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Fundamentals of Analytical Chemistry: 8th ed.

Chapter 8

Chapter 8

8-1 Step 1: Identification of the population from which the sample is to be drawn.

Step 2: Collection of a gross sample.

Step 3: Reduction of the gross sample to a small quantity of homogeneous material for

analysis.

8-2 The objective of the sampling step is to produce a homogeneous laboratory sample of a

few hundred grams or less having a composition that is identical to the average

composition of the bulk of the material being sampled.

8-3 The gross sample weight is determined by (1) the uncertainty that can be tolerated

between the composition of the gross sample and that of the whole, (2) the degree of

heterogeneity of the whole, and (3) the level of particle size at which heterogeneity

begins.

8-4 s02 = s s2 + s m2

From the NIST sample: s m2 = 0.00873

From the gross sample: s02 = 0.155

s s = 0.155 0.00873 = 0.38

s 0.38
The relative standard deviation = s 100% = 100% = 0.76%
x 49.92

8-5 (a) r = (1 p) / Np (where p = 14/250 = 0.0560)

r = (1 0.0560) /(250 0.0560) = 0.260 or 26%

(b) abs = 140.26 = 3.6 = 4 tablets


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

90% CI = 14 z N = 14 1.64 3.6 / 1 = 146

(where z = 1.64 was obtained from Table 7-1)

(c) N = (1-0.056)/[(0.10)20.056] = 1686 = 1.69103

8-6 (a) N =
(1 p ) = (1 0.02 ) =
49.0
= 784
2 2
p r 0.02(0.25) (0.25) 2

(b) N = 49.0/(0.1)2 = 4.9 103

(c) N = 49.0/(0.05)2 = 2.0 104

(d) N = 49.0/(0.01)2 = 4.9 105

8-7 (a) 250 =


(1 52 / 250)
(52 / 250) 2r

r = 0.12 = 12%

(b) Here, the absolute standard deviation of the estimate is sought.

abs = 750 12(52/250)0.12 = 224.6 = 220 broken bottles

(c) 90% CI = 750 12 52/250 zs / N = 1872 1.64224.6/ 1

= 1872 368 = 1900 400 broken bottles

(Note: In the first printing of the text, the answer in the back of the book was in error.)

(d) N =
(1 0.21) = 1.5 103 bottles
2
0.21(0.05)

2 2
d d P PB
8-8 N = p (1 p ) A 2 B A
d r P

(a) d = 7.3 0.15 + 2.6 0.85 = 3.3

P = 0.15 7.3 0.87 100 / 3.3 = 29%


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

2 2
7.3 2.6 87 0
N = 0.15(1 0.15)
2
4
= 3.5 10 particles
(3.3) 0.010 29

(b) mass = (4/3)(0.20 cm)3 3.3(g/cm3) 3.5 104

= 3.9 103 g

(c) 0.600 = (4/3)(r)3 3.3(g/cm3) 3.5 104

r = 0.011 cm (diameter = 0.22 mm)

8-9 Recall that s0 = (ss2 + sm2)1/2. For both Scheme A and Scheme B the contribution of the

method variance, sm2, will be both small relative to the sampling variance, ss2, and

essentially the same. The sampling variance, ss2, will be lower for Scheme A, however,

since the results from 5 samples are evaluated as opposed to 3 samples in Scheme B.

Thus, Scheme A will have the lower variance.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-10 (a) Single factor ANOVA generated using Excels Analysis ToolPak.

Anova: Single Factor

SUMMARY
Groups Count Sum Average Variance
Column 1 3 185 61.66667 2.333333333
Column 2 3 172 57.33333 0.333333333
Column 3 3 146 48.66667 4.333333333
Column 4 3 170 56.66667 6.333333333

ANOVA
Source of Variation SS df MS F P-value F crit
Between Groups 264.25 3 88.08333 26.425 0.000167 4.066180281
Within Groups 26.66666667 8 3.333333

Total 290.9166667 11

From ANOVA the Between Groups SS value of 264.25 indicates that the mean

concentrations do vary significantly from day to day.

