Fundamentals of Analytical Chemistry: 8th ed.

Chapter 7

Chapter 7

7-1 The mean of 5 measurements, x is a better estimate of the true value than any single measurement because the distribution of means is narrower than the distribution of individual results. 7-2 (a) By inspection of Table 7-1 CL = 99.7 % (b) CL = 90 % (c) CL = 68 % (d) CL = 95.4 % 7-3 (a) As the sample size, N, increases the confidence interval decreases in proportion to (b) As the desired confidence level increases the confidence interval increases. (c) As the standard deviation, s, increases the confidence interval increases in direct proportion. 7-4 For Set A: xi 3.5 3.1 3.1 3.3 2.5 xi =15.5 mean: x = 15.5/5 = 3.1 xi2 6.25 9.61 9.61 10.89 12.25 xi2 =48.61
N

Fundamentals of Analytical Chemistry: 8th ed.

48 .61 (15 .5) / 5 = 0.37 5 1
2

Chapter 7

standard deviation: s =

Since, for a small set of measurements we cannot be certain s is a good approximation of

, we will use the t statistic for confidence intervals. From Table 7-3, at 95%
confidence t for 4 degrees of freedom is 2.78, therefore

CI for = 3.1

( 2.78 )( 0.37 )
5

= 3.1 0.46 = 3.1 0.5

Results for Sets A through F, obtained in a similar way, are given in the following table. A B C D 2.86 0.24 E F

x
s CI

3.1 0.37

70.19 0.82 0.08 0.05

70.53 0.494 0.22 0.016

0.46 0.20 0.08 0.30 0.34 0.020

The 95% confidence interval establishes the range about the mean that we can be 95% confident that the true value lies within (in the absence of systematic errors). 7-5 If s is a good estimate of then we can use z at 95% confidence equal 1.96 and for set A,

CI for = 3.1 A CI B

(1.96 )( 0.20 )
5

= 0.18 E F

Similarly for sets B-F

0.18 0.079
2.5 3.1 3.5 2.5

0.009

0.26 0.15 0.013

7-6 For set A: Q =

= 0.6 and Qcrit for 5 observations at 95% confidence = 0.710.

Since Q < Qcrit the outlier value 2.5 cannot be rejected with 95% confidence.

Fundamentals of Analytical Chemistry: 8th ed. A Q Qcrit(95%) Decision 0.6 B 0.86 C 0.81 D 0.33 E 0.95 F 0.33

Chapter 7

0.710 0.970 0.829 0.710 0.829 0.710 Keep Keep Keep Keep Reject Keep

7-7 (a) 80% CL = 18.5 1.28 2.4 = 18.5 3.1 g Fe/mL 95% CL = 18.5 1.96 2.4 = 18.5 4.7 g Fe/mL
1.28 2.4 = 18.5 2.2 g Fe/mL 2

(b) 80% CL = 18.5

95% CL = 18.5

1.96 2.4 = 18.5 3.3 g Fe/mL 2

(c) 80% CL = 18.5

1.28 2.4 = 18.5 1.5 g Fe/mL 4

95% CL = 18.5

1.96 2.4 = 18.5 2.4 g Fe/mL 4

7-8 (a) 90% CL = 8.53 1.64 0.32 = 8.53 0.52 g Cu/mL 99% CL = 8.53 2.58 0.32 = 8.53 0.83 g Cu/mL
1.64 0.32 = 8.53 0.26 g Cu/mL 4

(b) 90% CL = 8.53

99% CL = 8.53

2.58 0.32 = 8.53 0.41 g Cu/mL 4

Fundamentals of Analytical Chemistry: 8th ed. (c) 90% CL = 8.53

1.64 0.32 = 8.53 0.13 g Cu/mL 16

Chapter 7

99% CL = 8.53

2.58 0.32 = 8.53 0.21 g Cu/mL 16

7-9 (a) 1.5 =

1.96 2.4 N

For a 95% CL, N = 9.8 10

(b)

1.5 =

2.58 2.4 N 1.96 0.32 N

For a 99% CL, N = 17

7-10

(a)

0.2 =

For a 95% CL, N = 9.8 10

(b)

0.2 =

2.58 0.32 N

For a 99% CL, N = 17

7-11

For the data set:

x = 3.22

and

s = 0.06

(a)

95% CL = 3.22

4.30 0.06 = 3.22 0.15 meq Ca/L 3

(b)

95% CL = 3.22

1.96 0.056 = 3.22 0.06 meq Ca/L 3

7-12

For the data set:

x = 7.24

and

s = 0.25

(a)

90% CL = 7.24

2.92 0.25 = 7.24 0.42 % lindane 3

(b)

90% CL = 7.24

1.64 0.28 = 7.24 0.27 % lindane 3

Fundamentals of Analytical Chemistry: 8th ed.

