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Topic 11
Measurement and
data processing
Third edition, 2015
 Table of Contents
11.1 Uncertainties and errors in measurement and results ......................................... 1
Measurements ................................................................................................................................. 1
Accuracy and precision .................................................................................................................... 1
Uncertainties ................................................................................................................................... 3
Significant figures ............................................................................................................................ 6
Practice ........................................................................................................................................... 7
Assignment 11.1 .............................................................................................................................. 8
Significant figures in calculations ..................................................................................................... 9
Rounding up/down ....................................................................................................................... 10
Units ............................................................................................................................................. 10
Assignment 11.2 ............................................................................................................................ 11
Types of errors ............................................................................................................................... 12
Recording measurements in the laboratory ..................................................................................... 15
Dealing with uncertainties in calculations ...................................................................................... 17

11.2 Graphical techniques ...................................................................................... 19

Graphing in science ....................................................................................................................... 19
What is a graph? ............................................................................................................................ 20
Graphing practice 1 ....................................................................................................................... 22
Graphing practice 2 ....................................................................................................................... 22

Notes.......................................................................... Error! Bookmark not defined.

Topic 11
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11.1 Uncertainties and errors in measurement and results

Measurements

In conducting science research and experiments, measurements are often taken.

Measurements are quantitative data involving numerical values with units that depend on
the physical quantity being measured. Table 1 lists the common measurements that are
made in a chemistry experiment.

Physical quantity Typical unit

Concentration mol dm-3
Length cm
Mass g (or mg for smaller masses)
Temperature o
C (usually converted to K for
calculations)
Time s
Volume cm3 or dm3
Table 1: Common measured physical quantities and their units

Accuracy and precision

It is important to be able to distinguish between the terms accuracy and precision in

measurements.

Accuracy refers to how close an experimental value is to its true, accepted or literature
value. It is analogous to the “validity” of a measure. In other words, the degree to which
the data is able to scientifically answer the questions it is intended to answer.

Precision refers to how close several experimental measurements of the same quantity are
to each other. It is analogous to the “reliability” of a measure. In other words, how close
repeated measurements under consistent conditions are to each other.

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Example

In an acid-base titration experiment, 20.00 cm3 of 1.0 mol dm-3 dilute hydrochloric acid
(HCl) was titrated with 1.0 mol dm-3 aqueous sodium hydroxide (NaOH). The true titre
volume is 20.00 cm3 as 1 mole of HCl reacts with 1 mole of NaOH. The table below shows
the results obtained by four students.

student titre 1/cm3 titre 2/cm3 titre 3/cm3 average

titre/cm3
A 19.80 20.00 19.90 19.90
B 18.40 18.50 18.60 18.50
C 21.00 21.60 20.20 20.90
D 19.60 20.40 20.00 20.00

 Student A’s results were …………………………………….…………………………….

 Student B’s results were …………………………………….…………………………….

 Student C’s results were …………………………………….…………………………….

 Student D’s results were …………………………………….…………………………….

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Uncertainties

No measure is ever exact due to errors in instrumentation and measuring skills. If you
were to obtain the mass of an object with a digital balance, the reading gives you a measure
with a specific set of values. We can assume that the actual measure lies either slightly
above or slightly below that reading. The range is the uncertainty of the measurement
taken. More precise instruments have a smaller range of uncertainty. Whenever you take
a measurement, the last recorded digit is your estimate. We call digits in a measurement
significant figures.

The accuracy of a measuring instrument is determined by the suitability of its range for
the spread of values being measured. For example, to measure the length of an object with
a spread of values between 0 and 1 cm, a meter ruler with a range of 0-100 cm would not
be appropriate. A micrometer would be appropriate in this case.

The precision of a measuring instrument is determined by the smallest unit to which it

can measure. The precision is said to be the same as the smallest fractional or decimal
division on the scale of the measuring instrument.