(b) SST is the total variance and is the sum of the within a days variance, SSE, and the

day-to-day variance, SSF; SST = SSE + SSF. The within a days variance, SSE, reflects

the method variance, SSM. The day-to-day variance, SSF, reflects the sum of the method

variance, SSM, and the sampling variance, SSS; SSF = SSM + SSS. Thus,

SST = SSM + SSM + SSS and SSS = SST - 2SSM

SSS = 290.92 - 226.67 = 237.58

(c) The best approach to lowering the overall variance would be to reduce the sampling

variance, SSS, since this is the major component of the total variance.

8-11 See Example 8-1

d = 7.3 0.01 + 2.6 0.99 = 2.6 g/cm3

P = 0.01 7.3 0.87 100 / 2.6 = 2.4%


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

2 2
7.3 2.6 87 0 4
N = 0.01(1-0.01) = 4.110 particles
2.6 2.6 0.05 2.4

mass = (4/3)(0.25)3 2.6 4.1 104 / 454 = 15 lb; insufficient sample

8-12 See Example 8-3

(1.96) 2 (0.2) 2
Using t = 1.96 for infinite samples N = = 5.0176
(3.5) 2 (0.05) 2

(2.45) 2 (0.2) 2
Using t = 2.45 for 6 samples N = = 7.84
(3.5) 2 (0.05) 2

(2.31) 2 (0.2) 2
Using t = 2.31 for 8 samples N = = 6.96
(3.5) 2 (0.05) 2

(2.36) 2 (0.2) 2
Using t = 2.36 for 7 samples N = = 7.2746
(3.5) 2 (0.05) 2

8 samples need to be analyzed to satisfy the requirements.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-13

A B C D E F G H I
2-
1 mg SO4 /L Reading
2 0.00 0.06
3 5.00 1.48
4 10.00 2.28
5 15.0 3.98
6 20.0 4.61
7 unknown 2.84
8 Part (b)
9 Slope 0.232
10 Intercept 0.162
11 Std Error 0.2752453
12 N 5
13 Sxx 250
14 ybar 2.482
15
16 Parts (e) & (f)
17 M 1
18 c unknwn 11.5431 SD in c 1.305 CV 11.3036
19 M 6
20 c unknwn 11.5431 SD in c 0.728 CV 6.3040
21
22 Spreadsheet Documentation
23 B9 = SLOPE(B2:B6,A2:A6)
24 B10 = INTERCEPT(B2:B6,A2:A6)
25 B11 = STEYX(B2:B6,A2:A6)
26 B12 = COUNT(B2:B6)
27 B13 = DEVSQ(A2:A6)
28 B14 = AVERAGE(B2:B6)
29 B18 = (B7-B10)/B9
30 E18 = (B11/B9)*SQRT(1/B17+1/B12+((B7-B14)^2)/((B9^2)*B13))
31 H18 = E18/B18*100

(a) See spreadsheet

(b) m = 0.232 and b = 0.162

(c) See spreadsheet


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

(d) ANOVA generated using Excels Analysis ToolPak.

SUMMARY OUTPUT

Regression Statistics
Multiple R 0.9916602
R Square 0.9833899
Adjusted R Square 0.9778533
Standard Error 0.2752453
Observations 5

ANOVA
Significance
df SS MS F F
Regression 1 13.456 13.456 177.6135 0.000913111
Residual 3 0.22728 0.07576
Total 4 13.68328

Standard Lower Upper Lower Upper


Coefficients Error t Stat P-value 95% 95% 95.0% 95.0%
Intercept 0.162 0.213204 0.759835 0.502609 -0.516511 0.840511 -0.51651 0.840511
X Variable 1 0.232 0.017408 13.32717 0.000913 0.176600 0.287400 0.1766 0.2874

The large F value of 177.6 indicates that the regression is significant. The R2 value of

0.9834 measures the fraction of the variation explained by the regression. The adjusted

R2 value of 0.9779 indicates the price to pay for adding an additional parameter.

