ANALYTICAL CHEMISTRY

RANDOM ERRORS IN CHEMICAL ANALYSES

 ERRORS IN CHEMICAL ANALYSES
Random errors are present in every measurement no
matter how careful the experimenter.
 THE NATURE OF RANDOM ERRORS

Random, or indeterminate, errors can never be totally eliminated

Random, or indeterminate, errors can never be totally eliminated
and are often the major source of uncertainty in a determination.
and are often the major source of uncertainty in a determination.
Random errors are caused by the many uncontrollable variables
Random errors are caused by the many uncontrollable variables
that accompany every measurement. Usually, most contributors
that accompany every measurement. Usually, most contributors
to random error cannot be positively identified. Even if we can
to random error cannot be positively identified. Even if we can
identify random error sources, it is often impossible to measure
identify random error sources, it is often impossible to measure
them because most are so small that they cannot be detected
them because most are so small that they cannot be detected
individually. The accumulated effect of the individual
individually. The accumulated effect of the individual
uncertainties, however, causes replicate results to fluctuate
uncertainties, however, causes replicate results to fluctuate
randomly around the mean of the set.
randomly around the mean of the set.
We can get a qualitative idea of the way small undetectable
We can get a qualitative idea of the way small undetectable
uncertainties produce a detectable random error in the following
uncertainties produce a detectable random error in the following
way. Imagine a situation in which just four small random errors
way. Imagine a situation in which just four small random errors
combine to give an overall error. We will assume that each error
combine to give an overall error. We will assume that each error
has an equal probability of occurring and that each can cause
has an equal probability of occurring and that each can cause
the final result to be high or low by a fixed amount ±U.
the final result to be high or low by a fixed amount ±U.

RANDOM ERROR
SOURCES
RANDOM ERROR
SOURCES
Table 6-1 shows all the possible ways the four errors can
Table 6-1 shows all the possible ways the four errors can
combine to give the indicated deviations from the mean value.
combine to give the indicated deviations from the mean value.
Note that only one combination leads to a deviation of 14 U, four
Note that only one combination leads to a deviation of 14 U, four
combinations give a deviation of 12 U, and six give a deviation of
combinations give a deviation of 12 U, and six give a deviation of
0 U. The negative errors have the same relationship. This ratio of
0 U. The negative errors have the same relationship. This ratio of
1:4:6:4:1 is a measure of the probability for a deviation of each
1:4:6:4:1 is a measure of the probability for a deviation of each
magnitude
magnitude

RANDOM ERROR
SOURCES
From experience with many determinations, we find that the
From experience with many determinations, we find that the
distribution of replicate data from most quantitative analytical
distribution of replicate data from most quantitative analytical
experiments approaches that of the Gaussian curve. A Gaussian,
experiments approaches that of the Gaussian curve. A Gaussian,
or normal error curve, is a curve that shows the symmetrical
or normal error curve, is a curve that shows the symmetrical
distribution of data around the mean of an infinite set of data.
distribution of data around the mean of an infinite set of data.

DISTRIBUTION OF
EXPERIMENTAL
Sources of random uncertainties in the calibration of a pipet
Sources of random uncertainties in the calibration of a pipet
include: (1) visual judgments, such as the level of the water with
include: (1) visual judgments, such as the level of the water with
respect to the marking on the pipet and the mercury level in the
respect to the marking on the pipet and the mercury level in the
thermometer; (2) variations in the drainage time and in the angle
thermometer; (2) variations in the drainage time and in the angle
of the pipet as it drains; (3) temperature fluctuations, which
of the pipet as it drains; (3) temperature fluctuations, which
affect the volume of the pipet, the viscosity of the liquid, and the
affect the volume of the pipet, the viscosity of the liquid, and the
performance of the balance; and (4) vibrations and drafts that
performance of the balance; and (4) vibrations and drafts that
cause small variations in the balance readings. Undoubtedly,
cause small variations in the balance readings. Undoubtedly,
there are many other sources of random uncertainty in this
there are many other sources of random uncertainty in this
calibration process that we have not listed. Even the simple
calibration process that we have not listed. Even the simple
process of calibrating a pipet is affected by many small and
process of calibrating a pipet is affected by many small and
uncontrollable variables. The cumulative influence of these
uncontrollable variables. The cumulative influence of these
variables is responsible for the observed scatter of results around
variables is responsible for the observed scatter of results around
the mean.
the mean.

