Topic 2: Evaluation of

Experimental Data
• Mean, median (Measures of Central
Tendency)
• Uncertainty in Measurement (precision
and accuracy)
• Errors
• Significant figures and rounding off
 Why study this topic?
• Chemistry professionals spend a rather
significant amount of time analyzing
samples that represent large bulk system.
• Eg. Analysis of environmental water for
pollutants, analysis of seafood for heavy
metals, etc.
• Such analyses require making
measurements on the samples by utilizing
measuring devices such as weighing
machines and sophisticated instruments.
• In any cases, a basic understanding of
accurate measurement technique is
fundamental to a chemist.
• Chemistry An Industry-Based Introduction with CD-ROM, John Kenkel, Paul
B. Kelter, David S. Hage CRC.
• Data handling often follows after the
collection data in an analysis.
• Statistic are necessary to understand the
significance of the data that are collected
and could therefore to set limitations on
analysis steps.
 Measures of Central Tendency
• Mean, X: Summation of all data and
divided by the number of measurements.
• Median, Xmed: middle value for a set of
data. In a set of odd data, the median is in
the middle. In a set of even data, the
median is the average of the central pair,
whereby, the values are arranged in an
ascending manner.
 Measures of Central Tendency
• Masses of seven Malaysia 50 cent
coins in circulation
Coin Mass (g)
1 3.080
2 3.094
3 3.107
4 3.056
5 3.112
6 3.174
7 3.198
• What is the mean for the data in previous
slide?
• Mean, X = (3.080 + 3.094 + 3.107 + 3.056 + 3.112 +
3.174 + 3.198) g / 7
= 3.117 g

• The mean is the most common estimator

of central tendency. It is not considered a
robust estimator, however, because
extreme measurements, those much
larger or smaller than the remainder of the
data, strongly influence the mean’s value.
• For example, mistakenly recording the
mass of the third coin as 31.07 g instead
of 3.107 g, changes the mean from 3.117
g to 7.112 g.

• What is the median for the same data?

• Arrange the data from smallest to largest:
3.056, 3.080, 3.094, 3.107, 3.112, 3.174,
3.198
• Median is 3.107 g.
• The mean and median provide similar
estimates of central tendency when all
data are similar in magnitude. The median,
however, provides a more robust estimate
of central tendency since it is less
sensitive to measurements with extreme
values. For example, introducing the
transcription error discussed earlier for the
mean only changes the median’s value
from 3.107 g to 3.112 g.
• 3.056, 3.080, 3.094, 3.112, 3.174, 3.198,
31.07
 Uncertainty in Measurement
• What is a measurement?
• A measurement tells us about a property
of something. It might tell us how heavy an
object is, or how hot, or how long it is.
• A measurement gives a number to that
property.
• Measurements are always made using an
instrument of some kind. Rulers,
stopwatches, weighing scales, and
thermometers are all measuring
instruments.
• The result of a measurement is normally in
two parts: a number and a unit of
measurement, e.g. ‘How long is it? ... 1.5
centimeters.’
• What is not a measurement?
• There are some processes that might
seem to be measurements, but are not.
For example, comparing two pieces of
string to see which is longer is not really a
measurement.
• Counting is not normally viewed as a
measurement.
• What is uncertainty of measurement?
• The uncertainty of a measurement tells us
something about its quality.
• Uncertainty of measurement is the doubt
that exists about the result of any
measurement.
• One might think that well-made rulers,
clocks and thermometers should be
trustworthy, and give the right answers.
• But for every measurement - even the
most careful - there is always a margin of
doubt.
• Precision and accuracy are often used in
discussing the uncertainties of measured
values.
 Precision
• When a sample is analyzed several times,
the individual results are rarely the same.
Instead, the results are randomly
scattered.
• Precision is a measure of this variability.
• The closer the agreement between
individual analyses, the more precise the
results.
 Precision
• Precision is a degree of agreement
between replicate measurements of the
same quantity or a measure of the spread
of data about a central value and may be
expressed as the range, the standard
deviation (a statistical measure of the
“average” deviation of data from the data’s
mean value, s), or the variance (the
square of the standard deviation, s2).
• Commonly divided into two categories:
repeatability and reproducibility.
• Repeatability: precision obtained when all
measurements are made by the same
analyst during a single period of laboratory
work, using the same solutions and
equipment.
• Reproducibility: precision obtained under
any other set of conditions, including that
between analysts, or between laboratory
sessions for a single analyst.
 Accuracy
• Accuracy is a measure of how close of
central tendency is to the true, or expected
value or a degree of measurement that is
approximately close to the accepted or
correct values, or the approximation of the
results to the true value.
• It is expressed as absolute error or relative
error.
Precision and Accuracy
 Accuracy
• Errors will show the closeness of
measurements to the accepted or correct
value.
• Absolute errors
• E=O–A
• Where: E = absolute error
• O = observed value
• A = accepted value
 Accuracy
• 18.24 % of calcium was found in a sample
from an analysis . Its true value is 18.30
%. What is the absolute error?
• Ans: E = O – A
• = 18.24 % - 18.30 %
• = -0.06 %
• The positive or negative sign is assigned
to show whether the errors are high or low.
 Accuracy
• Relative error
• Can be expressed in percentage or parts
per thousand.
• Relative error = absolute error
• --------------------- x 100 %
• accepted value
 Accuracy
• Calculate the relative error if the absolute
error is -0.06 % and the accepted value is
18.30 %.
• Ans: Relative error
• = (-0.06 % / 18.30 %) x 100
• = -0.33 % or -3.3 ppt
 An Example