(e) cUnk = 11.5 mg/mL; sUnk = 1.3 mg/mL; CV = 11.3%

(f) cUnk = 11.5 mg/mL; sUnk = 0.73 mg/mL; CV = 6.3%


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-14

A B C D E F G H I
1 pCa E, mV
2 5.00 -53.8
3 4.00 -27.7
4 3.00 2.7
5 2.00 31.9
6 1.00 65.1
7 unknown 10.7
8 Part (b)
9 Slope -29.74
10 Intercept 92.86
11 Std Error 2.1382
12 N 5
13 Sxx 10
14 ybar 3.64
15
16 Parts (d) & (e)
17 (d) M 1
18 (d) pCa unknwn 2.7626 (d) SD in pCa 0.0789 (d) RSD 0.0286
19 (e) M 2
20 (e) pCa unknwn 2.7626 (e) SD in pCa 0.0604 (e) RSD 0.0219
21 (e) M 8
22 (e) pCa unknwn 2.7626 (e) SD in pCa 0.0413 (e) RSD 0.0150
23
24 Spreadsheet Documentation
25 B9 = SLOPE(B2:B6,A2:A6)
26 B10 = INTERCEPT(B2:B6,A2:A6)
27 B11 = STEYX(B2:B6,A2:A6)
28 B12 = COUNT(B2:B6)
29 B13 = DEVSQ(A2:A6)
30 B14 = AVERAGE(B2:B6)
31 B18 = (B7-B10)/B9
32 E18 = ABS((B11/B9)*SQRT(1/B17+1/B12+((B7-B14)^2)/((B9^2)*B13)))
33 H18 = E18/B18

(a) See spreadsheet

(b) Equation of the line: y = -29.74 x + 92.86


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

(c) ANOVA generated using Excels Analysis ToolPak.

SUMMARY OUTPUT

Regression Statistics
Multiple R 0.9992255
R Square 0.9984516
Adjusted R Square 0.9979355
Standard Error 2.1382236
Observations 5

ANOVA
Significance
df SS MS F F
Regression 1 8844.68 8844.68 1934.53 2.587E-05
Residual 3 13.72 4.572
Total 4 8858.39

Standard Lower Upper Lower Upper


Coefficients Error t Stat P-value 95% 95% 95.0% 95.0%
Intercept 92.86 2.2426 41.408 3.1E-05 85.72308 99.99692 85.72308 99.99692
X Variable 1 -29.74 0.6762 -43.983 2.6E-05 -31.89186 -27.5881 -31.8919 -27.5881

The large F value of 1934.5 indicates that the regression is significant. The R2 value of

0.9985 measures the fraction of the variation explained by the regression. The adjusted

R2 value of 0.9979 indicates the price to pay for adding an additional parameter.

(d) pCaUnk = 2.763 spCa = 0.079 RSD = 0.0286 (CV = 2.9%)

(e) For 2 replicate measurements:

pCaUnk = 2.763 spCa = 0.060 RSD = 0.0219 (CV = 2.2%)

For 8 replicate measurements:

pCaUnk = 2.763 spCa = 0.041 RSD = 0.0150 (CV = 1.5%)


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-15

A B C D E F G H I

1 MVK Area
2 0.500 3.76
3 1.50 9.16
4 2.50 15.03
5 3.50 20.42
6 4.50 25.33
7 5.50 31.97
8 Unknown1 10.3
9 Unknown2 22.8
10 Part (a)
11 Slope 5.57
12 Intercept 0.901667
13 Std Error 0.40303
14 N 6
15 Sxx 17.5
16 ybar 17.61167
17 Parts (d)-(f)
18 M 1
19 c Unk 1 1.687313 SD c Unk 1 0.081386 RSD c Unk 1 0.048234
20 c Unk 2 3.931478 SD c Unk 2 0.079798 RSD c Unk 2 0.020297
21
22 M 4
23 c Unk 1 1.687313 SD c Unk 1 0.051933 RSD c Unk 1 0.030778
24 c Unk 2 3.931478 SD c Unk 2 0.049407 RSD c Unk 2 0.012567
25
26 Spreadsheet Documentation
27 B11 = SLOPE(B2:B7,A2:A7)
28 B12 = INTERCEPT(B2:B7,A2:A7)
29 B13 = STEYX(B2:B7,A2:A7)
30 B14 = COUNT(B2:B7)
31 B15 = DEVSQ(A2:A7)
32 B16 = AVERAGE(B2:B7)
33 B19 = (B8-B11)/B12
34 E19 = (B13/B11)*SQRT(1/B18+1/B14+((B8-B16)^2)/((B11^2)*B15))
35 H19 = E19/B19
36 E23 = (B13/B11)*SQRT(1/B22+1/B14+((B8-B16)^2)/((B11^2)*B15))
37 H23 = E23/B23

(a) m = 5.57 and b = 0.90


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

(b) ANOVA generated using Excels Analysis ToolPak.