RANDOM ERROR
SOURCES
 STATISTICAL TREATMENT OF RANDOM
ERRORS

Statistical analysis only reveals information that is already

Statistical analysis only reveals information that is already
present in a data set. No new information is created by statistical
present in a data set. No new information is created by statistical
treatments. Statistical methods, do allow us to categorize and
treatments. Statistical methods, do allow us to categorize and
characterize data in different ways and to make objective and
characterize data in different ways and to make objective and
intelligent decisions about data quality and interpretation.
intelligent decisions about data quality and interpretation.
Typically in a scientific study, we infer information about a
Typically in a scientific study, we infer information about a
population or universe from observations made on a subset or
population or universe from observations made on a subset or
sample. The population is the collection of all measurements of
sample. The population is the collection of all measurements of
interest and must be carefully defined by the experimenter. In
interest and must be carefully defined by the experimenter. In
some cases, the population is finite and real, while in others, the
some cases, the population is finite and real, while in others, the
population is hypothetical or conceptual in nature. In many of the
population is hypothetical or conceptual in nature. In many of the
cases encountered in analytical chemistry, the population is
cases encountered in analytical chemistry, the population is
conceptual.
conceptual.

SAMPLES AND
POPULATIONS
As shown, curves such as these can be described by an equation
As shown, curves such as these can be described by an equation
that contains just two parameters, the population mean m and
that contains just two parameters, the population mean m and
the population standard deviation s. The term parameter refers
the population standard deviation s. The term parameter refers
to quantities such as m and s that define a population or
to quantities such as m and s that define a population or
distribution. Data values such as x are variables. The term
distribution. Data values such as x are variables. The term
statistic refers to an estimate of a parameter that is made from
statistic refers to an estimate of a parameter that is made from
a sample of data as discussed below. The sample mean and the
a sample of data as discussed below. The sample mean and the
sample standard deviation are examples of statistics that
sample standard deviation are examples of statistics that
estimate parameters m and s respectively. the equation for a
estimate parameters m and s respectively. the equation for a
normalized Gaussian curve has the form
normalized Gaussian curve has the form

PROPERTIES OF
GAUSSIAN CURVES
 The Population Mean m and the Sample Mean
 The Population Mean m and the Sample Mean
Scientists find it useful to differentiate between the sample
Scientists find it useful to differentiate between the sample
mean and the population mean. The sample mean x is the
mean and the population mean. The sample mean x is the
arithmetic average of a limited sample drawn from a population
arithmetic average of a limited sample drawn from a population
of data. The sample mean is defined as the sum of the
of data. The sample mean is defined as the sum of the
measurement values divided by the number of measurements.
measurement values divided by the number of measurements.

PROPERTIES OF
GAUSSIAN CURVES
 Figure 6-4 Normal error curves. The standard deviation for curve
 Figure 6-4 Normal error curves. The standard deviation for curve
B is twice that for curve A, that is, B = 2 A.
B is twice that for curve A, that is, B = 2 A.

PROPERTIES OF
GAUSSIAN CURVES
 The sample mean x is found from
 The sample mean x is found from

where N is the number of measurements in the sample set.

where N is the number of measurements in the sample set.
The same equation is used to calculate the population mean
The same equation is used to calculate the population mean

where N is now the total number of measurements in the

where N is now the total number of measurements in the
population.
population.

