Chapter 1

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Chapter 1

STATISTICS FOR ANALYTICAL CHEMISTRY

K Chapter 1 Exercise k

1.1 Types of Error, Precision and Accuracy


1. A standard sample of pooled human blood serum contains 42.0 g of albumin per litre. Five laboratories
(A–E) each do six determinations (on the same day) of the albumin concentration, with the following
results (g l−1 throughout): Comment on the bias, precision and accuracy of each of these sets of results.

A B C D E
42.5 39.8 43.5 35.0 42.2
41.6 43.6 42.8 43.0 41.6
42.1 42.1 43.8 37.1 42.0
41.9 40.1 43.1 40.5 41.8
41.1 43.9 42.7 36.8 42.6
42.2 41.9 43.3 42.2 39.0

2. Using the same sample and method as in question 1, laboratory A makes six further determinations of the
albumin concentration, this time on six successive days. The values obtained are 41.5, 40.8, 43.3, 41.9,
42.2 and 41.7 g l−1 . Comment on these results.

1.2 Propagation of uncertainty, Standard deviations, Confidence intervals


3. Ten replicate analyses of the concentration of mercury in a sample of commercial gas condensate gave
the following results: 23.3 22.5 21.9 21.5 19.9 21.3 21.7 23.8 22.6 24.7 ng ml−1 . [1]
(a) Calculate the mean, standard deviation, relative standard deviation and 99% confidence limits of the
mean.
(b) Six replicate analyses on another sample gave the following values:13.8 14.0 13.2 11.9 12.0 12.1 ng
ml−1 . Repeat the calculations for these values.
4. In an evaluation of a method for the determination of fluorene in seawater, a synthetic sample of seawater
was spiked with 50 ng ml−1 of fluorene. Ten replicate determinations of the fluorene concentration in the
sample had a mean of 49.5 ng ml−1 with a standard deviation of 1.5 ng ml−1 .[2]
(a) Calculate the 95% confidence limits of the mean.
(b) Is the spiked value of 50 ng ml−1 within the 95% confidence limits?

1.3 Significance tests


5. In order to evaluate a spectrophotometric method for the determination of titanium, the method was
applied to alloy samples containing different certified amounts of titanium. The results (% Ti) are shown
below. For each alloy eight replicate determinations were made.[3]
(a) For each alloy, test whether the mean value differs significantly from the certified value.
1.3 Significance tests

Sample Certified value Mean Standard deviation


1 0.496 0.482 0.0257
2 0.995 1.009 0.0248
3 1.493 1.505 0.0287
4 1.990 2.002 0.0212

6. The following data give the recovery of bromide from spiked samples of vegetable matter, measured by
using a gas-liquid chromatographic method. The same amount of bromide was added to each specimen.[4]

Tomato: 777 790 759 790 770 758 764 mg g−1


Cucumber: 782 773 778 765 789 797 782 mg g−1

(a) Test whether the recoveries from the two vegetables have variances which differ significantly.
(b) Test whether the mean recovery rates differ significantly.
7. The following results show the percentage of the total available interstitial water recovered by centrifuging
samples taken at different depths in sandstone.

Depth of sample (m) Water recovered, %


7 33.3 33.3 35.7 38.1 31.0 33.3
8 43.6 45.2 47.7 45.4 43.8 46.5
16 73.2 68.7 73.6 70.9 72.5 74.5
23 72.5 70.4 65.2 66.7 77.6 69.8

Show that the percentage of water recovered differs significantly at different depths.
8. The following table gives the results of the determination of chromium in organic materials for two
different methods.
Method 1 mean = 2.15 s.d. = 0.26
Pine needles:
Method 2 mean = 2.45 s.d. = 0.14
Method 1 mean = 5.12 s.d. = 0.80
Beech leaves:
Method 2 mean = 7.27 s.d. = 0.44
Method 1 mean = 23.08 s.d. = 2.63
Aquatic plant:
Method 2 mean = 32.01 s.d. = 4.66

In each case the mean is the average of five values. For each material test whether the mean results
obtained by the two methods differ significantly

2
1.4 Calibration Methods in instrumental analysis

9. Six analysts each made six determinations of the paracetamol content of the same batch of tablets [5].
The results are shown below:

Analist Paracetamol content (% m/m)


A 84.32 84.51 84.63 84.61 84.64 84.51
B 84.24 84.25 84.41 84.13 84.00 84.30
C 84.29 84.40 84.68 84.28 84.40 84.36
D 84.14 84.22 84.02 84.48 84.27 84.33
E 84.50 83.88 84.49 83.91 84.11 84.06
F 84.17 84.70 84.11 84.36 84.61 83.81

(a) Test whether there is any significant difference between the means obtained by the six analysts.
10. A new flame atomic-absorption spectroscopic method of determining antimony in the atmosphere was
compared with the recommended calorimetric method [6]. For samples from an urban atmosphere the
following results were obtained:

Sample N◦ Antimony found (mg m−3 )


New method Standard method
1 22.2 25.0
2 19.2 19.5
3 15.7 16.6
4 20.4 21.3
5 19.6 20.7
6 15.7 16.8

Do the results obtained by the two methods differ significantly?