SUMMARY OUTPUT

Regression Statistics
Multiple R 0.9994022
R Square 0.9988047
Adjusted R Square 0.9985059
Standard Error 0.4030302
Observations 6

ANOVA
Significance
df SS MS F F
Regression 1 542.9358 542.936 3342.51 5.3597E-07
Residual 4 0.6497 0.16243
Total 5 543.5855

Standard Lower Upper Lower Upper


Coefficients Error t Stat P-value 95% 95% 95.0% 95.0%
Intercept 0.9016667 0.332580 2.71113 0.05347 -0.021725 1.8251 -0.0217 1.8251
X Variable 1 5.57 0.096343 57.8145 5.4E-07 5.302509 5.8375 5.3025 5.8375

(c) See Spreadsheet

(d) cMVK = 1.69 mmol/L

(e) For 1 measurement

sMVK = 0.080 RSD = 0.0482 (CV = 4.8%)

For 4 replicate measurements

sMVK = 0.052 RSD = 0.308 (CV = 3.1%)

(f) cMVK = 3.93 mmol/L

sMVK = 0.08 RSD = 0.0203 (CV = 2.03%)

cMVK = 3.93 mmol/L

sMVK = 0.05 RSD = 0.0126 (CV = 1.26%


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-16

A B C D E F G H I
1 Glucose, M A
2 0.0 0.002
3 2.0 0.150
4 4.0 0.294
5 6.0 0.434
6 8.0 0.570
7 10.0 0.704
8 Unknown 0.350
9
10 Part (a)
11 Slope 0.0701429
12 Intercept 0.0082857
13 Std Error 0.0055806
14 N 6
15 Sxx 70
16 ybar 0.359
17
18 Parts (b) & (c) LINEST Values
19 SD m 0.0006670 m 0.070143 0.008286 b
20 SD b 0.0040389 SD m 0.000667 0.004039 SD b
21 t(0.05,4) 2.7764509 r2 0.999638 0.005581 SE
22 95%CI for m 0.0018519 F 11058.76 4 df
23 95% CI for b 0.0112139 SSR 0.344401 0.000125 SSE
24 Part (d)
25 M 1
26 c Unk 4.8716904
27 SD c Unk 0.0859435
28 t(0.05,4) 2.7764509
29 95%CI c Unk 0.2386179
30
31 Spreadsheet Documentation
32 B11 = SLOPE(B2:B7,A2:A7) E19:F23 = LINEST(B2:B7,A2:A7,TRUE,TRUE)
33 B12 = INTERCEPT(B2:B7,A2:A7) B21 = TINV(0.05,4)
34 B13 = STEYX(B2:B7,A2:A7) B22 = B21*B19
35 B14 = COUNT(B2:B7) B23 = B21*B20
36 B15 = DEVSQ(A2:A7) B26 = (B8-B12)/B11
37 B16 = AVERAGE(B2:B7) B27 = (B13/B11)*SQRT(1/B25+1/B14+((B8-B16)^2)/((B11^2)*B15))
38 B19 = E20 B28 = TINV(0.05,4)
39 B20 = F20 B29 = B27*B28

