ERROR IN CHEMICAL

ANALYSIS
 Errors can sometimes be
calamitous, as this picture of the
famous train accident at Montparnasse
station in Paris illustrates.
On October 22, 1895, a train
from Granville, France, crashed
through the platform and the station
wall because the brakes failed. The
engine fell thirty feet into the street
below killing a woman.
Mars Climate orbiter
 ERROR
Error has two slightly different meanings.

• First, error refers to the difference between a measured

value and the “true” or “known” value.
• Second, error often denotes the estimated uncertainty in a
measurement or experiment.
 Results from six replicate
determinations of iron in
aqueous samples of a
standard solution containing
20.0 ppm iron(III). The mean
value of 19.78 has been
rounded to 19.8 ppm.
The symbol ppm stands for parts per
million, that is, 20.00 parts of iron(III)
per million parts of solution. For
aqueous solutions, 20 ppm = 20 mg/dL.
 SOME IMPORTANT TERMS
• Replicates are samples of about the same size that are
carried through an analysis in exactly the same way.

– First, the central value of a set should be more reliable than any
of the individual results.Usually, the mean or the median is
used as the central value for a set of replicate measurements.
– Second, an analysis of the variation in the data allows us to
estimate the uncertainty associated with the central value.
 SOME IMPORTANT TERMS
MEAN AND MEDIAN

Mean
- also called the arithmetic mean or the average, is
obtained by dividing the sum of replicate
measurements by the number of measurements in a
set.
 SOME IMPORTANT TERMS
Median
The median
is the middle value in a set of data that has been
arranged in numerical order. The median is used
advantageously when a set of data contain an
outlier, a result that differs significantly from others
in the set.
An outlier can have a significant effect on the
mean of the set but has no effect on the median.
 SOME IMPORTANT TERMS
• Calculate the mean and median for this set:

19.4 + 19.5 + 19.6 + 19.8 + 20.1 + 20.3

 SOME IMPORTANT TERMS
PRECISION

Precision describes the reproducibility of

measurements—in other words, the closeness of
results that have been obtained in exactly the same
way.

Generally, the
precision of a measurement is readily determined by
• Three terms are widely used to describe the
precision of a set of replicate data: standard
deviation, variance, and coefficient of variation.
These three are functions of how much an
individual result xi differs from the mean, called the
deviation from the mean di.
 SOME IMPORTANT TERMS

Accuracy is the closeness of a measured value to

the true or accepted value.
– The absolute error of a measurement is the
difference between the measured value and the true
value. The sign of the absolute error tells you whether
the value in question is high or low. If the
measurement result is low, the sign is negative; if the
measurement result is high, the sign is positive.
–The relative error of a measurement is the
absolute error divided by the true value.
Types of Errors in Experimental Data
Chemical analyses are affected by at least two types of
errors.
– Random (indeterminate) error causes data to be
scattered more or less symmetrically around a mean
value.
– Systematic (or determinate) error causes the mean of
a data set to differ from the accepted value.
• A third type of error is gross error. Gross errors differ
from indeterminate and determinate errors. They usually
occur only occasionally, are often large, and may cause a
result to be either high or low. They are often the product
of human errors.
– For example, if part of a precipitate is lost before weighing,
analytical results will be low. Touching a weighing bottle with
your fingers after its empty mass is determined will cause a
high mass reading for a solid weighed in the contaminated
bottle. Gross errors lead to outliers.
 SYSTEMATIC ERRORS

1. Instrumental. are caused by nonideal instrument

behavior, by faulty calibrations, or by use under
inappropriate conditions.
For example, a poor calibrated instrument such as a
thermometer that reads 102⁰C when immersed in boiling water
and 2⁰C when immersed in ice waer a atmospheric pressure.
Such a thermometer would result in measured values that are
consistently too high.
2. Observational. For example, parallax in reading a
volume in graduated cylinder.
3. Environmental. For example, maintaining the
humidity and temperature in constant in the
laboratory.
4. Personal. Errorsresult from the carelessness,
inattention, or personal limitations of the
experimenter.