1.4 Calibration Methods in instrumental analysis


11. The following results were obtained when each of a series of standard silver solutions was analysed by
flame atomic-absorption spectrometry.

Concentration, ng ml−1 0 5 10 15 20 25 30
Absorbance 0.003 0.127 0.251 0.390 0.498 0.625 0.763

a Determine the slope and intercept of the calibration plot, and their confidence limits
b Estimate the confidence limits for the silver concentrations in
i a sample giving an absorbance of 0.456 in a single determination, and
ii a sample giving absorbance values of 0.308, 0.314, 0.347 and 0.312 in four separate analyses.
c Estimate the limit of detection of the silver analysis.

3
1.4 Calibration Methods in instrumental analysis

12. The gold content of a concentrated seawater sample was determined by using atomic-absorption spec-
trometry with the method of standard additions. The results obtained were as follows.

Gold added,
ng per ml of
concentrated
sample 0 10 20 30 40 50 60 70
Absorbance 0.257 0.314 0.364 0.413 0.468 0.528 0.574 0.635

Estimate the concentration of the gold in the concentrated seawater, and determine confidence limits for
this concentration.
13. In a study of the complex formed between europium (III) ions and pyridine-2, 6-dicarboxylic acid (DPA),
the absorbance values of solutions containing different DPA:Eu concentrations were determined, with the
following results: [7]

Absorbance 0.008 0.014 0.024 0.034 0.042 0.050 0.055 0.065


DPA:Eu 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Absorbance 0.068 0.076 0.077 0.073 0.066 0.063 0.058
DPA:Eu 1.8 2.0 2.4 2.8 3.2 3.6 4.0

Use these two rows of data to determine the slopes and intercepts of two separate straight lines. Estimate
their intersection point and its standard deviation, thus determining the composition of the DPA-europium
complex formed.

4
Bibliography

[1] Azman Shafawi et al. “Determination of total mercury in hydrocarbons and natural gas condensate by
atomic fluorescence spectrometry”. In: Analyst 124 (2 1999), pp. 185–189. doi: 10.1039/A809679A.
url: http://dx.doi.org/10.1039/A809679A.
[2] Manuel Algarra González and Miguel Hernández López. “Determination of fluorene in sea-water by room
temperature phosphorescence in organised media”. In: Analyst 123.11 (1998), pp. 2217–2221.
[3] Qiu Xing-Chu and Zhu Ying-Quan. “Spectrophotometric study of the reaction of titanium (IV) with
chlorophosphonazo I”. In: Analyst 108.1286 (1983), pp. 641–644.
[4] John A Roughan, Patricia A Roughan, and John PG Wilkins. “Modified gas-liquid chromatographic method
for determining bromide/total bromine in foodstuffs and soils”. In: Analyst 108.1287 (1983), pp. 742–747.
[5] Andrew D Trafford et al. “A rapid quantitative assay of intact paracetamol tablets by reflectance near-
infrared spectroscopy”. In: Analyst 124.2 (1999), pp. 163–167. url: https : / / doi . org / 10 . 1039 /
A806629I.
[6] JR Castillo et al. “Flame atomic-absorption spectroscopic determination of antimony in atmospheric
particulates by using direct atomisation of the covalent hydride”. In: Analyst 107.1281 (1982), pp. 1488–
1492. url: https://doi.org/10.1039/AN9820701488.
[7] Nadine Arnaud, Eric Vaquer, and Joseph Georges. “Comparative study of the luminescent properties
of europium and terbium coordinated with thenoyltrifluoroacetone or pyridine-2, 6-dicarboxylic acid in
aqueous solutions”. In: Analyst 123.2 (1998), pp. 261–265. url: https://doi.org/10.1039/A706522A.
[8] J.N. Miller and J.C. Miller. Statistics and Chemometrics for Analytical Chemistry. Pearson/Prentice Hall,
2005. isbn: 9780131291928. url: https://books.google.com.ec/books?id=Efx77dxOC3sC.
[9] D.A. Skoog, F.J. Holler, and S.R. Crouch. Principles of Instrumental Analysis. Cengage Learning, 2017.
isbn: 9781337468039. url: https://books.google.com.ec/books?id=D13EDQAAQBAJ.

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