PROPERTIES OF
GAUSSIAN CURVES
 The Population Standard Deviation
 The Population Standard Deviation
The population standard deviation s, which is a measure of the
The population standard deviation s, which is a measure of the
precision of the population, is given by the equation
precision of the population, is given by the equation

where N is the number of data points making up the population.

where N is the number of data points making up the population.
In the absence of systematic error, the population mean m is the
In the absence of systematic error, the population mean m is the
true value of a measured quantity.
true value of a measured quantity.

PROPERTIES OF
GAUSSIAN CURVES
Another type of normal error curve in which the x axis is now a
Another type of normal error curve in which the x axis is now a
new variable z, which is defined as
new variable z, which is defined as

The quantity z represents the deviation of a result from the

The quantity z represents the deviation of a result from the
population mean relative to the standard deviation. It is
population mean relative to the standard deviation. It is
commonly given as a variable in statistical tables since it is a
commonly given as a variable in statistical tables since it is a
dimensionless quantity.
dimensionless quantity.

PROPERTIES OF
GAUSSIAN CURVES
The equation for the Gaussian error curve is
The equation for the Gaussian error curve is

A normal error curve has several general properties: (a) The

A normal error curve has several general properties: (a) The
mean occurs at the central point of maximum frequency, (b)
mean occurs at the central point of maximum frequency, (b)
there is a symmetrical distribution of positive and negative
there is a symmetrical distribution of positive and negative
deviations about the maximum, and (c) there is an exponential
deviations about the maximum, and (c) there is an exponential
decrease in frequency as the magnitude of the deviations
decrease in frequency as the magnitude of the deviations
increases. Thus, small uncertainties are observed much more
increases. Thus, small uncertainties are observed much more
often than very large ones.
often than very large ones.

PROPERTIES OF
GAUSSIAN CURVES
Areas under a Gaussian Curve
Areas under a Gaussian Curve
Because of area relationships such as these, the standard
Because of area relationships such as these, the standard
deviation of a population of data is a useful predictive tool.
deviation of a population of data is a useful predictive tool.

PROPERTIES OF
GAUSSIAN CURVES
The sample standard deviation s is given by the equation
The sample standard deviation s is given by the equation

where the quantity (xi 2 x) represents the deviation di of value xi

where the quantity (xi 2 x) represents the deviation di of value xi
from the mean x. Note that Equation 6-4 differs from Equation 6-
from the mean x. Note that Equation 6-4 differs from Equation 6-
1 in two ways. First, the sample mean, x, appears in the
1 in two ways. First, the sample mean, x, appears in the
numerator in place of the population mean, m. Second, N in
numerator in place of the population mean, m. Second, N in
Equation 6-1 is replaced by the number of degrees of freedom (N
Equation 6-1 is replaced by the number of degrees of freedom (N
2 1). When N 2 1 is used instead of N, s is said to be an unbiased
2 1). When N 2 1 is used instead of N, s is said to be an unbiased
estimator of the population standard deviation s. If this
estimator of the population standard deviation s. If this
substitution is not used, the calculated s will be less on average
substitution is not used, the calculated s will be less on average
than the true standard deviation s, that is, s will have a negative
than the true standard deviation s, that is, s will have a negative
bias.
bias.

THE SAMPLE STANDARD

DEVIATION: A MEASURE
An Alternative Expression for Sample Standard Deviation
An Alternative Expression for Sample Standard Deviation
To find s with a calculator that does not have a standard
To find s with a calculator that does not have a standard
deviation key, the following rearrangement is easier to use than
deviation key, the following rearrangement is easier to use than
directly applying
directly applying

THE SAMPLE STANDARD

DEVIATION: A MEASURE
Standard Error of the Mean
Standard Error of the Mean
Thestandard error of a mean, sm, is the standard deviation of
Thestandard error of a mean, sm, is the standard deviation of
a set of data divided by the square root of the number of data
a set of data divided by the square root of the number of data
points in the set.
points in the set.