(a) m = 0.07014 and b = 0.008286

(b) sm = 0.00067 sb = 0.004039 SE = 0.00558


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

(c) 95% CLm = m t sm = 0.07014 0.0019

95% CLb = b t sb = 0.0083 0.0112

(d) cUnk = 4.8717 mM sUnk = 0.0859

95% CLUnk = cUnk t sUnk = 4.87 0.24 mM


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-17

A B C D E F G H
1 c, M E, mV
2 0.20000 106
3 0.07940 115
4 0.06310 121
5 0.03160 139
6 0.02000 153
7 0.01260 158
8 0.00794 174
9 0.00631 182
10 0.00398 187
11 0.00200 211
12 0.00126 220
13 0.00100 226
14 Part (a)
15 -log c E
16 0.69897 106
17 1.10018 115
18 1.19997 121 LINEST Values Parts (d) & (e)
19 1.50031 139 m 55.3722306 58.03845931 b
20 1.69897 153 SDm 1.75551156 3.639896675 SDb
21 1.89963 158 r2 0.9900487 4.289517151 SE
22 2.10018 174 F 994.893631 10 df
23 2.19997 182 SSR 18306.0004 183.9995739 SSE
24 2.40012 187 Part (b)
25 2.69897 211 Slope 55.37223
26 2.89963 220 Intercept 58.03846
27 3.00000 226 Part (c) t(0.05,10) 2.2281392
28 SD m 1.75551 95%CL for m 3.9115242
29 SD b 3.63990 95% CL for b 8.1101966
30
31 Spreadsheet Documentation
32 A16 = -LOG(A2) E29 = F20
33 E19:F23 = LINEST(B16:B27,A16:A27,TRUE,TRUE) G27 = TINV(0.05,10)
34 E25 = E19 G28 = G27*E28
35 E26 = F19 G29 = G27*E29
36 E28 = E20

(a) See Spreadsheet

(b) y = 55.37 x + 58.04

(c) 95% CLm = 55.37 3.91 and 95% CLb = 58.04 8.11

(d) From the LINEST values F = 994.9. The large value of F indicates that the
Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

regression is significant.

(e) ANOVA generated using Excels Analysis ToolPak.

SUMMARY OUTPUT

Regression Statistics
Multiple R 0.9950119
R Square 0.9900487
2
Adjusted R 0.9890536
Standard Error 4.2895172
Observations 12

ANOVA
Significance
df SS MS F F
Regression 1 18306 18306 994.894 2.4116E-11
Residual 10 183.9996 18.39996
Total 11 18490

Standard Lower Upper Lower Upper


Coefficients Error t Stat P-value 95% 95% 95.0% 95.0%
Intercept 58.03845931 3.639897 15.94508 1.9E-08 49.9282627 66.14866 49.92826 66.14866
X Variable 1 55.37223056 1.755512 31.54193 2.4E-11 51.4607064 59.28375 51.46071 59.28375

(e) From ANOVA the standard error of the estimate is 4.29. The correlation coefficient,

R, is (0.9900487)1/2 = 0.995 and the multiple R is 0.995.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-18

A B C D E F G H I
-1
1 Temp, K k, s
2 599 0.00054
3 629 0.0025
4 647 0.0052
5 666 0.014
6 683 0.025
7 700 0.064
8 Part (a)
9 1000/Temp log(k)
10 1.6694491 -3.26761
11 1.5898251 -2.60206
12 1.5455951 -2.284
13 1.5015015 -1.85387
14 1.4641288 -1.60206
15 1.4285714 -1.19382
16
17 Part (b)
18 Slope -8.45629 LINEST Values
19 Intercept 10.8311 m -8.45629 10.8311 b
20 Std Error 0.045927 SD m 0.23362 0.358671 SD b
21 N 6 r2 0.996956 0.045927 SE
22 Sxx 0.038647 F 1310.21 4 df
23 ybar -2.1339 SSR 2.763575 0.008437 SSE
24 Part (c)
25 EA = 38697 cal/mol SD EA = 1069
26
27 Spreadsheet Documentation
28 A10 = 1000/A2 B22 = DEVSQ(A10:A15)
29 B10 = -LOG(B2) B23 = AVERAGE(B10:B15)
30 B18 = SLOPE(B10:B15,A10:A15) E19:F23 = LINEST(B10:B15,A10:A15,TRUE,TRUE)
31 B19 = INTERCEPT(B10:B15,A10:A15) B25 = -B18*2.303*1.987*1000
32 B20 = STEYX(B10:B15,A10:A15) F25 = E20*2.303*1.987*1000
33 B21 = COUNT(B10:B15)

(a) See Spreadsheet

(b) m = -8.456 and b = 10.831 and SE = 0.0459

(c) EA = -m 2.303 R 1000 (Note: m has units of mK)

= -(-8.456 mK)(2.303)(1.987 cal mol-1 K-1)(1000 K/mK)

= 38697 cal/mol
Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

sEA = sm 2.303 R 1000

= 1069 cal/mol

Thus, EA = 38,697 1069 cal/mol or 38.7 1.1 kcal/mol

(d) H0: EA = 41.00 kcal/mol; HA: EA 41.00 kcal/mol.

t = (38.697 41.00)/1.069 = -2.15

t(0.025, 4) = 2.776

Since t > tcrit we retain H0. There is no reason to doubt that EA is not 41.00 kcal/mol at

the 95% confidence level.


