APPENDIX
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During chemical experiments, it is important to
reduce errors in measurements. The measurements
we make have a certain degree of uncertainty. Our
aim is to reduce this uncertainty.
Systematic errors: The instruments you use may not
be calibrated accurately so the measurements show a
regular (or systematic) error. For example, if you boil
pure water at 101.3 kPa and use a thermometer to
measure the boiling point, you should read a temp-
erature of 100 °C. If your thermometer reads (say)
102 °C, it has a systematic error of +2 °C. Instru-
ments should be calibrated, therefore, against known
standards before they are used. Another source of
systematic error is experimenter bias. Parallax error is
an example of experimenter bias. You must ensure
that you use the instrument correctly to avoid paral-
lax error. Probes and data loggers can help minimise
this problem.
Random (accidental) errors: You should always
conduct experiments with the greatest precision
using calibrated instruments. You will find, however,
that repeated measurements do not yield exactly the
same results. These small differences are the result
of unknown factors, so cannot be controlled. They
are called random or accidental errors. Making
many measurements (>5) will help to ensure the
reliability of your data.
Limits of reading: Each measuring instrument’s accu-
racy is affected by the ‘limit of reading’ of its scale. For
example, a thermometer may have 1 °C graduations.
This is its limit of reading. The error is half the limit
of reading (that is, ±0.5 °C). To reduce this error, you
could use a thermometer with smaller graduations.
For example, using a thermometer with graduations
0.2 °C apart reduces the error to ±0.1 °C.
Experimental accuracy: The accuracy of a result is
how close a measurement is to the accepted value.
The absolute error or percentage error is a measure of the
degree of accuracy of the measurement.
350 APPENDIX
If a student measures the heat of combustion of
ethanol and obtains a value of 1310 kJ/mol instead
of the accepted value of 1367 kJ/mol, the:
(a) absolute error = 1367 – 1310 = 57 kJ
(b) percentage error = 57/1367 x 100/1 = 4%.
Precision: It is important that the result of an experi-
ment is reproducible each time you or other chem-
ists repeat the experiment. Precision is a measure of
the reproducibility of the measurement. The results of
all the repeated experiments should be consistent
and clustered around the mean. Some results lie
close to the mean while others deviate by a larger
amount. The size of the average deviation from the
mean is one measure of the uncertainty or absolute
error of the measurement. The maximum deviation or
standard deviation from the mean are other statistical
methods of estimating precision. If the uncertainty is
small, the measurements are very precise.
Consider the following experimental measurements
of the enthalpy of combustion of methane using two
different pieces of equipment. The average devia-
tions from the mean in the experimental measure-
ments and the accepted values from the literature
are shown.
Apparatus 1: ∆H(methane) = –920 ± 20 kJ/mol
Apparatus 2: ∆H(methane) = –880 ± 80 kJ/mol
Accepted value: ∆H(methane) = –890 kJ/mol
Measurement of the heat of combustion of methane
in apparatus 1 was more precise than that in appara-
tus 2; the average deviation from the mean was lower
because successive measurements were more closely
grouped. However, the accuracy of measurements
in apparatus 2 was greater as the percentage error
in apparatus 2 (1%) was lower than in apparatus 1
(3%). This means that apparatus 2 produced more
accurate results.
Deviation from the mean: Statistical procedures
can be used to measure the uncertainty in a meas-
urement from the range of results obtained by
repetitions. Spreadsheet applications (such as Micro-
soft Excel) can be used to measure the standard
deviation of a measurement. Alternatively, the
maximum deviation from the mean can be used as
simpler means of estimating uncertainty.
Sample data: Each group of students in a class meas-
ures the mass of 25.0 mL of ethanol (delivered from
a burette) using a calibrated electronic balance.
Each result is recorded and the mean calculated.
The reading with the greatest deviation from this
mean is used as a measure of the uncertainty or abso-
lute error. The mass (in grams) measured by each
group is: 19.60, 19.55, 19.65, 19.52, 19.64, 19.56,
19.55, 19.62.
Mean = 19.59 g
Maximum deviation from the mean = 0.07 g
Thus, mass of 25.0 mL of ethanol = 19.59 ± 0.07 g
Accepted mass of 25.0 mL ethanol = 19.63 g
(from SI Chemical Data 5th edition)
Precision of measurement = ± 0.07 g
Accuracy of measurement = ± 0.04 g = 0.2%

APPENDIX 351