THE SAMPLE STANDARD

DEVIATION: A MEASURE
We describe several statistical tests that are used to test
We describe several statistical tests that are used to test
hypotheses, to produce confidence intervals for results, and to
hypotheses, to produce confidence intervals for results, and to
reject outlying data points. Most of these tests are based on
reject outlying data points. Most of these tests are based on
sample standard deviations. The probability that these statistical
sample standard deviations. The probability that these statistical
tests provide correct results increases as the reliability of s
tests provide correct results increases as the reliability of s
becomes greater.
becomes greater.

RELIABILITY OF S AS A
MEASURE OF PRECISION
 Pooling Data to Improve the Reliability of s
 Pooling Data to Improve the Reliability of s
If we have several subsets of data, a better estimate of the
If we have several subsets of data, a better estimate of the
population standard deviation can be obtained by pooling
population standard deviation can be obtained by pooling
(combining) the data instead of using only one data set. Again,
(combining) the data instead of using only one data set. Again,
we must assume the same sources of random error in all the
we must assume the same sources of random error in all the
measurements. This assumption is usually valid if the samples
measurements. This assumption is usually valid if the samples
have similar compositions and have been analyzed in exactly the
have similar compositions and have been analyzed in exactly the
same way. We must also assume that the samples are randomly
same way. We must also assume that the samples are randomly
drawn from the same population and thus have a common value
drawn from the same population and thus have a common value
of .
of .

RELIABILITY OF S AS A
MEASURE OF PRECISION
Variance (s2)2
Variance (s )
The variance is just the square of the standard deviation. The
The variance is just the square of the standard deviation. The
sample variance s2 is an estimate of the population variance s 2 2
sample variance s2 is an estimate of the population variance s
and is given by
and is given by

Note that the standard deviation has the same units as the data,
Note that the standard deviation has the same units as the data,
while the variance has the units of the data squared. Scientists
while the variance has the units of the data squared. Scientists
tend to use standard deviation rather than variance because it is
tend to use standard deviation rather than variance because it is
easier to relate a measurement and its precision if they both
easier to relate a measurement and its precision if they both
have the same units.
have the same units.

VARIANCE AND OTHER

MEASURES OF PRECISION
Relative Standard Deviation (RSD) and Coefficient of Variation
Relative Standard Deviation (RSD) and Coefficient of Variation
(CV)
(CV)
Frequently standard deviations are given in relative rather than
Frequently standard deviations are given in relative rather than
absolute terms. We calculate the relative standard deviation by
absolute terms. We calculate the relative standard deviation by
dividing the standard deviation by the mean value of the data
dividing the standard deviation by the mean value of the data
set. The relative standard deviation, RSD, is sometimes given the
set. The relative standard deviation, RSD, is sometimes given the
symbol Sr.
symbol Sr.

VARIANCE AND OTHER

MEASURES OF PRECISION
The relative standard deviation multiplied by 100% is called the
The relative standard deviation multiplied by 100% is called the
coefficient of variation (CV).
coefficient of variation (CV).

VARIANCE AND OTHER

MEASURES OF PRECISION
Spread or Range (w)
Spread or Range (w)
The spread, or range, w, is another term that is sometimes used
The spread, or range, w, is another term that is sometimes used
to describe the precision of a set of replicate results. It is the
to describe the precision of a set of replicate results. It is the
difference between the largest value in the set and the smallest.
difference between the largest value in the set and the smallest.

VARIANCE AND OTHER

MEASURES OF PRECISION
 STANDARD DEVIATION OF CALCULATED
RESULTS
Often we must estimate the standard deviation of a result that
Often we must estimate the standard deviation of a result that
has been calculated from two or more experimental data points,
has been calculated from two or more experimental data points,
each of which has a known sample standard deviation. As shown
each of which has a known sample standard deviation. As shown
in Table 6-4, the way such estimates are made depends on the
in Table 6-4, the way such estimates are made depends on the
types of calculations that are involved. The relationships shown
types of calculations that are involved. The relationships shown
in this table are derived in Appendix 9.
in this table are derived in Appendix 9.
The variance of a sum or difference is equal to the sum of the
The variance of a sum or difference is equal to the sum of the
variances of the numbers making up that sum or difference.
variances of the numbers making up that sum or difference.
Hence, the standard deviation of the result Sr is
Hence, the standard deviation of the result Sr is

For a sum or a difference, the standard deviation of the answer is

For a sum or a difference, the standard deviation of the answer is
the square root of the sum of the squares of the standard
the square root of the sum of the squares of the standard
deviations of the numbers used in the calculation.
deviations of the numbers used in the calculation.
where Sa, Sb, and Sc are the standard deviations of the three
where Sa, Sb, and Sc are the standard deviations of the three
terms making up the result.
terms making up the result.