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-19

A B C D E F G H I
1 % Water Asample Part (a)
2 4.00 0.15
3 8.00 0.23
4 12.00 0.19
5 16.00 0.57
6 20.00 0.43
7
8 LINEST Values
9 m 0.0225 0.044 b
10 SD m 0.00993 0.13172 SD b
11 r2 0.63123 0.12559 SE
12 F 5.13525 3 df
13 SSR 0.081 0.04732 SSE
14
15 Part (b)
16 % Water Asample Astd Ratio
17 4.00 0.15 0.75 0.2000
18 8.00 0.23 0.60 0.3833
19 12.00 0.19 0.31 0.6129
20 16.00 0.57 0.70 0.8143
21 20.00 0.43 0.45 0.9556
22 Unknown 0.37 0.47 0.7872
23
24 LINEST Values
25 m 0.04855 0.0106 b
26 SD m 0.00207 0.02747 SD b
27 r2 0.99457 0.02619 SE
28 F 549.836 3 df
29 SSR 0.37716 0.00206 SSE
30
31 Part (c)
32 With Internal Standard Spreadsheet Documentation
33 % Water Unknown 15.996 B9:C13 = LINEST(B2:B6,A2:A6,TRUE,TRUE)
34 D17 = B17/C17
35 B25:C29 = LINEST(D17:D21,A17:A21,TRUE,TRUE)
36 C33 = (D22-C25)/B25

(a) See Spreadsheet

(b) The linearity is much better when using internal standards (compare R2 and F values).

Taking the ratio compensates for systematic errors that affect both the sample and the
Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

internal standard.

(c) 15.996% (Note: In the first printing of the text, the answer in the back of the book

was in error.)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-20

A B C D E F G H I
1 c K, ppm I(K) Part (a)
2 1.0 10.0
3 2.0 15.3
4 5.0 34.7
5 7.5 65.2
6 10.0 95.8
7 20.0 110.2
8
9 LINEST Values
10 m 5.61133 12.6474 b
11 SD m 1.13079 11.1776 SD b
12 r2 0.86026 17.5622 SE
13 F 24.6245 4 df
14 SSR 7594.94 1233.72 SSE
15 Part (b)
Ratio
16 c K, ppm I(K) I(Li) I(K) / I(Li)
17 1.0 10.0 10.0 1.000
18 2.0 15.3 7.5 2.040
19 5.0 34.7 6.8 5.103
20 7.5 65.2 8.5 7.671
21 10.0 95.8 10.0 9.580
22 20.0 110.2 5.8 19.000
23 Unknown 47.3 9.1 5.198
24
25 LINEST Values
26 m 0.94223 0.25369 b
27 SD m 0.0147 0.14534 SD b
28 r2 0.99903 0.22836 SE
29 F 4106.56 4 df
30 SSR 214.143 0.20859 SSE
31
32 Part (c) Spreadsheet Documentation
33 With Internal Standard B10:C14 = LINEST(B2:B7,A2:A7,TRUE,TRUE)
34 c K, Unknown 5.24725 D17 = B17/C17
35 B26:C30 = LINEST(D17:D22,A17:A22,TRUE,TRUE)
36 C34 = (D23-C26)/B26

(a) and (c) See Spreadsheet

(b) The linearity is much better when using internal standards (compare R2 and F values). Taking

the ratio compensates for systematic errors that affect both the sample and the internal standard.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

c Unk A(sample - blank)


8-21 (a) =
(VStd cStd + VUnk cUnk ) / VTot A(sample + addition - blank)

c Unk (0.520 0.020)


=
(0.1000 mL 1000 g/mL + 100.0 mL cUnk ) 1.020
(100.1 mL)

c Unk
= 0.490196
0.99900 + 0.99900c Unk

cUnk = 0.490196(0.99900 + 0.99900 cUnk)

