Page 137 - Modern Analytical Chemistry
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1400-CH05  9/8/99  3:59 PM  Page 120





              120    Modern Analytical Chemistry


                                                                                      x 2
                                                         x i           y i                          x i y i
                                                                                       i
                                                        0.000         0.00           0.000         0.000
                                                        0.100        12.36           0.010         1.236
                                                        0.200        24.83           0.040         4.966
                                                        0.300        35.91           0.090        10.773
                                                        0.400        48.79           0.160        19.516
                                                        0.500        60.42           0.250        30.210
                                                  Adding the values in each column gives
                                                                                     2
                                                        Sx i = 1.500  Sy i = 182.31  Sx i = 0.550  Sx iy i = 66.701
                                                  Substituting these values into equations 5.12 and 5.13 gives the estimated slope
                                                                   ()( .       1 500 182 31)
                                                                                        .
                                                                                   )(
                                                                    6 66 701) – ( .
                                                               b 1 =                  2     = 120 706
                                                                                                .
                                                                       6 0 550) – ( .
                                                                       ()(.      1 500)
                                                  and the estimated y-intercept
                                                                                 .
                                                                                    )
                                                                      182 31 – ( 120 706 1 500)
                                                                         .
                                                                                      .
                                                                                     (
                                                                 b 0 =                      = 0 209
                                                                                              .
                                                                                6
                                                  The relationship between the signal and the analyte, therefore, is
                                                                       S meas = 120.70 ´C S + 0.21
                                                  Note that for now we keep enough significant figures to match the number of
                                                  decimal places to which the signal was measured. The resulting calibration
                                                  curve is shown in Figure 5.10.
                                                     80

                                                     60


                                                   S meas  40




                                                     20



                                                      0
                                                      0.0    0.1   0.2   0.3    0.4   0.5   0.6
                                                                          C A
                                                  Figure 5.10
                                                  Normal calibration curve for the hypothetical data in Table 5.1,
                                                  showing the regression line.



                                              Uncertainty in the Regression Analysis  As shown in Figure 5.10, the regression
                                              line need not pass through the data points (this is the consequence of indeter-
                                              minate errors affecting the signal). The cumulative deviation of the data from
                                              the regression line is used to calculate the uncertainty in the regression due to
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