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Errors in Chemical
Analysis

Technological University of the Philippines

Addie Albano

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What’s one mistake you’ve committed that you will

never forget or regret about a lot?

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Titanic, 1912

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Piper alpha oil rig, 1988 (Afghanistan)

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Errors in Chemical Analysis

Error refers to the difference between a measured value
and the “true” or “known” value. Often denotes the
estimated uncertainty in a measurement or experiment.

• Measurements invariably involve errors and

uncertainties. It is impossible to perform a
chemical analysis that is totally free of errors or
uncertainties.

• The greater the error, the less representative the

data are of the population and the less reliable
are the results of the study.

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Replicates

Replicates are samples of about the same size

that are carried through an analysis in exactly the
same way.

In order to improve the reliability and to obtain

information about the variability of results, two to
five portions (replicates) of a sample are usually
carried through an entire analytical procedure.

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Measurement of Central Tendency

The mean, also called the arithmetic mean or the average, is obtained by dividing the sum of replicate
measurements by the number of measurements.

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.

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Accuracy and Precision

Accuracy indicates the closeness of the measurement 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. Relative error may be
expressed in percent, parts per thousand, or parts per million, depending on the magnitude of the result.

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Accuracy and Precision

Precision is the closeness of results to others obtained in exactly the same way.

• Standard deviation

• Variance

• Coefficient of variation

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Accuracy and Precision

Types of Precision

1. Instrument precision, also called injection precision, is the reproducibility observed when the same quantity of
one sample is repeatedly introduced (>10 times) into an instrument.

2. Intra-assay precision is evaluated by analyzing aliquots of a homogeneous material several times by one
person on one day with the same equipment.

3. Intermediate precision, formerly called ruggedness, is the variation observed when an assay is performed by
different people on different instruments on different days in the same lab.

4. Interlaboratory precision, also called reproducibility, is the most general measure of reproducibility observed
when aliquots of the same sample are analyzed by different people in different laboratories.

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Accuracy and Precision

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Errors in Chemical Analysis

Systematic Errors
Determinate error, affects accuracy

The presence of this type of error can be traced and identified in a chemical measurement;
hence, it is also called determinate error
Instrumental error Personal error Method error
Instrumental errors are caused by Personal errors result from the Errors due to method are caused
nonideal instrument behavior, by faulty carelessness, inattention, or by the nonideal chemical or
calibrations, or by use under personal limitations of the analyst. physical behavior of the reagents
inappropriate conditions. and reactions on which an
Example: analysis is based.
Examples: • Include personal judgments
• Glassware may hold or deliver such as estimating the position Examples:
volumes slightly different from those of a pointer between two scale • Slowness of some reactions or
indicated by their graduations. divisions, the color of a incompleteness of others
• Electronic instruments can be solution, or the level of a liquid • Possible occurrence of side
influenced by noise, temperature, pH with respect to a graduation. reactions that interfere with
and are also subject to systematic the measurement process
errors.
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Detection and Elimination of Systematic Errors

For Instrumental and Personal Errors:

1. 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.
2. Most personal errors can be minimized by careful, disciplined laboratory work.
3. It is a good habit to check instrument readings, notebook entries, and calculations systematically.

For Method Errors:

1. Analysis of Standard Samples – Certified Reference Materials (CRM) are 'controls' or standards used to check the
quality and metrological traceability of products, to validate analytical measurement methods, or for the calibration
of instruments.
2. Independent Analysis – Round robin experiment.
3. Blank determination – A blank solution contains the reagents and solvents used in a determination, but no analyte.
4. Variation in Sample Size – As the size of a measurement increases, the effect of a constant error decreases. The
more information you have, the more accurate your results are going to be. Thus, constant errors can often be
detected by varying the sample size.

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Errors in Chemical Analysis

Random Errors
Indeterminate error, affects precision
Arises from natural limitation on our ability to make physical measurements.
Causes data to be scattered more or less systematically around a mean value.
Always present and cannot be corrected has an equal chance of being positive or negative.

✓ No identifiable cause
✓ Always present
✓ Cannot be eliminated
✓ The ultimate limitation on the determination of a quantity

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Minimizing Random Errors

The sources of random errors cannot be traced (indeterminate); these can only be evaluated using statistics. Cannot
be eliminated, but it might be reduced by a better experiment.

Example:

• Sample source - Changes in experimental conditions

• How to minimize them? Take repeated measurements and use of statistics like mean, standard deviation, variance,
coefficient of variation, etc.

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Errors in Chemical Analysis

Gross Errors
Gross errors lead to outliers that there is no alternative to abandoning the experiment and making a
completely fresh start. Often the product of human errors. They usually occur only occasionally, are often
large, and may cause a result to be either extremely high or low

Examples:
1. Complete instrument breakdown
2. Accidentally dropping or discarding a crucial sample
3. Discovering during the course of the experiment that a supposedly pure reagent was in fact badly
contaminated

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Practice Problem
Categorize each as a determinate or indeterminate error and further classify determinate errors as instrumental,
method or personal.
1. An unknown sample being weighed is hygroscopic.
2. One component of a mixture being analyzed quantitatively by GC reacts with the column packing.
3. A radioactive sample being counted repeatedly without any change in condition yields a slightly different
count at each trial.
4. The tip of the pipet used in the analysis is broken.
5. In measuring the same peak heights of a chromatogram, two technician each report different heights.

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References
Christian et al. (2014). Analytical Chemistry, 7th ed. USA: John Wiley & Sons
Hargis, L. (1988). Analytical Chemistry. New Jersey: Prentice-Hall International Edition.
Harris, D. (2016) Quantitative Chemical Analysis, 9th edition. New York: W.H. Freeman and Company.
Harvey, D. (2016) Analytical Chemistry 2.0. Electronic version
Skoog et al. (2014). Fundamentals of Analytical Chemistry, 9th edition. Canada: Brooks/Cole Publishers Company

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