0.510294 cUnk = 0.489706

cUnk = 0.96 g/mL

c Unk (0.520 0.100)


(b) =
(0.1000 mL 1000 g/mL + 100.0 mL cUnk ) (1.020 0.080)
(100.1 mL)

Proceeding as in (a) we obtain cUnk = 0.81 g/mL

%error = (0.96 0.81)/0.81 100% = 19%

8-22 See Example 8-8

(0.300)(1.00 10 3 )(1.00)
cu = = 2.493810-5 M
(0.530)(51.00) (0.300)(50.00)

To obtain the concentration of the original sample, we need to multiply by 25.00/1.00.

cu = (2.493810-5 M)(25.00)/(1.00) = 6.2310-4 M


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-23

A B C D E F G
1 cZn, ng/mL A A A Mean A SD A
2 0.0 0 0 0 0.00000 0.0047
3 5.0 0.0519 0.0463 0.0485 0.04890 0.002821
4 10.0 0.0980 0.1033 0.0925 0.09793 0.005400
5 Unknown 0.0672 0.0614 0.0661 0.06490 0.003081
6 Part (c) Part (a)
7 calibration sensit. 0.0097933
8 analytical sensit. 3.4711550at 5.0 ng/mL
9
10 DL = ksb/m 1.4397549
11 Part (b) & (d)
12 Slope 0.0097933
13 Intercept -0.0000222
14 c unknwn 6.6292262
15 Std Error 0.0000544
16 N 3
17 Sxx 50
18 ybar 0.0489
19 M 3
20 SD in c 0.004768913
21
22
23
24
25 Spreadsheet Documentation
26 E2 = AVERAGE(B2:D2) B14 = (E5-B13)/B12
27 F2 = STDEV(B2:D2) B15 = STEYX(E2:E4,A2:A4)
28 B7 = SLOPE(E2:E4,A2:A4) B16 = COUNT(E2:E4)
29 B8 = B7/F3 B17 = DEVSQ(A2:A4)
30 B10 = 3*F2/B7 B18 = AVERAGE(E2:E4)
31 B12 = SLOPE(E2:E4,A2:A4) B20 = (B15/B12)*SQRT(1/B19+1/B16+((B5-B18)^2)/((B12^2)*B17))
32 B13 = INTERCEPT(E2:E4,A2:A4)

(a) See Spreadsheet

(b) calibration sensitivity = 0.0098 analytical sensitivity = 3.47

(c) For k = 3, DL = 1.44 ng/mL

(d) cZn = 6.629 0.005 ng/mL


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-24

A B C D E F G
1 cNa, ng/mL I I I Mean I SD I
2 0.0 0 0 0 0.00000 0.0071
3 5.0 0.51 0.49 0.48 0.49333 0.015275
4 10.0 1.0200 1.00 0.99 1.00333 0.015275
5 Unknown 0.71 0.77 0.78 0.75333 0.037859
6 Part (c) Part (a)
7 calibration sensit. 0.1003333
8 analytical sensit. 6.5683585at 5.0 ng/mL
9
10 k 2
11 DL = ksb/m 0.1415282
12 k 3
13 DL = ksb/m 0.2122924
14 Parts (b) & (d)
15 Slope 0.1003333
16 Intercept -0.0027778
17 c unknwn 7.5359911
18 Std Error 0.0068041
19 N 3
20 Sxx 50
21 ybar 0.4989
22 M 3
23 SD in c 0.058933
24
25 Spreadsheet Documentation
26 E2 = AVERAGE(B2:D2) B16 = INTERCEPT(E2:E4,A2:A4)
27 F2 = STDEV(B2:D2) B17 = (E5-B16)/B15
28 B7 = SLOPE(E2:E4,A2:A4) B18 = STEYX(E2:E4,A2:A4)
29 B8 = B7/F3 B19 = COUNT(E2:E4)
30 B11 = 2*F2/B7 B20 = DEVSQ(A2:A4)
31 B12 = 3*F2/B7 B21 = AVERAGE(E2:E4)
32 B15 = SLOPE(E2:E4,A2:A4) B22 = (B18/B15)*SQRT(1/B22+1/B19+((B5-B21)^2)/((B15^2)*B20))

(a) See Spreadsheet

(b) calibration sensitivity = 0.100 analytical sensitivity = 6.57

(c) For k = 2, DL = 0.142 ng/mL for k = 3, DL = 0.212 ng/mL

k = 2 corresponds to a 92.1% k = 3 corresponds to a 98.3%

confidence level. confidence level.