The uncertainty of a measurement taken with an analogue measuring instrument is

usually taken to be half the division on the scale of the instrument while the uncertainty
of a measurement taken with a digital measuring instrument is usually taken to be the
same as the precision of the instrument.

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Physical Instrument Precision Uncertainty Examples of

quantity recording
Length half metre rule 0.1 cm ±0.05 cm 12.05 cm,
or metre rule 12.10 cm
Mass electronic 0.1 g ±0.1 g 2.2 g
balance 0.01 g ±0.01 g 2.25 g
Temperature thermometer (- 1 oC ± 0.5 oC 23.0 oC, 23.5
10 oC to 110 o
C
o
C)
temperature 0.1 oC ± 0.1 oC 23.0 oC, 23.1
probe (attached o
C
to a data
logger)
Time stopwatch 0.1 s ±0.1 s 36.0 s, 36.1 s
(analogue)
stopwatch 0.1 s ±0.1 s 28.1 s
(digital) 0.01 s ±0.2 s (human 28.0 s, 28.1 s
reaction time)
Volume measuring 1 cm3 ± 0.5 cm3 20.0 cm3, 20.5
cylinder (50 cm3
cm3)
volumetric varies ± 0.03 cm3 10.00 cm3,
pipette according to (typically) 20.00 cm3,
manufacturer 25.00 cm3
graduated 0.10 cm3 ± 0.05 cm3 2.50 cm3
pipette
burette 0.10 cm3 ± 0.05 cm3 23.50 cm3,
23.55 cm3
volumetric 0.1 cm3 ± 0.1 cm3 250.0 cm3
flask
Table 2: Common measuring instruments and their precision and uncertainties

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Accuracy, precision and consistency (the variation in the value obtained when the
determination is repeated) of measurements are illustrated in the diagram below, which
represents eight separate determinations of a particular quantity:

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Significant figures

One of the most abused aspects of chemical calculations is the frequent disregard for the
information that is contained in the numbers obtained from physical measurements. The
most common symptom of this carelessness is the carrying out of calculations to too many
decimal places.

When recording a measurement, you should record the digits known with certainty plus
one last digit which is assumed to be in doubt. The known digits plus the doubtful digit
constitute what are called significant figures. Thus if a beaker is weighed and its weight
recorded as 1.234 g – this is 4 significant figures of which 3 are known with certainty (1,
2, 3) and the fourth (4) is uncertain. Deciding how many significant figures to record
depends on the measuring instrument that has been used. The more precise the measuring
instrument, the more significant figures the measurement can have.

The number of significant figures in a numerical result is an indication of the accepted

error in a number. In counting the number of significant figures the problem is the digit
zero (0). There are five rules used in counting the number of significant figures in a
number:

1. All non zero digits are significant

e.g., 12.3 has three significant figures and 549 has three significant figures.

2. Zeros between non-zero digits are significant

e.g., 1.03 has three significant figures and 4023 has four significant figures.

3. Zeros at the end of a number are significant

For numbers with decimal points, zeros to the right of a non zero digit are significant.
E.g., 2.00 has three significant figures, but 0.050 has two (the 5 and 0) in the second
and third decimal places.

4. Zeros to the left of a non-zero digit are not significant

e.g., 0.84 has two significant figures (the 8 and 4) and 0.024 has two significant figures.
The zero is termed a placeholder, meaning the zero is not part of the measurement, i.e.,
it is not significant.

5. Zeros at the end of a number without a decimal point are ambiguous,

e.g., 80 could have one or two significant figures. It is not clear whether the 0 is the
doubtful digit or if is just a placeholder. In cases like this the number of significant
figures should be made clear:
e.g. 1 significant figure: 80 ± 10 or 8 x 101
or 2 significant figures 80 ± 1 or 8.0 x 101

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Ambiguity can be removed by reporting such numbers using scientific or standard

notation. Writing 80 as 8.0 x 101 means that two significant figures are present. It is
also better to write numbers with a large number of zeros in this form. For example,
0.0000456 should be 4.56 x 10-5 .