• A chemist is asked to determine the

concentration of a chemical dissolved in a
solution. The chemist performs the
experiment three times for good measure,
and the concentration determined to be
1.74 M, (moles/liter), 1.73 M and 1.75 M.
The average of these numbers is 1.74 M.
• This result is extremely precise, but
suppose the chemist is not a very good
chemist and made the same mistake in all
three experiments: the true concentration
of the chemical in solution is 2.32 M.
• Even though this experiment was done
three times, and the concentration was
determined very precisely, it is not an
accurate result.
• Now let's say that another chemist
performs three more experiments to
determine the concentration of the same
chemical in solution, and finds the
following values: 2.87, 1.48 and 2.61 M.
When averaged, these values accurately
give 2.32 M, but the experiments were not
precise. In fact, it may have been lucky
that they averaged out perfectly.
Types of Errors in Experimental data

• i) Determinate or systematic errors

• ii) Indeterminate or random or accidental
errors
Determinate or systematic errors

• Errors that occur because of some reasons and

have specific values.
• Characteristic of determinate errors:
• i) Cause of error is known.
• ii) one sided, example having the same sign.
• iii) Consistency, that is the values are almost the
same.
• iv) Will give effect to accuracy of the method.
• v) Can be traced to an identifiable source/can
be corrected.
Types of Determinate or systematic
errors
• a) Personal errors
• An error due to biases introduced by the
analyst.
• Also known as observation error and is
caused by carelessness, clumsiness or
not using the right techniques by the
operators.
• Eg. Recording wrong burette reading as
9.36 cm3, while the correct reading is 9.35
cm3. To avoid this error is by reading the
volume correctly
• b) Instrumental errors
• The faulty equipments, uncalibrated
weight and glasswares used may cause
instrumental errors.
• Eg. Using instruments that are not
calibrated and this can be corrected by
calibrating the instruments before using.
• c) Method errors
• Caused by the nature of the methods
used. This error cannot be eliminated by
running the experiments several times. It
can be recognized and corrected by
calculations or by changing to a difference
methods or techniques. This type of errors
is present in volumetric analysis that is
caused by reagent volume.
• Examples
• Use of a “bad” indicator for an acid-base
titration
• Presence of an interferent.
• An excess of volume used as compared to
theory will result in the change of colours.
• Eg. Mistakes made in determining end
point caused by co precipitation.
• d) Errors of the reagent
• Occur if the reagents used are not pure.
Correction is made by using pure reagents
or by doing back-titration.
• e) Sampling errors
• When sampling fails to provide a
representative samples.
• Especially important when sampling
heterogeneous (not uniform in
composition) materials.
• Example, determining the environmental
quality of a lake by sampling a single
location near a point source of pollution,
such as an outlet for industrial effluent,
gives misleading results.
 Indeterminate or random errors
• Errors that occur at all measurements do
not have specific values and are
unpredictable.
• Can be traced to several sources,
including the collection of samples, the
manipulation of samples during the
analysis, and the making of
measurements.
• When collecting a sample, for instance,
only a small portion of the available
material is taken, increasing the likelihood
that small-scale inhomogeneities in the
 sample will affect the repeatability of the
analysis.
• Individual coins, for example, are expected
to show variation from several sources,
including the manufacturing process, and
the loss of small amounts of metal or the
addition of dirt during circulation.
• These variations are sources of
indeterminate error associated with the
sampling process.
• During the analysis numerous
opportunities arise for random variations in
the way individual samples are treated.
• In determining the mass of a coin, for
example, each coin should be handled in
the same manner.
• Cleaning some coins but not cleaning
others introduces an indeterminate error.
• Also, any measuring device is subject to
an indeterminate error in reading its scale.
• For example, a buret with scale divisions
every 0.1 mL has an inherent
 indeterminate error ±0.01-0.03 mL when
estimating the volume to the hundredth of
milliliter (0.01 mL).
 Error versus uncertainty

