 95%
                       confidence intervals as follows:

                                         β 0 =  0.566 ± 1.023  or   – 0.457 <  β 0 <  1.589
                                         β 1 =  139.759 ± 6.242  or  133.52 <  β 1 <  146.00

                       Using the Calibration Curve to Predict Concentrations

                       Suppose that the chemist measured a peak area of 22.0. The predicted concentration is read from the
                       calibration line or computed from the calibration equation:

                                          x ˆ =  ( yb 0 )/b 1 =  ( 22.0 0.566)/139.76 =  0.153.
                                                –
                                                              –
                       To establish confidence limits for the true concentration, first determine the confidence limits for the
                       value y = 22.0. Then, using the Working-Hotelling confidence band for the calibration line, translate the
                       confidence limits for y into confidence limits for x. Figure 36.2 shows the fitted calibration line with
                       Working-Hotelling 95% confidence band. Only part of the range of dye concentration is shown in order
                       to expand the scale.


                                              30
                                                       24.25
                                                     y = 22.0
                                            HPLC Peak Area  10       0. 132  ^  0.176
                                              20
                                                       19.78








                                               0                      x = 0.153
                                                0.00             0.05              0.10              0.15             0.20
                                                         Dye Concentration

                       FIGURE 36.2 The lower-concentration portion of the fitted calibration curve with its Working-Hotelling 95% band showing
                       an example of predicting x from y = 22.0.
                       © 2002 By CRC Press LLC
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