STANDARD DEVIATION OF
A SUM OR DIFFERENCE
The relative standard deviation of a product or quotient is
The relative standard deviation of a product or quotient is
determined by the relative standard deviations of the numbers
determined by the relative standard deviations of the numbers
forming the computed result. For example, in the case of
forming the computed result. For example, in the case of

we obtain the relative standard deviation S y/y of the result by

we obtain the relative standard deviation S y/y of the result by
summing the squares of the relative standard deviations of a, b,
summing the squares of the relative standard deviations of a, b,
and c and then calculating the square root of the sum:
and c and then calculating the square root of the sum:

For multiplication or division, the relative standard deviation of

For multiplication or division, the relative standard deviation of
the answer is the square root of the sum of the squares of the
the answer is the square root of the sum of the squares of the
relative standard deviations of the numbers that are multiplied
relative standard deviations of the numbers that are multiplied
or divided.
or divided.

 STANDARD DEVIATION OF
A PRODUCT OR QUOTIENT
Consider the relationship
Consider the relationship

where the exponent x can be considered to be free of

where the exponent x can be considered to be free of
uncertainty. As shown in Table 6-4 and Appendix 9, the relative
uncertainty. As shown in Table 6-4 and Appendix 9, the relative
standard deviation in y resulting from the uncertainty in a is
standard deviation in y resulting from the uncertainty in a is

Therefore, the relative standard deviation of the square of a

Therefore, the relative standard deviation of the square of a
number is twice the relative standard deviation of the number,
number is twice the relative standard deviation of the number,
the relative standard deviation of the cube root of a number is
the relative standard deviation of the cube root of a number is
one third that of the number, and so forth.
one third that of the number, and so forth.

STANDARD DEVIATIONS IN
EXPONENTIAL
The absolute standard deviation of the logarithm of a number is
The absolute standard deviation of the logarithm of a number is
determined by the relative standard deviation of the number;
determined by the relative standard deviation of the number;
conversely, the relative standard deviation of the antilogarithm of
conversely, the relative standard deviation of the antilogarithm of
a number is determined by the absolute standard deviation of
a number is determined by the absolute standard deviation of
the number.
the number.

STANDARD DEVIATIONS OF
LOGARITHMS AND
 REPORTING COMPUTED DATA

A numerical result is worthless to users of the data unless they

A numerical result is worthless to users of the data unless they
know something about its quality. Therefore, it is always
know something about its quality. Therefore, it is always
essential to indicate your best estimate of the reliability of your
essential to indicate your best estimate of the reliability of your
data. One of the best ways of indicating reliability is to give a
data. One of the best ways of indicating reliability is to give a
confidence interval at the 90% or 95% confidence level.
confidence interval at the 90% or 95% confidence level.
Another method is to report the absolute standard deviation or
Another method is to report the absolute standard deviation or
the coefficient of variation of the data. If one of these is reported,
the coefficient of variation of the data. If one of these is reported,
it is a good idea to indicate the number of data points that were
it is a good idea to indicate the number of data points that were
used to obtain the standard deviation so that the user has some
used to obtain the standard deviation so that the user has some
idea of the reliability of s. A much less satisfactory but more
idea of the reliability of s. A much less satisfactory but more
common indicator of the quality of data is the significant figure
common indicator of the quality of data is the significant figure
convention.
convention.
The significant figures in a number are all of the certain digits
The significant figures in a number are all of the certain digits
plus the first uncertain digit. We often indicate the probable
plus the first uncertain digit. We often indicate the probable
uncertainty associated with an experimental measurement by
uncertainty associated with an experimental measurement by
rounding the result so that it contains only significant figures.
rounding the result so that it contains only significant figures.
Rules for determining the number of significant figures:
Rules for determining the number of significant figures:
1. Disregard all initial zeros.
1. Disregard all initial zeros.
2. Disregard all final zeros unless they follow a decimal point.
2. Disregard all final zeros unless they follow a decimal point.
3. All remaining digits including zeros between nonzero digits
3. All remaining digits including zeros between nonzero digits
are significant.
are significant.

