ERRORS IN CHEMICAL ANALYSIS

Lecture Notes 04
Analytical Chemistry 01
CHEM 20105
OUTLINE

1. Some important terms

2. Systematic errors
3. Additional problems
4. References

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
1. SOME IMPORTANT TERMS
• Replicates are samples of about the same size that are
carried through an analysis in exactly the same way.

• Mean, arithmetic mean or the average, is obtained by

dividing the sum of replicate measurements by the
number of measurements in the set.

• The median is the middle result when replicate data are

arranged in increasing or decreasing order. For an odd
number of results, the median can be found by arranging
the results in order and locating the middle result. For an
even number, the average value of the middle pair is
used.
Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
1. SOME IMPORTANT TERMS
• Precision describes the reproducibility of
measurements or the closeness of results that
have been obtained in exactly the same way. The
precision of a measurement is readily determined
by simply repeating the measurement on
replicate samples.

• Ways of expressing precision:

standard deviation
variance
coefficient of variation
Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
1. SOME IMPORTANT TERMS
• Accuracy indicates the closeness of the
measurement to the true or accepted value and is
expressed by the error.

• Absolute error is the difference between the

measured value and the true value. Note: Sign is
kept in stating the error.

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
1. SOME IMPORTANT TERMS
• Relative error is the absolute error divided by the
true value.

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
1. SOME IMPORTANT TERMS

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
1. SOME IMPORTANT TERMS
TYPES OF ERRORS

1. Random, or indeterminate, errors affect measurement

precision. They cause data to be scattered more or less
symmetrically around a mean value.
2. Systematic, or determinate, errors affect the accuracy of
results. They cause the mean of a data set to differ from
the accepted value.
3. Gross errors usually occur occasionally, are often large,
and may cause a result to be either high or low. They are
often the product of human errors. They lead to outliers,
results that appear to differ markedly from all other data
in a set of replicate measurements.

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
2. SYSTEMATIC ERRORS
• Systematic errors have a definite value, an
assignable cause, and are of the same magnitude
for replicate measurements made in the same
way. They lead to bias in measurement results.

• Bias measures the systematic error associated

with an analysis. It has a negative sign if it causes
the results to be low and a positive sign
otherwise.

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
2. SYSTEMATIC ERRORS
SOURCES OF SYSTEMATIC ERRORS

1. Instrumental errors are caused by nonideal

instrument behavior, by faulty calibrations, or by use
under inappropriate conditions.

2. Method errors arise from nonideal chemical or

physical behavior of analytical systems.

3. Personal errors result from the carelessness,

inattention, or personal limitations of the
experimenter.
Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
2. SYSTEMATIC ERRORS
EFFECT OF SYSTEMATIC ERRORS IN ANALYTICAL
RESULTS

Constant error - The magnitude of the error stays

essentially the same as the size of the quantity
measured is varied.

Proportional errors – The magnitude of error

increase or decrease according to the size of the
sample taken for analysis.
Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
2. SYSTEMATIC ERRORS
DETECTION OF SYSTEMATIC INSTRUMENT AND PERSONAL
ERRORS

• Some systematic instrument errors can be found and corrected

by calibration. Periodic calibration of equipment is always
desirable because the response of most instruments changes
with time as a result of component aging, corrosion, or
mistreatment.

• Many systematic instrument errors involve interferences where

a species present in the sample affects the response of the
analyte.

• Most personal errors can be minimized by careful, disciplined

laboratory work. It is a good habit to check instrument readings,
notebook entries, and calculations systematically.
Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
2. SYSTEMATIC ERRORS
DETECTION OF SYSTEMATIC METHOD
ERRORS

1. Analysis of Standard Samples

• The best way to estimate the bias

of an analytical method is by
analyzing standard reference
materials (SRMs), materials that
contain one or more analytes at
known concentration levels.

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
2. SYSTEMATIC ERRORS
2. Independent Analysis

A second independent and reliable analytical method can be used in parallel

with the method being evaluated. The independent method should differ as
much as possible from the one under study.

3. Blank Determinations

A blank contains the reagents and solvents used in a determination, but no

analyte. In a blank determination, all steps of the analysis are performed on
the blank material. The results are then applied as a correction to the
sample measurements. Blank determinations reveal errors due to
interfering contaminants from the reagents and vessels employed in the
analysis.

4. Variation of Sample Size

Constant errors can often be detected by varying the sample size.

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
3. ADDITIONAL PROBLEMS (1)
A loss of 0.4 mg of Zn occurs in the course of an
analysis for that element. Calculate the percent
relative error due to this loss if the mass of Zn in the
sample is
(a) 30 mg.
(b) 150 mg.
(c) 300 mg
(d) 500 mg.

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
3. ADDITIONAL PROBLEMS (2)
• Find the mean and median of each of the following sets of data.
Determine the deviation from the mean for each data point
within the sets and find the mean deviation for each set.

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
3. ADDITIONAL PROBLEMS (Answers)

Skoog, D.A., West, D.M., Holler, F.J. & Crouch, S.R. (2013) Fundamentals of Analytical Chemistry, 9 th
REFERENCES/SOURCES:

• Skoog, D.A., West, D.M., Holler, F.J. & Crouch,

S.R. (2013) Fundamentals of Analytical
Chemistry, 9th Edition. Brookes/Cole, Cengage
Learning, Belmont, USA