Solutions to exercises chapter 1 1

Bolouri

Q1. 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 throughout):
Comment on the bias, precision and accuracy of each of these sets of results.

Answer.
First we draw dot plot diagram for 5 laboratoey.

Laboratory A

35 37 39 41 43 45

Laboratory B

35 37 39 41 43 45

Laboratory C

35 37 39 41 43 45

Laboratory D
35 37 39 41 43 45

Laboratory E
35 37 39 41 43 45
 Solutions to exercises chapter 1 2
Bolouri

with calculate the mean for 5 laboratories and pay attention to dot plots we can say:

laboratory A B C D E

Mean 41.9 41.9 43.2 39.1 41.5

STD 0.5 1.7 0.42 3.2 1.3

poor precision,
precise, little poor precision, little precise but biased similar to A, but the
Bias/precision biased to low
bias, mean bias, mean accurate to high values, last result might be an
/accuracy values, poor
accurate but not very reliable poor accuracy ‘outlier’
accuracy

Q2. 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 Comment on these results.

Answer.

Laboratory A : 5 test in a
day
35 37 39 41 43 45

Laboratory A : 6 tests in 6
successive days
35 37 39 41 43 45

A A
laboratory 5 test in a day 6 tests in 6 successive days
(within-day precision) ( between-day precision)

Mean 41.9 41.9

STD 0.5 0.8

A still shows little bias, but precision is poorer,

reflecting reproducibility (i.e. between-day
Bias/precision precise, little bias, mean
precision) rather than repeatability (within-day
/accuracy accurate precision).
 Solutions to exercises chapter 1 3
Bolouri

Q3. The number of binding sites per molecule in a sample of monoclonal antibody is determined
four times, with results of 1.95, 1.95, 1.92 and 1.97. Comment on the bias, precision and
accuracy of these results.

Number of binding sites must be an integer, clearly 2 here, so results are precise,but biased to
low values. The bias does not matter much, as two binding sites can be deduced.

Q4. Discuss the degrees of bias and precision desirable or acceptable in the following analyses:
(i) Determination of the lactate concentration of human blood samples.
(ii) Determination of uranium in an ore sample.
(iii) Determination of a drug in blood plasma after an overdose.
(iv) Study of the stability of a colorimetric reagent by determination of its absorbance at a single
wavelength over a period of several weeks.

(i) Blood lactate levels vary a lot in healthy patients, so great precision and accuracy are not
needed.
(ii) Unbiased results could be crucial because of the great economic importance of Uranium.
(iii) Speed of analysis is crucial here, so precision and accuracy are less important.
(iv) The aim is to detect even small changes over time, so precision is most important.

Q5. For each of the following experiments, try to identify the major probable sources of random
and systematic errors, and consider how such errors may be minimized:
(i) The iron content of a large lump of ore is determined by taking a single small sample,
dissolving it in acid, and titrating with ceric sulphate after reduction of Fe(III) to Fe(II).
(ii) The same sampling and dissolution procedure is used as in (i) but the iron is determined
colorimetrically after addition of a chelating reagent and extraction of the resulting coloured
complex into an organic solvent.(iii) The sulphate content of an aqueous solution.

i. Sample might not be representative, and/or reduction of Fe(III) to Fe(II) might be

incomplete, giving biased results in each case. Completeness of reduction could be tested
using a standard material. Random errors in each stage, including titrimetry, where they
should be small.

ii. Sampling problem as in (i), and also incomplete extraction, leading to bias (checked with
standard). Random errors inspectrometry, which again should be relatively small.

iii. Random errors in gravimetry should be very small: more significant will be chemical
problems such as co-precipitation, giving biased results.