Whenever you use data in a calculation, you should not round your data until you have
performed the last calculation.

Calculated data should be expressed to the same number of significant figures as the least
precise piece of measured data.

Practice

How many significant figures are in the following numbers?

Number # of s.f. Number # of s.f. Number # of s.f.

274 3 25.632 5 8.987 4
504 3 60002 5 9.077 4
32.0 3 19.000 5 105.0020 7
0.0002 1 6.02 x 1023 3 100.000 6
150000 2 to 6 800 1 0.0073 2
100.020 6 2500 2 7.90 x 10-3 3
670.0 4 0.00001 1 18.84 4

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Assignment 11.1

1. How many significant figures in each of the following?

(a) 2.54 g 3 (b) 2.205 g 4 (c) 1.1 g 2 (d) 14.0 cm3 3
5
(e) 1.86 x 10 s 3 (f) 127000 kg 3 - 6 (g) 9.993 g cm-3 4 (h) 2.0070 g 5

2. How many significant figures in each of the following?

(a) 100 g 1 - 3 (b) 100 ± 1 g 3 (c) 100 ± 10 g 2-3 (d) 1 x 102 g 1
2
(e) 1.0 x 10 g 2 2
(f) 1.00 x 10 g 3

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Significant figures in calculations

The result of a calculation that involves measured quantities cannot be more certain than
the least certain of the information you used. The precision of your final answer is limited
by the least precise measurement. A common mistake by students is to simply copy down
the final answer from the display of a calculator. This often has far more significant figures
than the measurements justify. There are rules to help you decide on the number of
significant figures you are allowed in a final answer.

For additions and subtractions the answer must have the same number of decimal places as there
are in the measurement with the fewest decimal places. Applying this rule will make certain
that your final answer is as precise as your least precise measurement and that is contains
only one ‘doubtful’ digit. For example:

An empty beaker weighs 42 g. Into this beaker you put 0.257 g of salt. What is the total
weight of beaker + salt?

The calculator would give: 42 g + 0.257 g = 42.257 g

However, this implies that the first four digits (42.25) are known with certainty and the 7
is uncertain. This is incorrect because the weight of the beaker is 42 g and the 2 is uncertain.
Not only is the 2 uncertain but any numbers following the decimal are completely
unknown. Consequently any digits added to these must also be uncertain and should not
be reported.

The correct response is: 42 g + 0.257 g = 42 g

For multiplication and division the result should contain the same number of significant figures
as the number with the least number of significant figures. This once again makes sure that
your answer is as precise as your least precise measurement. For example:

How many grams of salt are there in 0.12 dm3 of a solution which contains 0.345 g of salt
per dm3?

The calculator would give: 0.12 dm3 x 0.345 g dm-3 = 0.04140 g

Once again, your result cannot be more precise than your least precise measurement.

Thus the result should be reported as 0.041 g.

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A calculation will often involve both addition/subtraction and multiplication/division.

Here, you apply the appropriate rule at each step. For example:

A sample contains 2.0 g hydrogen, 32.1 g sulfur and 64.0 g oxygen. What is the % of sulfur
in the sample?

Total weight = 2.0 g + 32.1 g + 64.0 g

= 98.1 g
%S = (32.1/98.1) x 100
= 32.7%

N.B. The result is reported to 3 significant figures even though one piece of data - the
weight of hydrogen - has only 2 significant figures. The point is the 2.0 is involved in an
addition the result of which has 3 significant figures.

Rounding up/down

When we round off a number that has more significant figures than are justified, we round
up if the last figure is between 5 and 9 inclusive and round down if it is between 0 and 4
inclusive.

For example, the number 360.99 rounded to:

 4 sig fig is 361.0 (rounded up – the fifth figure is 9)

 3 sig fig is 361 (rounded up – the fourth figure is 9)
 2 sig fig is 360 (rounded down – the third figure is 0)
 1 sig fig is 400 (rounded up – the second figure is 6)

The other point to be careful about is when to round off in calculation with two or more steps.
This is best left to the very end of the calculation. Rounding off after each step and using this
rounded figure as the starting figure for the next step could make a difference to the final
answer.