• It is important not to confuse the terms

‘error’ and ‘uncertainty’.
• Error is the difference between the
measured value and the ‘true value’ of the
thing being or a measure of bias in a
result/measurement
• Uncertainty is a quantification of the doubt
about the measurement result or the range
of possible values for a measurement.
 Significant Figures
• Measured quantities are generally
reported in such a way that only last digit
is uncertain.
 Significant Figures
• There are three rules on determining how
many significant figures are in a number:
• a) Non-zero digits are always significant.
• b) Any zeros between two significant digits
are significant.
• c) A final zero or trailing zeros in the
decimal portion ONLY are significant.
 Significant Figures
• In science, all numbers are based upon
measurements (except for a very few that
are defined). Since all measurements are
uncertain, only those numbers that are
meaningful are used.
 Significant Figures
• A common ruler cannot measure
something to be 13.5322643 cm long. Not
all of the digits have meaning
(significance) and, therefore, should not be
written down. In science, only the numbers
that have significance (derived from
measurement) are written.
 Significant Figures
• Addition and Subtraction
• In mathematical operations involving
significant figures, the answer is reported
in such a way that it reflects the reliability
of the least precise operation. It can be
stated that a chain is no stronger than its
weakest link. An answer is no more
precise that the least precise number used
to get the answer.
 Significant Figures
• Imagine a team race where you and your
team must finish together. Who dictates
the speed of the team? Of course, the
slowest member of the team. Your answer
cannot be MORE precise than the least
precise measurement
 Significant Figures
• For addition and subtraction, look at the
decimal portion (i.e., to the right of the
decimal point) of the numbers ONLY.
Follow the steps below:
• 1) Count the number of significant figures
in the decimal portion of each number in
the problem. (The digits to the left of the
decimal place are not used to determine
the number of decimal places in the final
answer.)
 Significant Figures
• 2) Add or subtract in the normal fashion.
• 3) Round the answer to the LEAST
number of places in the decimal portion of
any number in the problem.
 Significant Figures
43.7 g + 4.432 g + 12.68 g
= 60.812 g (from calculator)
• But the answer needs to be reported as
60.8 g

74.5 mL - 23.63 mL
= 50.87 mL (from calculator)
• Answer is 50.9 mL
 Significant Figures
• 25.46 g + 32.886 g – 12.3 g
= 46.0 g
 Significant Figures
• The following rule applies for multiplication
and division:
• The LEAST number of significant figures
in any number of the problem determines
the number of significant figures in the
answer.
 Significant Figures
• 2.098 x 3.23
= 6.77654 (calculator)
= 6.78

• 1.0923 x 207
= 226.1061 (calculator)
= 226
 Rounding Off (Rules)
• If it is less than 5, drop it and all the
figures to the right of it.
• If it is more than 5, increase by 1 the
number to be rounded, that is, the
preceding figure.
• The “even/odd” rule is a rule for rounding
when the digit immediately to the right of
the last digit to be retained is a 5 with no
more digits to its right, or with only zeros
to its right.
 Rounding Off (Rules)
• In that case, if the last digit to be retained
is odd, then increase it by one. If it is even,
keep it the same.
 Rounding Off
• Round 42.6348 to four significant figures.
Ans: 42.63

• Round 3.68739 to three significant figures

Ans: 3.69
 Rounding Off
• Round 226.875 (“even/odd”) rule to five
significant figures
Ans: 226.88

• Round 74.4526 to three significant figures

Ans: 74.5
 Rounding Off
• Round 74.4500 to three significant figures
• Ans: 74.4
 Rounding Off
• 2.85 (round to 2 digits)

• 7.335 (round to 3 digits)

• 1) RM 2346
• Round to 3 significant digits.
• RM235 or RM 2350
 Reading a measuring device
Chemistry An Industry-Based Introduction with CD-ROM, John Kenkel, Paul B.
Kelter, David S. Hage CRC.

• Fundamental Rule:
• When recording a reading from a digital
measuring device, record all digits shown.
• When recording a reading from a
nondigital measuring device, write down
all the digits that are known with certainty
plus one digit that is estimated.
 Control Charts
• For any laboratory that performs a particular activity time
and timeagain, showing the results in a control chart is a
good way to monitor the activity and to discover whether
a change has caused some deviation in the expected
results.
• Walter Shewhart in 1924 designed a chart to indicate
whether or not the observed variations in the percent of
defective apparatus of a given type are significant; that
is, to indicate whether or not the product is satisfactory”
• This was the first control chart, and it has been the basis
of statistical quality control ever since.
• The data obtained regularly from the QC
materials are, in general, evaluated by
control charts.
• The user can define warning and action
limits on the chart to act as ‘alarm bells’
when the system is going out of control.
• •A control chart is simply a chart on which
measured values of whatever is being
measured are plotted in time sequence.
Basic Shewhart
(pronounced like “shoe-heart”) Control
Chart