ANALYTICAL CHEMISTRY

ERRORS IN CHEMICAL ANALYSES

ERRORS IN CHEMICAL ANALYSES
Measurements invariably involve errors and uncertainties. Only a
Measurements invariably involve errors and uncertainties. Only a
few of these are due to mistakes on the part of the
few of these are due to mistakes on the part of the
experimenter. More commonly, errors are caused by faulty
experimenter. More commonly, errors are caused by faulty
calibrations or standardizations or by random variations and
calibrations or standardizations or by random variations and
uncertainties in results. Frequent calibrations, standardizations,
uncertainties in results. Frequent calibrations, standardizations,
and analyses of known samples can sometimes be used to
and analyses of known samples can sometimes be used to
lessen all but the random errors and uncertainties. however,
lessen all but the random errors and uncertainties. however,
measurement errors are an inherent part of the quantized world
measurement errors are an inherent part of the quantized world
in which we live. Because of this, it is impossible to perform a
in which we live. Because of this, it is impossible to perform a
chemical analysis that is totally free of errors or uncertainties.
chemical analysis that is totally free of errors or uncertainties.
We can only hope to minimize errors and estimate their size with
We can only hope to minimize errors and estimate their size with
acceptable accuracy.
acceptable accuracy.

ERRORS AND
UNCERTAINTIES
 SOME IMPORTANT TERMS

In order to improve the reliability and to obtain information about

In order to improve the reliability and to obtain information about
the variability of results, two to five portions (replicates) of a
the variability of results, two to five portions (replicates) of a
sample are usually carried through an entire analytical
sample are usually carried through an entire analytical
procedure. Replicates are samples of about the same size that
procedure. Replicates are samples of about the same size that
are carried through an analysis in exactly the same way.
are carried through an analysis in exactly the same way.
The most widely used measure of central value is the mean, x.
The most widely used measure of central value is the mean, x.
The mean, also called the arithmetic mean or the average, is
The mean, also called the arithmetic mean or the average, is
obtained by dividing the sum of replicate measurements by
obtained by dividing the sum of replicate measurements by
the number of measurements in the set:
the number of measurements in the set:

where xi represents the individual values of x making up the

where xi represents the individual values of x making up the
set of N replicate measurements.
set of N replicate measurements.

THE MEAN AND THE

MEDIAN
The median is the middle result when replicate data are
The median is the middle result when replicate data are
arranged in increasing or decreasing order. The median is the
arranged in increasing or decreasing order. The median is the
middle value in a set of data that has been arranged in
middle value in a set of data that has been arranged in
numerical order. The median is used advantageously when a
numerical order. The median is used advantageously when a
set of data contain an outlier, a result that differs significantly
set of data contain an outlier, a result that differs significantly
from others in the set. An outlier can have a significant effect
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.
on the mean of the set but has no effect on the median.

THE MEAN AND THE

MEDIAN
Precision describes the reproducibility of measurements—in
Precision describes the reproducibility of measurements—in
other words, the closeness of results that have been obtained
other words, the closeness of results that have been obtained
in exactly the same way. Precision is the closeness of results
in exactly the same way. Precision is the closeness of results
to others obtained in exactly the same way.
to others obtained in exactly the same way.
Three terms are widely used to describe the precision of a set
Three terms are widely used to describe the precision of a set
of replicate data: standard deviation, variance, and coefficient
of replicate data: standard deviation, variance, and coefficient
of variation. These three are functions of how much an
of variation. These three are functions of how much an
individual result xi differs from the mean, called the deviation
individual result xi differs from the mean, called the deviation
from the mean di.
from the mean di.

Note: deviations from the mean are calculated without regard

Note: deviations from the mean are calculated without regard
to sign.
to sign.

PRECISION
Accuracy indicates the closeness of the measurement to the
Accuracy indicates the closeness of the measurement to the
true or accepted value and is expressed by the error. Note that
true or accepted value and is expressed by the error. Note that
accuracy measures agreement between a result and the
accuracy measures agreement between a result and the
accepted value. Accuracy is often more difficult to determine
accepted value. Accuracy is often more difficult to determine
because the true value is usually unknown. An accepted value
because the true value is usually unknown. An accepted value
must be used instead. Accuracy is expressed in terms of either
must be used instead. Accuracy is expressed in terms of either
absolute or relative error.
absolute or relative error.

