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.