Units

When doing calculations it is good practice to include the units along with the numerical
quantity. The units multiply and cancel in just the same way as do numbers. So the units of
the quantity being calculated are derived from those of the quantities used to calculate it.

In terms of significant figures, changing the size of the unit of measurement should have no
effect on the precision with which the measurement has been made.

E.g. 0.0019 g, 1.9 mg and 0.0000019 kg are all quoted to two significant figures.

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Assignment 11.2

1. Add the following quantities, giving your answers to the appropriate significant
figures:
(a) 46.247 cm3, 3.219 cm3, 0.224 cm3 49.690cm3
(b) 26.6 cm3, 0.0028 cm3, 0.00002 cm3 26.6cm3
(c) 2.40 cm3, 3.65584 cm3, 0.029 cm3 6.08cm3
(d) 0.0034 dm3, 0.094 dm3, 0.552 dm3 0.649dm3
(e) 203 g, 4 g, 0.77 g 208g

2. Perform the following subtractions, giving your answers to the appropriate

significant figures.
(a) 7.26 g - 0.2 g 7.1 (c) 539.27 g - 12.8 g 526.5
(b) 4.0 m - 0.623 m 3.4 (d) 76 cm3 - 0.3 cm3 76

3. Calculate the density (g cm-3) of an object which weighs 17.32 g and has a volume
of 2.4 cm3. 7.2 g/cm3

4. Multiply the following, expressing your answer to the correct number of significant
figures (give appropriate units):
(a) 0.11 mol dm-3 x 0.0272 dm3 0.0030 mol
(b) 2.43 mol x 27.9 g mol-1 67.8g
(c) 0.34 g cm-3 x 24.54 cm3 8.3g

5. Divide the following, expressing your answer to the correct number of significant
figures (give appropriate units):
(a) 9.2 g 0.48mol
(b) 0.20 g 2g/cm3
19.00 g mol -1
0.1 cm3

6. Lithium is the least dense metal known (density 0.53 g cm-3). What volume is
occupied by 1.20 x 103 g of lithium? 2300cm3

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Types of errors

Random errors are due to the accuracy of the equipment and systematic errors are due to
how well the equipment was used or how well the experiment was controlled.

1. Random errors: Precision (Errors inherent in apparatus.)

A random error makes the measured value both smaller and larger than the true value.
Chance alone determines if it is smaller or larger. Reading the scales of a balance,
graduated cylinder, thermometer, etc. produces random errors. In other words, you can
weigh a dish on a balance and get a different answer each time simply due to random
errors. They cannot be avoided; they are part of the measuring process.

Uncertainties are measures of random errors. These are errors incurred as a result of
making measurements on imperfect tools which can only have certain degree of accuracy.
They are predictable, and the degree of error can be calculated. Generally, they can be
estimated to be half of the smallest division on a scale. For a digital reading such as an
electronic balance the last digit is rounded up or down by the instrument and so will also
have a random error of ± half the last digit.

2. Systematic errors: Accuracy (Errors due to "incorrect" use of equipment or poor

experimental design.)

A systematic error makes the measured value always smaller or larger than the true value,
but not both. An experiment may involve more than one systematic error and these errors
may nullify one another, but each alters the true value in one way only. Accuracy (or
validity) is a measure of the systematic error. If an experiment is accurate or valid then the
systematic error is very small.

Accuracy is a measure of how well an experiment measures what it was trying to measure.
These are difficult to evaluate unless you have an idea of the expected value (e.g. a text
book value or a calculated value from a data book). Compare your experimental value to
the literature value. If it is within the margin of error for the random errors then it is most
likely that the systematic errors are smaller than the random errors. If it is larger then you
need to determine where the errors have occurred.