ACCURACY
The absolute error of a measurement is the difference
The absolute error of a measurement is the difference
between the measured value and the true value. The sign of
between the measured value and the true value. The sign of
the absolute error tells you whether the value in question is
the absolute error tells you whether the value in question is
high or low. If the measurement result is low, the sign is
high or low. If the measurement result is low, the sign is
negative; if the measurement result is high, the sign is
negative; if the measurement result is high, the sign is
positive. The absolute error E in the measurement of a
positive. The absolute error E in the measurement of a
quantity x is given by the equation:
quantity x is given by the equation:

where xt is the true or accepted value of the quantity.

where xt is the true or accepted value of the quantity.

ACCURACY
Illustration of accuracy and precision using the pattern of darts on a dartboard.
Note that we can have very precise results (upper right) with a mean that is not
accurate and an accurate mean (lower left) with data points that are imprecise.
The relative error of a measurement is the absolute error
The relative error of a measurement is the absolute error
divided by the true value. Relative error may be expressed in
divided by the true value. Relative error may be expressed in
percent, parts per thousand, or parts per million, depending on
percent, parts per thousand, or parts per million, depending on
the magnitude of the result. As used in this chapter, relative
the magnitude of the result. As used in this chapter, relative
error refers to the relative absolute error. The relative error Er
error refers to the relative absolute error. The relative error Er
is often a more useful quantity than the absolute error. The
is often a more useful quantity than the absolute error. The
percent relative error is given by the expression:
percent relative error is given by the expression:

Relative error is also expressed in parts per thousand (ppt).

Relative error is also expressed in parts per thousand (ppt).

ACCURACY
 The precision of a measurement is readily determined by
The precision of a measurement is readily determined by
comparing data from carefully replicated experiments.
comparing data from carefully replicated experiments.
Unfortunately, an estimate of the accuracy is not as easy to
Unfortunately, an estimate of the accuracy is not as easy to
obtain. To determine the accuracy, we have to know the true
obtain. To determine the accuracy, we have to know the true
value, which is usually what we are seeking in the analysis.
value, which is usually what we are seeking in the analysis.
that chemical analyses are affected by at least two types of
that chemical analyses are affected by at least two types of
errors.
errors.
One type, called random (or indeterminate) error, causes
One type, called random (or indeterminate) error, causes
data to be scattered more or less symmetrically around a
data to be scattered more or less symmetrically around a
mean value. that chemical analyses are affected by at least
mean value. that chemical analyses are affected by at least
two types of errors. Random, or indeterminate, errors
two types of errors. Random, or indeterminate, errors
affect measurement precision.
affect measurement precision.

TYPES OF ERRORS IN
EXPERIMENTAL DATA
 A second type of error, called systematic (or determinate)
A second type of error, called systematic (or determinate)
error, causes the mean of a data set to differ from the
error, causes the mean of a data set to differ from the
accepted value. Systematic, or determinate, errors affect the
accepted value. Systematic, or determinate, errors affect the
accuracy of results.
accuracy of results.
A third type of error is gross error. Gross errors differ from
A third type of error is gross error. Gross errors differ from
indeterminate and determinate errors. They usually occur only
indeterminate and determinate errors. They usually occur only
occasionally, are often large, and may cause a result to be
occasionally, are often large, and may cause a result to be
either high or low. They are often the product of human errors.
either high or low. They are often the product of human errors.

TYPES OF ERRORS IN
EXPERIMENTAL DATA
 SYSTEMATIC ERRORS

Systematic errors have a definite value, an assignable cause,

Systematic errors have a definite value, an assignable cause,
and are of the same magnitude for replicate measurements
and are of the same magnitude for replicate measurements
made in the same way. They lead to bias in measurement
made in the same way. They lead to bias in measurement
results. Bias measures the systematic error associated with an
results. Bias measures the systematic error associated with an
analysis. It has a negative sign if it causes the results to be low
analysis. It has a negative sign if it causes the results to be low
and a positive sign otherwise.
and a positive sign otherwise.
There are three types of systematic errors:
There are three types of systematic errors:
• Instrumental errors are caused by nonideal instrument
• Instrumental errors are caused by nonideal instrument
behavior, by faulty calibrations, or by use under
behavior, by faulty calibrations, or by use under
inappropriate conditions.
inappropriate conditions.
• Method errors arise from nonideal chemical or physical
• Method errors arise from nonideal chemical or physical
behavior of analytical systems.
behavior of analytical systems.
• Personal errors result from the carelessness, inattention, or
• Personal errors result from the carelessness, inattention, or
personal limitations of the experimenter.
personal limitations of the experimenter.