2.58 0.40 N

Chapter 7

7-13

(a)

0.3 =

For a 99% CL, N = 11.8 12

(b)

0.3 =

1.96 0.40 N

For a 95% CL, N = 6.8 7

(c)

0.2 =

1.64 0.40 N

For a 90% CL, N = 10.8 11

7-14

The null hypothesis is that = 30.15% and the alternative hypothesis is that 30.15%. This is a two-tailed test and from Table 7-1, zcrit = 1.96 for the 95% confidence level.
30 .26 30 .15 = 2.34 0.094 / 4

(a)

z=

Since 2.34 1.96, systematic error IS indicated at 95% confidence. (b) From Table 7-3, t for 3 degrees of freedom = 3.18 for the 95% confidence level.
30 .26 30 .15 = 2.59 0.085 / 4

t=

Since 2.59 3.18, systematic error is NOT indicated at 95% confidence. 7-15 This is a two-tailed test and from Table 7-1, zcrit = 1.96 for the 95% confidence level.
68 .5 68 .8 = 1.54 0.004 68 .8% / 2

(a)

z=

Since 1.54 -1.96, systematic error is NOT indicated at 95% confidence for C.

Fundamentals of Analytical Chemistry: 8th ed.

z= 4.882 4.953 = 3.38 0.006 4.953 % / 2

Chapter 7

(b)

Since 3.38 -1.96, systematic error IS indicated at 95% confidence for H. 7-16 This is a two-tailed test where s and from Table 7-1, zcrit = 2.58 for the 99% confidence level.

For As:

z=

129 119 =1.28 3 +3 9. 5 3 3

Since 1.28 2.58, no significant difference exists at 99% confidence.

Proceeding in a similar fashion for the other elements Element Co La Sb Th 7-17 z Difference?

-3.42 Yes 2.45 0.20 No No

-3.42 Yes

H0: = 5.0 ppm dissolved O2; Ha: < 5.0 ppm dissolved O2. This is a one-tailed test and from Table 7-3, for = 0.10 and 7 DOF, t = -1.90. For the data set:
x = 4.888

and

s = 0.40

t=

4.888 5.0 = -0.79 0.40 / 8

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 7

Since 0.79 -1.90, we must accept H0 and we cannot state that the dissolved O2 is less than 5.0 ppm at the 95% confidence level.
5.6 5.1 5.6 4.3

7-18

Q=

= 0.385 and Qcrit for 8 observations at 95% confidence = 0.526.

Since Q < Qcrit the outlier value 5.6 cannot be rejected with 95% confidence. 7-19 H0: = 1.0 ppb: Ha: < 1.0 ppb. This would be a one-tailed test. The type I error for this situation would be that we reject H0, when in fact, it is true, i.e. we decide the impurity is < 1.0 ppb at some level of confidence when, in fact, it is not < 1.0 ppb. The type II error would be that we accept H0 when, in fact, it is false, i.e. we decide the impurity is not < 1.0 ppb at some level of confidence when, in fact, it is < 1.0 ppb. 7-20 H0: = the previous level; Ha: > the previous level. This would be a one-tailed test. The type I error for this situation would be that we reject H0 when in fact, it is true, i.e. we decide the level of the pollutant is > the previous level at some level of confidence when, in fact, it is not. The type II error would be that we accept H0 when, in fact, it is false, i.e. we decide the level of the pollutant = the previous level when, in fact, it is > than the previous level. 7-21 (a) H0: = 7.03 ppm; Ha: = < 7.03 ppm. This would be a one-tailed test. The

type I error for this situation would be that we reject H0 decide that a systematic error exists when it does not. The type II error would be that we accept H0 decide a systematic error does not exist when it does. (b) H0: (atomic absorption) = (titration); Ha: (atomic absorption)

(titration). This would be a two-tailed test. The type I error for this situation would be

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 7

that we decide the methods agree when they do not. The type II error would be that we decide the methods do not agree when they do. (c) H0:
2 AA

EC

; Ha:

