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EXAMPLE 10.

13

An overall extraction and analysis method for lindane gave the following
results when applied to lindane-free soil samples: μg/L lindane = 0.3, 1.5, -
0.5, 0.7, - 1.0, 1.2, 0.1. Calculate the lindane detection limit for the analysis
(at the 99% confidence level) for (a) a single analysis, and (b) the mean of
four analyses.

Solution:

We calculate ss as follows:

∑ xi = 0.3 + 1.5 - 0.5 + 0.7 - 1.0 + 1.2 + 0.1 = 2.3

∑ xi2 = 0.09 + 2.25 + 0.25 + 0.49 + 1.0 + 1 .44 + 0.01 = 5.53

ss =
√ 5.53−(2.3 2/7)
7−1
= 0.89 μg/L

(a) For a single analysis, n = 1 and the number of degrees of freedom is 1


+ 7 - 2 = 6. From Table 10.1, we see t = 3.707. Thus,

(b)
MDL = 3.707(0.89)
√ 1+7
1 (7 )
= 3.96(0.89) = 3.5 μg/L
For four analyses, n = 4, the number of degrees of freedom is 9 and t =
3.25. For this case,

MDL = 3.25(0.89)
√ 4+7
4 (7 )
= 2.04(0.89) = 1.8 μg/L

EXAMPLE 10.14
Determine the slope and intercept for the regression line in Fig. 10.7, and
determine the standard deviation for each,
The data upon which Fig. 10.7 is based and relevant calculations are
contained in the following table.

Benzene Peak
xi , μg/L Area xi2 yi2 xiyi
yi , cm2
25 0.54 625 0.2916 13.5
50 0.96 2,500 0.9216 48
100 1.82 10,000 3.3124 182
150 2.30 22,500 5.2900 345
200 3.20 40,000 10.2400 640
300 5.17 90,000 26.7289 1,551
∑ = 825 13.99 165,625 46.7845 2,780
Average = 137.5 2.331

Solution:

Relevant calculations then are:

165,625 ( 13.99 )−825(2780)


a= 6 ( 165,625 )−(825) 2
= 0.077

6 (2780 )−825(13.99)
b= = 0.0164
6 (165,625 )−(825) 2

sy =
√ [ 46.7845−( 13.99) 2/6 ] − ( 0.0164 ) 2[165,625−(825) 2/6]
6−2
= 0.179

sa =
√ 0.179 2(165,625)
6 ( 165,625 ) −(825)2
= 0.130

sb =
√ 6( 0.179) 2
6 ( 165,625 ) −(825)2
= 0.00078
EXAMPLE 10.15

A sample is analyzed by gas chromatography for benzene, giving a peak


area of 1.97 cm2. Determine the benzene concentration and the 95% CL
assuming (a) one sample only is analyzed, and (b) four replicates of the
sample are analyzed.

Solution:

For both cases, the benzene concentration is given by Eq. (10.27). Using the
results of Example 10.14,

y i−a 1.97−0.075
xi = b
= 0.0164
= 115 μg/L

(a) For the first case, m = 1. There is only one sample, and thus yy c = 1.97
cm2. The standard deviation is found with Eq. (10.33):

sc =
0.179
0.0164 √ 1 1
+ +
6( 1.97−2.331)2
1 6 ( 0.0164 ) 2[6 ( 165,625 )−(825)2]
= 11.8

For the 95% confidence interval we have 6 - 2 or 4 degrees of freedom, as we


lose one degree of freedom each for the determination of a and b: From Table
10.1, t equals 2.776, and

95% CL = xy ± tsc = 115 ± 2.776(11.8)

= 115 ± 33 μg/L

(b) For the second case, m = 4, for which,

sc =
0.179
0.0164 √ 1 1
+ +
6 (1.97−2.331) 2
4 6 ( 0.0164 ) 2[6 ( 165,625 )−(825) 2]
= 7.12

95% CL = xy ± tsc = 115 ± 2.776(7.12)

= 115 ± 20 μg/L

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