SOURCES OF
SYSTEMATIC ERRORS
Systematic errors may be either constant or proportional. The
Systematic errors may be either constant or proportional. The
magnitude of a constant error stays essentially the same as
magnitude of a constant error stays essentially the same as
the size of the quantity measured is varied. With constant
the size of the quantity measured is varied. With constant
errors, the absolute error is constant with sample size, but the
errors, the absolute error is constant with sample size, but the
relative error varies when the sample size is changed.
relative error varies when the sample size is changed.
Proportional errors increase or decrease according to the size
Proportional errors increase or decrease according to the size
of the sample taken for analysis. With proportional errors, the
of the sample taken for analysis. With proportional errors, the
absolute error varies with sample size, but the relative error
absolute error varies with sample size, but the relative error
stays constant when the sample size is changed.
stays constant when the sample size is changed.
• Proportional errors decrease or increase in proportion to the
• Proportional errors decrease or increase in proportion to the
size of the sample.
size of the sample.
• Constant errors are independent of the size of the sample
• Constant errors are independent of the size of the sample
being analyzed.
being analyzed.

THE EFFECT OF
SYSTEMATIC ERRORS ON
 Some systematic instrument errors can be found and
Some systematic instrument errors can be found and
corrected by calibration. Periodic calibration of equipment is
corrected by calibration. Periodic calibration of equipment is
always desirable because the response of most instruments
always desirable because the response of most instruments
changes with time as a result of component aging, corrosion,
changes with time as a result of component aging, corrosion,
or mistreatment.
or mistreatment.
Most personal errors can be minimized by careful,
Most personal errors can be minimized by careful,
disciplined laboratory work.
disciplined laboratory work.
After entering a reading into the laboratory notebook, many
After entering a reading into the laboratory notebook, many
scientists habitually make a second reading and then check
scientists habitually make a second reading and then check
this against what has been entered to ensure the correctness
this against what has been entered to ensure the correctness
of the entry.
of the entry.

DETECTION OF SYSTEMATIC
INSTRUMENT AND
Analysis of Standard Samples
Analysis of Standard Samples
The best way to estimate the bias of an analytical method is
The best way to estimate the bias of an analytical method is
by analyzing standard reference materials (SRMs), materials
by analyzing standard reference materials (SRMs), materials
that contain one or more analytes at known concentration
that contain one or more analytes at known concentration
levels. Standard reference materials are obtained in several
levels. Standard reference materials are obtained in several
ways.
ways.
Independent Analysis
Independent Analysis
If standard samples are not available, a second independent
If standard samples are not available, a second independent
and reliable analytical method can be used in parallel with the
and reliable analytical method can be used in parallel with the
method being evaluated. The independent method should
method being evaluated. The independent method should
differ as much as possible from the one under study.
differ as much as possible from the one under study.

DETECTION OF
SYSTEMATIC METHOD
Blank Determinations
Blank Determinations
A blank contains the reagents and solvents used in a
A blank contains the reagents and solvents used in a
determination, but no analyte. Often, many of the sample
determination, but no analyte. Often, many of the sample
constituents are added to simulate the analyte environment,
constituents are added to simulate the analyte environment,
which is called the sample matrix. A blank solution contains
which is called the sample matrix. A blank solution contains
the solvent and all of the reagents in an analysis. Whenever
the solvent and all of the reagents in an analysis. Whenever
feasible, blanks may also contain added constituents to
feasible, blanks may also contain added constituents to
simulate the sample matrix. The term matrix refers to the
simulate the sample matrix. The term matrix refers to the
collection of all the constituents in the sample.
collection of all the constituents in the sample.
Variation in Sample Size
Variation in Sample Size
constant errors can often be detected by varying the sample
constant errors can often be detected by varying the sample
size.
size.

DETECTION OF
SYSTEMATIC METHOD
THANK YOU