AA

<

EC

. This would be a one-tailed test. The type I

error for this situation would be that we decide AA results are less precise than electrochemistry results, when the precision is the same. The type II error would be that we decide the precision is the same when they electrochemical results are more precise. (d) H0: [impurity]X = [impurity]Y; Ha: [impurity]X < [impurity]Y. This would be a

one-tailed test. The type I error would be that we decide the [impurity]X < [impurity]Y when it is not. The type II error would be that we decide the [impurity]X = [impurity]Y when it does not. 7-22 (a) For the Top data set: For the Bottom data set: spooled = 0.1199 degrees of freedom = 5 +5 2 = 8 For 8 degrees of freedom at 95% confidence t = 2.31
x = 26 .338 x = 26 .254

t=

26 .338 26 .254 =1.11 5 +5 0.1199 5 5

Since 1.11 < 2.31, no significant difference exists at 95% confidence (b) From the data N = 5, d = 0.084 and sd = 0.015 For 4 degrees of freedom at 95% confidence t = 2.78
0.084 0 = 12 .52 0.015 / 5

t=

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 7

Since 12.52 > 2.78, a significant difference does exist at 95% confidence. (c) The large sample-to-sample variability causes sTop and sBottom to be large and masks

the differences between the samples taken from the top and the bottom. 7-23 (a) A paired t test should definitely be used in this case due to the large variation in

the Cl concentrations resulting from the various contact times and various locations from which the samples were obtained. (b) H0: d = 0; Ha:
A

0, where d is the mean difference between the methods.

From the data N = 8, d = -0.414 and sd = 0.32 For 7 degrees of freedom at 90% confidence t = 1.90
0.414 0 = 3.65 0.32 / 8

t=

Since 3.65 > 1.90, a significant difference in the 2 methods exists at 90% confidence. Similarly, for 7 degrees of freedom at 95% confidence t = 2.36 indicating a significant difference in the 2 methods exists at 95% confidence. Also, for 7 degrees of freedom at 99% confidence t = 3.50 indicating a significant difference in the 2 methods exists at 99% confidence, as well. (c) For this example the same conclusion is obtained at all three confidence levels. 7-24 For the first data set: For the second data set: spooled = 0.0027 degrees of freedom = 4 + 3 2 = 5
x = 2.2978 x = 2.3106

Fundamentals of Analytical Chemistry: 8th ed.

t= 2.2978 2.3106 = 6.207 4 +3 0.0027 4 3

Chapter 7

The Excel TDIST(x,df,tails) function can be used to calculate the probability of getting a t value of 6.207. In this case we find TDIST(6.207,5,2) = 0.0016. Therefore, we can be 99.84% confident that the nitrogen prepared in the two ways is different. There is a 0.16% probability of this conclusion being in error. 7-25 (a) Variation source Between soils Within soils Total (b) (c) 0.374 H0:
samp1

SS

df

MS

F 17.09

0.374-0.0972=0.2768 12 0.0081=0.0972

3-1=2 0.2768/2=0.1384 15-3=12 0.0081

15-1=14 =
samp2

samp3

; Ha: at least two of the means differ.

From Table 7-4 the F value for 12 degrees of freedom in the denominator and 2

degrees of freedom in the numerator at 95% confidence is 3.89. Since F calculated exceeds F tabulated we reject H0 and conclude that the phosphorous contents of the soil samples taken from the 3 locations are not equal. 7-26 (a) Variation source Juice brands Within juices Total (b) 53.68 H0:
brand1

SS 4 7.715=30.86 25 0.913=22.825

df

MS

F 8.45

5-1=4 0.913 8.45=7.715 30-5=25 30-1=29 0.913

brand2

brand3

brand4

brand5

; Ha: at least two of the means

Fundamentals of Analytical Chemistry: 8th ed. differ. (c)

Chapter 7

The Excel FINV(prob,df1,df2) function can be used to calculate the F value for

the above problem. In this case we find FINV(0.05,4,25) = 2.76. Since F calculated exceeds F tabulated we reject the null hypothesis and conclude that the average ascorbic acid contents of the 5 brands of orange juice are not equal.

Fundamentals of Analytical Chemistry: 8th ed. 7-27 (a) (b)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 A Result No. 1 2 3 Average = Stan. Dev. = Variance = Grand Mean = SSF = SSE = SST = MSF = MSE = F= LSD = B Lab A 10.3 11.4 9.8 10.50 0.81854 0.67000 10.020 5.57733 2.00667 7.58400 1.39433 0.20067 6.94850 0.816 C Lab B 9.5 9.9 9.6 9.67 0.20817 0.04333 D Lab C 10.1 10.0 10.4 10.17 0.20817 0.04333 E Lab D 8.6 9.3 9.2 9.03 0.37859 0.14333 F Lab E 10.6 10.5 11.1 10.73 0.32146 0.10333

Chapter 7
LabD

H0:

LabA

LabB

LabC

LabE

; Ha: at least two of the means differ.

