UNIVERSITY OF SOUTHERN MINDANAO

ERRORS IN CHEMICAL
ANALYSIS
2ND Semester
A.Y 2022-2023
 Topic Outline

Measurement Uncertainty and Statistics

Errors in analytical measurement

Treatment of data and statistics

Paeldin, 2023 2
 Errors
Errors are differences between observed values and what is true in
nature. Error causes results that are inaccurate or misleading and can
misrepresent nature.

It is impossible to perform a chemical analysis that is totally free of

errors or uncertainties
We can only hope to minimize errors and estimate their size with
acceptable accuracy

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Figure 2. Results from six replicate determination of iron in
aqueous sample of standard solution containing 20.0 ppm iron (III).

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 However,
“The probable magnitude of the error in a measurement can
often be evaluated. It is then possible to define limits within
which the true value of a measured quantity lies with a given
level of probability”

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 Some important terms
Replicates – are samples of about the same size that are carried through an analysis in
exactly the same way.

Why do we need to replicate?

Replicates can be used to measure variation in an analysis so that the statistical

analysis can be applied to evaluate the results.
Individual results from a set of measurements are seldom the same
Usually, the “best” estimate is considered to be the central value for the set.
The central value of a set should be more reliable than any of the individual results.
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 Some important terms
Mean ( ) -the most widely used measure of central value is the
mean. Also called the arithmetic mean or the average.

Median – is the middle result when replicate data are arranged in

increasing or decreasing order.
For odd number of results, the median can be found by arranging the
results in order and locate the middle result.
For an even number, the average value of the middle pair is used.

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 Exercise 2.1
Calculate the mean and median for the data shown in the figure.

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 Some important terms
Precision – describes the reproducibility of measurements. The
closeness of the results that have been obtained in exactly the same
way.
Generally, the precision of a measurement is readily determined by
simply repeating the measurement on replicate samples.

There are three terms widely used to describe the precision of a set of
replicate data: standard deviation, variance, and coefficient of
variation.

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 Some important terms
Accuracy – indicates the closeness of the measurement to the true or
accepted value and is expressed in terms of either absolute or relative
error.

Absolute error (E) – in the measurement of a quantity x is given by the

equation

Where Xt is the true or accepted value

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Example 2.1

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 Some important terms
Relative error – is often a more useful quantity than the absolute
error. The percent relative error is given by the expression.

Relative error maybe expressed in percent, parts per thousand, or

parts per million, depending on the magnitude of the result

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Figure 2.2. Illustration of Accuracy and Precision using the pattern of darts

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 Types of error in Experimental Data
Chemical analyses are affected by at least two types of errors:

1. Systematic error (determinate error) –causes the mean of a data

set to differ from the accepted value. Affects the accuracy of the
results

2. Random error ( Indeterminate error) – causes the data to be more

scattered, more or less symmetrically around a mean value. Affects
the precision of the results

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A third type of error is gross error. It differs from both determinate
and indeterminate.
Usually occur only occasionally
Often large and may cause the result to be either high or low
Often product of human errors
Gross errors lead to outliers, results that appear to differ markedly
from all other data in a set of replicate measurements.

Outlier – is an occasional result in replicate measurements that differs

significantly from the other results.
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 Systematic errors
Have a definite value, an assignable cause, and are of the same magnitude for
replicate measurements made in the same way. The lead to bias in
measurement results.

Bias – measures the systematic error associated with an analysis. It has a

negative sign if it causes the result to be low and positive if otherwise.

3 types of Systematic error:

1. Instrumental error
2. Method error
3. Personal error
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 Systematic errors
Instrumental error – are cause by nonideal instrument behaviour, by
faulty calibrations, or by used under in appropriate conditions.

• Pipets, burets, and volumetric flasks may hold or deliver volumes

slightly different from those indicated by their graduations.
• Calibration eliminates most systematic errors of this type.
• Electronic instruments can be influenced by noise, temperature, pH
and are also subject to systematic errors.
Errors of these types usually are detectable and correctable.

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 Method error
The nonideal chemical or physical behavior of the reagents and
reactions on which an analysis is based often introduce systematic
method errors.
Such sources of nonideality include the slowness of some reactions,
the incompleteness of others, the instability of some species, the
lack of specificity of most reagents, and the possible occurrence of
side reactions that interfere with the measurement process.
Errors inherent in a method are often difficult to detect and hence,
these errors are usually the most difficult to identify and correct.

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 Personal errors
result from the carelessness, inattention, or personal limitations of
the experimenter.
 Many measurements require personal judgments.
Examples include estimating the position of a pointer between two
scale divisions, the color of a solution at the end point in a titration,
or the level of a liquid with respect to a graduation in a pipet or
buret.
Judgments of this type are often subject to systematic,
unidirectional errors.

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A universal source of personal error is prejudice, or bias.
 Number bias is another source of personal error that varies
considerably from person to person.
The most frequent number bias encountered in estimating the
position of a needle on a scale involves a preference for the digits 0
and 5.
Also common is a prejudice favoring small digits over large and even
numbers over odd.
Digital and computer displays on pH meters, laboratory balances,
and other electronic instruments eliminate number bias because no
judgment is involved in taking a reading
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 Detection of Systematic Instrument and
Personal error
Instrument errors can be found and corrected by calibrating the
equipment

Personal errors can be minimized by exercising care and self-discipline

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 Detection of Systematic Method Errors

Method errors are the hardest to overcome; some ideas to overcome

this one include using standard reference materials, independent
analysis running blank determinations, etc.

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 Exercise
Experiment Molar Mass, g/mol
Richard and Willard determined the molar
mass of lithium and collected the following 1 6.9391
data.
2 6.9407

(a)Find the mean molar mass 3 6.9409

(b)Find the median
4 6.9399
(c)Assuming that the currently accepted
molar mass of lithium (6.941 g/mol) as 5 6.9407
the true value, calculate the percent
relative error of the mean value 6 6.9391

determined by Richard and Willard 7 6.9406

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