Chapter 5:

E r ro rs i n c h e m i c a l a n a l ys i s

Definition of terms: Measurand, Accuracy

and Precision, Error, Bias and
Measurement uncertainty
Types of error
Relative error
Measures of spread
Measurand
Accuracy
Trueness

Average
Precision
Error
Systematic
Error
 Bias

Random Error
 Ways to d ete c t syste m at i c e r ro r :
1.) Analyze samples of known composition, such as a Standard
Reference Material. Your method should reproduce the known
answer.
2.) Analyze “blank” samples containing none of the analyte being
sought. If you observe a nonzero result, your method responds to
more than you intend.
3.) Use different analytical methods to measure the same quantity. If
the results do not agree, there is error in one (or more) of the
methods.
4.) Round Robin experiment: Assign different persons in several
laboratories to analyze identical samples by the same or different
methods. Disagreement beyond the estimated random error is
systematic error.
 Relative error
Accuracy is how closely the result of an experiment agrees with
the “true” or expected result. We can express accuracy as an
absolute error, e
𝒆 = 𝒐𝒃𝒕𝒂𝒊𝒏𝒆𝒅 𝒓𝒆𝒔𝒖𝒍𝒕 − 𝒆𝒙𝒑𝒆𝒄𝒕𝒆𝒅 𝒓𝒆𝒔𝒖𝒍𝒕

Or as a percentage relative error, %er

𝒐𝒃𝒕𝒂𝒊𝒏𝒆𝒅 𝒓𝒆𝒔𝒖𝒍𝒕 − 𝒆𝒙𝒑𝒆𝒄𝒕𝒆𝒅 𝒓𝒆𝒔𝒖𝒍𝒕
%𝒆𝒓 = 𝒙 𝟏𝟎𝟎%
𝒆𝒙𝒑𝒆𝒄𝒕𝒆𝒅 𝒓𝒆𝒔𝒖𝒍𝒕

Or as relative error in parts per thousands, er

𝒐𝒃𝒕𝒂𝒊𝒏𝒆𝒅 𝒓𝒆𝒔𝒖𝒍𝒕 − 𝒆𝒙𝒑𝒆𝒄𝒕𝒆𝒅 𝒓𝒆𝒔𝒖𝒍𝒕
𝒆𝒓 = 𝒙 𝟏, 𝟎𝟎𝟎
𝒆𝒙𝒑𝒆𝒄𝒕𝒆𝒅 𝒓𝒆𝒔𝒖𝒍𝒕
 Measures of spread
The range, w, is the difference between a data set’s largest and
smallest values.
𝒘 = 𝑿𝒍𝒂𝒓𝒈𝒆𝒔𝒕 − 𝑿𝒔𝒎𝒂𝒍𝒍𝒆𝒔𝒕
The range provides information about the total variability in the data
set, but does not provide information about the distribution of
individual values. The range is not a robust estimate of spread.

The standard deviation, s, describes the spread of individual values

about their mean, and is given as:

where Xi is one of n individual values in the data set, and 𝑋ത is the data
set’s mean value.
 Measures of spread
Relative standard deviation, sr:
𝒔
𝒔𝒓 =
𝑿ഥ
which can be expressed as %sr (% RSD or coefficient of variation) or sr
(in parts per thousands, ppt).

Variance, s2, which is the square of the standard deviation. We usually

report a data set’s standard deviation, rather than its variance,
because the mean value and the standard deviation share the same
unit. the variance is a useful measure of spread because its values are
additive.