10.73 - 9.03 = 10.50 - 9.03 = 10.17 - 9.03 = 9.67 - 9.03 = 10.73 - 9.67 = 10.50 - 9.67 = 10.17 - 9.67 = 10.73 - 10.17 = 10.50 - 10.17 = 10.73 - 10.50 =

1.70 1.47 1.14 0.64 1.06 0.83 0.5 0.56 0.33 0.23

(a significant difference) (a significant difference) (a significant difference) (no significant difference) (a significant difference) (a significant difference) (no significant difference) (no significant difference) (no significant difference) (no significant difference)

Spreadsheet Documentation B6 = AVERAGE(B2:B4) B7 = STDEV(B2:B4) B8 = B7^2 B10 = SUM(B2:F4)/15 B11 = 3*((B6-B10)^2+(C6-B10)^2+(D6-B10)^2+(E6-B10)^2+(F6-B10)^2) B12 = 2*SUM(B8:F8) B13 = B11+B12 B15 = B11/4 B16 = B12/10 B18 = B15/B16 B20 = 2.23*SQRT(2*B16/3)

From Table 7-4 the F value for 4 degrees of freedom in the numerator and 10 degrees of freedom in the denominator at 95% is 3.48. Since F calculated exceeds F tabulated we reject H0 and conclude that the laboratories differ at 95% confidence. We can also be

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 7

99% confident that the laboratories differ, but we cannot be 99.9% confident that the laboratories differ. (c) Based on the calculated LSD value laboratories A, C and E differ from laboratory D, but laboratory B does not. Laboratories E and A differ from laboratory B, but laboratory C does not. No significant difference exists between laboratories E and A.

Fundamentals of Analytical Chemistry: 8th ed. 7-28 (a) (b)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 A Result No. 1 2 3 4 Average = Stan. Dev. = Variance = Grand Mean = SSF = SSE = SST = MSF = MSE = F= LSD = B A1 10.24 10.26 10.29 10.23 10.26 0.02646 0.00070 10.160 0.05595 0.01645 0.07240 0.01865 0.00137 13.60486 0.057 C A2 10.14 10.12 10.04 10.07 10.09 0.04573 0.00209 D A3 10.19 10.1 10.15 10.12 10.14 0.03594 0.00129 E A4 10.19 10.15 10.16 10.1 10.15 0.03742 0.00140 F

Chapter 7 =
Analyst4

H0:

Analyst1

Analyst2

Analyst3

; Ha: at least two of the means differ.

10.26 - 10.09 = 10.15 - 10.09 = 10.14 - 10.09 = 10.26 - 10.14 = 10.15 - 10.14 = 10.26 - 10.15 =

0.17 0.06 0.05 0.12 0.01 0.11

(a significant difference) (a significant difference) (no significant difference) (a significant difference) (no significant difference) (a significant difference)

Spreadsheet Documentation B7 = AVERAGE(B2:B5) B8 = STDEV(B2:B5) B9 = B8^2 B11 = SUM(B2:E5)/16 B12 = 4*((B7-B11)^2+(C7-B11)^2+(D7-B11)^2+(E7-B11)^2) B13 = 3*SUM(B9:F9) B14 = B12+B13 B16 = B12/3 B17 = B13/12 B19 = B16/B17 B21 = 2.19*SQRT(2*B17/4)

From Table 7-4 the F value for 3 degrees of freedom in the numerator and 12 degrees of freedom in the denominator at 95% is 3.49. Since F calculated exceeds F tabulated we reject H0 and conclude that the analysts differ at 95% confidence. We can also be 99% and 99.9% confident that the analysts differ.

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 7

(c) Based on the calculated LSD value there is a significant difference between analyst 2 and analysts 1 and 4, but not analyst 3. There is a significant difference between analyst 3 and analyst 1, but not analyst 4. There is a significant difference between analyst 1 and analyst 4.

