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Skoog CH 5
Skoog CH 5
Analytical Chemistry
CHAPTER 5
ERRORS, RANDOM ERRORS,
AND STATISTICAL DATA IN
CHEMICAL ANALYSES
Errors, Random Errors, and Statistical
Data in Chemical Analyses
Impossible: The analytical results are free of errors or
uncertainties.
Possible: Minimize these errors and estimate their size
with acceptable accuracy.
Statistical calculations for use to judge the quality of
experimental measurements are many.
Figure 3-1 Results from six replicate determinations for iron in aqueous samples of a standard
solution containing 20.00 ppm of iron(III).
3-4 Copyright © 2011 Cengage Learning
Errors, Random Errors, and Statistical
Data in Chemical Analyses
Measurements are always accompanied by uncertainty.
The true value always falls within a range due to
uncertainty.
The probable magnitude of the error defines the limit
within which the true value lies.
Data of unknown quality are worthless.
The true value of a measurement is never known
exactly.
No one can afford to waste time generating data that are more
reliable than is needed.
(3-1)
x
i
(3-2)
Figure 3-2 Illustration of accuracy and precision using the pattern of darts on a
dartboard
3-15 Copyright © 2011 Cengage Learning
3A-3 How About Accuracy?
Absolute Error
The absolute error E in the measurement of a quantity xi is
given by the equation
(3-3)
where xt is the true, or accepted, value of the quantity.
Note that we retain the sign in stating the error.
(3-4)
e.g.
Figure 3-3 Absolute error in the micro-Kjeldahl determination of nitrogen. Each dot represents the error associated
with a single determination. Each vertical line labeled (xi - xt ) is the absolute average deviation of the set from the true
value. (Data from C. O. Willits and C. L. Ogg, J. Assoc. Anal. Chem., 1949, 32, 561. With permission.)
3-20 Copyright © 2011 Cengage Learning
3A-4 Classifying Experimental
Errors
Figures 3-1 and 3-3 suggest that chemical analyses
are affected by at least two types of errors.
One type, called random (or indeterminate) error,
causes data to be scattered more or less
symmetrically around a mean value.
Refer to Figure 3-3: Notice that the scatter in the
data, and thus the random error, for analysts 1 and
3 is significantly less than that for analysts 2 and 4.
Standard reference
materials from NIST.
(Photo courtesy of the
National Institute of
Standards and
Technology.)
Figure 3-4
Frequency
distribution for
measurements
containing (a)
four random
uncertainties, (b)
ten random
uncertainties,
and (c) a very
large number of
random
uncertainties.
Figure 3-5 A histogram (A) showing distribution of the 50 results in Table 3-3
and a Gaussian curve (B) for data having the same mean and same standard
deviation as the data in the histogram.
3-54 Copyright © 2011 Cengage Learning
Sources of random uncertainties
Many small and uncontrollable variables affect even
the simple process of calibrating a pipet.
The cumulative effect of random uncertainties is
responsible for the scatter of data points around the
mean.
Statistics only reveal information that is already present
in a data set.
Do not confuse the statistical sample with the
analytical sample.
(3-5)
where N is the number of data points making up the
population.
(3-6)
(3-7)
The quantity N – 1 is called the number of degrees of
freedom.
(3-8)
( x i ) / N
2
(3-9)
(3-10)
(3-11)
(3-15)
(3-17)
2. The intercept b: