Question 5.13: The following data were recorded during the preparation of a...

The following data were recorded during the preparation of a calibration curve, where \bar S_{meas} and s are the mean and standard deviation, respectively, for three replicate measurements of the signal.

C_A \bar S_{meas} s
0.000 0.00 0.02
0.100 12.36 0.02
0.200 24.83 0.07
0.300 35.91 0.13
0.400 48.79 0.22
0.500 60.42 0.33

Determine the relationship between \bar S_{meas}  and  C_A using a weighted linear regression model.

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Once again, as you work through this example, remember that x represents the concentration of analyte in the standards (C_S), and y corresponds to the average signal (\bar S_{meas}). We begin by setting up a table to aid in the calculation of the weighting factor.

x_i y_i s_i s_i^{-2} w_i
0.000 0.00 0.02 2500.00 2.8339
0.100 12.36 0.02 2500.00 2.8339
0.200 24.83 0.07 204.08 0.2313
0.300 35.91 0.13 59.17 0.0671
0.400 48.79 0.22 20.66 0.0234
0.500 60.42 0.33 9.18 0.0104

Adding together the values in the forth column gives

Σs_i^{–2} = 5293.09

which is used to calculate the weights in the last column. As a check on the calculation, the sum of the weights in the last column should equal the number of calibration standards, n. In this case

Σw_i = 6.0000

After the individual weights have been calculated, a second table is used to aid in calculating the four summation terms in equations 5.22 and 5.23.

b_1=\frac{n\sum w_ix_iy_i-\sum w_ix_i \sum w_iy_i}{n\sum{w_ix_i^2-(\sum{w_ix_i} )^2}}                  5.22

 

b_0=\frac{\sum w_iy_i-b_1\sum w_ix_i}{n}            5.23

 

x_i y_i w_i w_ix_i w_iy_i w_ix_i² w_ix_iy_i
0.000 0.00 2.8339 0.0000 0.0000 0.0000 0.0000
0.100 12.36 2.8339 0.2834 35.0270 0.0283 3.5027
0.200 24.83 0.2313 0.0463 5.7432 0.0093 1.1486
0.300 35.91 0.0671 0.0201 2.4096 0.0060 0.7229
0.400 48.79 0.0234 0.0094 1.1417 0.0037 0.4567
0.500 60.42 0.0104 0.0052 0.6284 0.0026 0.3142

Adding the values in the last four columns gives

Σw_ix_i = 0.3644           Σw_iy_i = 44.9499            Σw_ix_i^2= 0.0499            Σw_ix_iy_i = 6.1451

Substituting these values into the equations 5.22 and 5.23 gives the estimated slope

b_1=\frac{(6)(6.1451)-(0.3644)(44.9499)}{(6)(0.0499)-(0.3644)^2} =122.985

and the estimated y-intercept

b_0=\frac{44.9499-(122.985)(0.3644)}{6} =0.0224

The relationship between the signal and the concentration of the analyte, therefore, is

\bar S_{meas}= 122.98 × C_A + 0.02

with the calibration curve shown in Figure 5.12.

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