Fundamentals of Analytical Chemistry: 8th ed. 7-29 (a) (b)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 A Result No. 1 2 3 4 Average = Stan. Dev. = Variance = Grand Mean = SSF = SSE = SST = MSF = MSE = F= B Des 1 72 93 76 90 82.75 10.30776 106.2500 87.750 181.5 983.5 1165 60.50000 81.95833 0.73818 C Des 2 93 88 97 74 D Des 3 96 95.0 79 82 E Des 4 100 84 91 94 92.25 6.65207 44.2500

Chapter 7 ; Ha: at least two of the means differ.

H0:

Des1

Des2

Des3

Des4

88.00 88.00 10.03328 8.75595 100.6667 76.6667

Spreadsheet Documentation B7 = AVERAGE(B2:B5) B8 = STDEV(B2:B5) B9 = B8^2 B11 = SUM(B2:E5)/16 B12 = 4*((B7-B11)^2+(C7-B11)^2+(D7-B11)^2+(E7-B11)^2) B13 = 3*SUM(B9:F9) B14 = B12+B13 B16 = B12/3 B17 = B13/12 B19 = B16/B17 B21 = 2.19*SQRT(2*B17/4)

From Table 7-4 the F value for 3 degrees of freedom in the numerator and 12 degrees of freedom in the denominator at 95% is 3.49. Since F calculated is less than F tabulated we accept H0 and conclude that 4 flow cell designs give the same results at 95% confidence. (c) No differences.

Fundamentals of Analytical Chemistry: 8th ed. 7-30 (a) (b)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 A Result No. 1 2 3 4 5 Average = Stan. Dev. = Variance = Grand Mean = SSF = SSE = SST = MSF = MSE = F= LSD = B Color. 3.92 3.28 4.18 3.53 3.35 3.65 0.38571 0.1488 3.667 3.649773 3.49196 7.141733 1.82489 0.29100 6.27116 0.747 4.28 - 3.07 = 3.65 - 3.07 = 4.28 - 3.65 = 1.21 0.58 0.63 C EDTA 2.99 2.87 2.17 3.40 3.92 3.07 0.64958 0.42195 D AA 4.40 4.92 3.51 3.97 4.59 4.28 0.54979 0.3023 E F G

Chapter 7 ; Ha: at least two of the means differ.

H0:

Colorimetry

EDTA Tit

AA

(a significant difference) (no significant difference) (no significant difference)

Spreadsheet Documentation B8 = AVERAGE(B2:B6) B9 = STDEV(B2:B6) B10 = B9^2 B12 = SUM(B2:D6)/15 B13 = 5*((B8-B12)^2+(C8-B12)^2+(D8-B12)^2) B14 = 4*SUM(B10:D10) B15 = B13+B14 B17 = B13/2 B18 = B14/12 B20 = B17/B18 B22 = 2.19*SQRT(2*B18/5)

From Table 7-4 the F value for 2 degrees of freedom in the numerator and 12 degrees of freedom in the denominator at 95% is 3.89. Since F calculated is greater than F tabulated we reject H0 and conclude that the 3 methods give different results at 95% confidence.

Fundamentals of Analytical Chemistry: 8th ed. (c)

Chapter 7

Based on the calculated LSD value there is a significant difference between the

atomic absorption method and the EDTA titration. There is no significant difference between the EDTA titration method and the colorimetry method and there is no significant difference between the atomic absorption method and the colorimetry method.
41 .27 41 .61 41 .84 41 .27

7-31

(a) Q =

= 0.596 and Qcrit for 4 observations at 95% confidence = 0.829.

Since Q < Qcrit the outlier value 41.27 cannot be rejected with 95% confidence.
7.388 7.295 7.388 7.284

(b) Q =

= 0.894 and Qcrit for 4 observations at 95% confidence = 0.829.

Since Q > Qcrit the outlier value 7.388 can be rejected with 95% confidence.
85 .10 84 .70 85 .10 84 .62

7-32

(a) Q =

= 0.833 and Qcrit for 3 observations at 95% confidence = 0.970.

Since Q < Qcrit the outlier value 85.10 cannot be rejected with 95% confidence.
85 .10 84 .70 85 .10 84 .62

(b) Q =

= 0.833 and Qcrit for 4 observations at 95% confidence = 0.829.

Since Q > Qcrit the outlier value 85.10 can be rejected with 95% confidence.
4.60 4.50 4.60 4.40

7-33

Q=

= 0.5 and Qcrit for 5 observations at 95% confidence = 0.710.

Since Q < Qcrit the outlier value 4.60 ppm cannot be rejected with 95% confidence.