SIGNIFICANT FIGURES
Sums and Differences
Sums and Differences
For addition and subtraction, the number of significant figures
For addition and subtraction, the number of significant figures
can be found by visual inspection.
can be found by visual inspection.
Products and Quotients
Products and Quotients
Sometimes it is suggested for multiplication and division that the
Sometimes it is suggested for multiplication and division that the
answer should be rounded so that it contains the same number
answer should be rounded so that it contains the same number
of significant digits as the original number with the smallest
of significant digits as the original number with the smallest
number of significant digits. Unfortunately, this procedure
number of significant digits. Unfortunately, this procedure
sometimes leads to incorrect rounding.
sometimes leads to incorrect rounding.

SIGNIFICANT FIGURES IN
NUMERICAL
Logarithms and Antilogarithms
Logarithms and Antilogarithms
Be especially careful in rounding the results of calculations
Be especially careful in rounding the results of calculations
involving logarithms. The following rules apply to most situations:
involving logarithms. The following rules apply to most situations:
1. In a logarithm of a number, keep as many digits to the right
1. In a logarithm of a number, keep as many digits to the right
of the decimal point as there are significant figures in the
of the decimal point as there are significant figures in the
original number.
original number.
2. In an antilogarithm of a number, keep as many digits as
2. In an antilogarithm of a number, keep as many digits as
there are digits to the right of the decimal point in the original
there are digits to the right of the decimal point in the original
number.
number.

SIGNIFICANT FIGURES IN
NUMERICAL
Always round the computed results of a chemical analysis in an
Always round the computed results of a chemical analysis in an
appropriate way. We should note that it is seldom justifiable to
appropriate way. We should note that it is seldom justifiable to
keep more than one significant figure in the standard deviation
keep more than one significant figure in the standard deviation
because the standard deviation contains error as well. For
because the standard deviation contains error as well. For
certain specialized purposes, such as reporting uncertainties in
certain specialized purposes, such as reporting uncertainties in
physical constants in research articles, it may be useful to keep
physical constants in research articles, it may be useful to keep
two significant figures, and there is certainly nothing wrong with
two significant figures, and there is certainly nothing wrong with
including a second digit in the standard deviation. However, it is
including a second digit in the standard deviation. However, it is
important to recognize that the uncertainty usually lies in the
important to recognize that the uncertainty usually lies in the
first digit.
first digit.

ROUNDING DATA
Two cases are encountered when reporting the results of
Two cases are encountered when reporting the results of
chemical calculations. It is especially important to postpone
chemical calculations. It is especially important to postpone
rounding until the calculation is completed. At least one extra
rounding until the calculation is completed. At least one extra
digit beyond the significant digits should be carried through all of
digit beyond the significant digits should be carried through all of
the computations in order to avoid a rounding error. This extra
the computations in order to avoid a rounding error. This extra
digit is sometimes called a “guard” digit. Modern calculators
digit is sometimes called a “guard” digit. Modern calculators
generally retain several extra digits that are not significant, and
generally retain several extra digits that are not significant, and
the user must be careful to round final results properly so that
the user must be careful to round final results properly so that
only significant figures are included. Example 6-8 illustrates this
only significant figures are included. Example 6-8 illustrates this
procedure.
procedure.

EXPRESSING RESULTS OF
CHEMICAL CALCULATIONS
THANK YOU