(d) cNa = 7.536 0.059 ng/mL


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-25

A B C D E F G H I J
1 Day Value UCL LCL
2 1 49.8 56.9 43.7
3 2 48.4 56.9 43.7
4 3 49.8 56.9 43.7
5 4 50.8 56.9 43.7
6 5 49.6 56.9 43.7
7 6 50.2 56.9 43.7
8 7 51.7 56.9 43.7
9 8 50.5 56.9 43.7
10 9 47.7 56.9 43.7
11 10 50.3 56.9 43.7
12 11 49.5 56.9 43.7
13 12 50.5 56.9 43.7
14 13 48.9 56.9 43.7
15 14 49.7 56.9 43.7
16 15 48.9 56.9 43.7
17 16 48.8 56.9 43.7
18 17 48.6 56.9 43.7
19 18 48.1 56.9 43.7
20 19 53.8 56.9 43.7
21 20 49.6 56.9 43.7
22 21 58.8 56.9 43.7
23 22 51.3 56.9 43.7
24 23 50.6 56.9 43.7
25 24 48.8 56.9 43.7
26 25 52.6 56.9 43.7
27 26 54.2 56.9 43.7
28 27 49.3 56.9 43.7
29 28 47.9 56.9 43.7
30 29 51.3 56.9 43.7
31 30 49.3 56.9 43.7 Spreadsheet Documentation
32 Mean 50.31 B32 = AVERAGE(B2:B31)
33 Sigma 2.207 B33 = STDEV(B2:B31)
34 UCL 56.931 B34 = B32+(3*B33/SQRT(1))
35 LCL 43.689 B35 = B32-(3*B33/SQRT(1))

There appears to be a loss of statistical control on Day 21. (Note: In the first printing of the text,

the answer in the back of the book was in error.)


Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-26

A B C D E F G H I
2
1 Day Mean SD (xi-xave) UCL LCL
2 1 96.50 0.80 3.20 98.08 94.97
3 2 97.38 0.88 3.87 98.08 94.97
4 3 96.85 1.43 10.22 98.08 94.97
5 4 96.64 1.59 12.64 98.08 94.97
6 5 96.87 1.52 11.55 98.08 94.97
7 6 95.52 1.27 8.06 98.08 94.97
8 7 96.08 1.16 6.73 98.08 94.97
9 8 96.48 0.79 3.12 98.08 94.97
10 9 96.63 1.48 10.95 98.08 94.97
11 10 95.47 1.30 8.45 98.08 94.97
12 11 97.38 0.88 3.87 98.08 94.97
13 12 96.85 1.43 10.22 98.08 94.97
14 13 96.64 1.59 12.64 98.08 94.97
15 14 96.87 1.52 11.55 98.08 94.97
16 15 95.52 1.27 8.06 98.08 94.97
17 16 96.08 1.16 6.73 98.08 94.97
18 17 96.48 0.79 3.12 98.08 94.97
19 18 96.63 1.48 10.95 98.08 94.97
20 19 95.47 1.30 8.45 98.08 94.97
21 20 96.43 0.75 2.81 98.08 94.97
22 21 97.06 1.34 8.98 98.08 94.97
23 22 98.34 1.60 12.80 98.08 94.97
24 23 96.42 1.22 7.44 98.08 94.97
25 24 95.99 1.18 6.96 98.08 94.97
26
27 Mean 96.5242
28 N 24
29 spooled 1.269523
30 UCL 98.07901
31 LCL 94.96933
32
33 1.24
34
35
36
37
38
39
40 Spreadsheet Documentation
41 D2 = C2^2*5
42 B27 = AVERAGE(B2:B25)
43 B28 = COUNT(D2:D25)
44 B29 = SQRT(SUM(D2:D25)/(B28*6-B28))
45 B30 = B27+3*B29/SQRT(6)
46 B31 = B27-3*B29/SQRT(6)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 8

8-26 (cont.)

There appears to be a loss of statistical control on Day 22.