Solutions to exercises chapter 1 1

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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 36 37 38 39 40 41 42 43 44 45

Laboratory B

35 36 37 38 39 40 41 42 43 44 45

Laboratory C

35 36 37 38 39 40 41 42 43 44 45

Laboratory D

35 36 37 38 39 40 41 42 43 44 45

Laboratory E

35 36 37 38 39 40 41 42 43 44 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, poor

precise, precise but similar to A, but
Bias/preci little bias, mean precision,
little bias, biased to high the
sion accurate biased to low
mean values, poor last result might
/accuracy but not very values, poor
accurate accuracy be an ‘outlier’
reliable 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 36 37 38 39 40 41 42 43 44 45

Laboratory A : 6 tests in 6
successive days
35 36 37 38 39 40 41 42 43 44 45

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

Mean 41.9 41.9

STD 0.5 0.8

 Solutions to exercises chapter 1 3
Bolouri

A still shows little bias, but precision is

poorer, reflecting reproducibility (i.e.
Bias/precision precise, little bias, between-day precision) rather than
/accuracy mean accurate repeatability (within-day
precision).

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.
 Solutions to exercises chapter 1 4
Bolouri

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.