Assuming that no heat is lost in a calorimetry experiment is a systematic error when a

Styrofoam cup is used as a calorimeter. Thus, the measured value for heat gain by water
will always be too low. When an accepted value is available for a result determined by
experiment, the percent error can be calculated.

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When evaluating an experiment, you would compare your experimental value to the
expected value – i.e. compare the % experimental error with the % precision uncertainty.

 % experimental error < % precision uncertainty – the result is within the margin of
error for the precision uncertainties. Thus, systematic errors or other random errors are
smaller than the random errors caused by precision uncertainties. If the precision
uncertainty is large you probably want to suggest ways of reducing it. It is possible that
two systematic errors cancelled each other out.

 % experimental error > % precision uncertainty - you need to estimate where the
systematic errors or other random errors have occurred. Systematic errors can also
occur in data processing.

Categories of systematic errors and how to eliminate them:

a. Personal errors: These errors are the result of ignorance, carelessness, prejudices, or
physical limitations on the experimenter. This type of error can be greatly reduced if you
are familiar with the experiment you are doing. Be sure to thoroughly read over every lab
before you come to class and be familiar with the equipment you are using. Be Prepared!!!

b. Instrumental Errors: Instrumental errors are attributed to imperfections in the tools

with which the analyst works. For example, volumetric equipment such as burets, pipets,
and volumetric flasks frequently deliver or contain volumes slightly different from those
indicated by their graduations. Calibration can eliminate this type of error.

c. Method Errors: This type of error many times results when you do not consider how to
control an experiment. For any experiment, ideally you should have only one manipulated
(independent) variable. Many times this is very difficult to accomplish. The more variables
you can control in an experiment the fewer method errors you will have.

Examples of systematic errors

Faulty or incorrect use of equipment:

 Sticking or leaking gas syringes.
 Calibration errors in pH meters – result of an error in pH of buffer solution used
for calibration.
 Stop clock running slow.
 A faulty thermometer.
 Incorrect reading of scales (e.g. a burette).

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Design errors
 Incomplete reaction in a thermochemical measurement.
 Differences in the observed end point and stoichiometric end point.
 Changes in external influences such as temperature and atmospheric pressure affect
the measurement of gas volumes, etc.
 Unaccounted heat loss.
 Liquids evaporating.

Reagent errors:
 The use of impure reagents (only state if there is evidence that this has occurred).
 The reaction of the reagents with glassware or with air.

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Recording measurements in the laboratory

When you record a measurement in the laboratory, you need to record the correct number
of significant figures. As a general rule:

 When using a digital measuring device (such as a modern top pan balance or
ammeter), record all the digits shown.

 When using a non-digital device (such as a ruler or a burette) record all the figures that
are known for certain plus one that is estimated.

 If the scale on a measuring device is too fine for an estimation to be made (e.g. a
thermometer) then the measurement is recorded to the smallest division or the last digit
capable of precise measurement.

You should also indicate the precision uncertainty in the measurement. This indicates the
variation that would be expected in the result because of the limitations of the measuring
instrument. Use the rules below to help you decide on the precision uncertainty.

(1) If reading a digital output; i.e. a reading on a balance or a pH meter, the precision
uncertainty is taken as ± 1 of the last unit.

The reading would be 0.66±0.01g

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(2) If reading a scale, it is usual practice to record all the digits you are certain of, plus one
estimated digit. The precision uncertainty is taken as  5 of the last unit.

The reading would be 10.25 ± 0.05 cm3

If a volume of 8.5 cm3 of water is measured in various measuring devices, the values would
normally be reported as follows:

 100 cm3 measuring cylinder (has divisions in 2 cm3): 8 ± 1 cm3 (the first digit is
already estimated and could vary from one student to the next)
 25 cm3 measuring cylinder (has divisions in l cm3): 8.5 ± 0.5 cm3 (the first digit is
known but the second one is estimated but can only be a 0 or a 5)
 10 cm3 measuring cylinder (has divisions in 0.2 cm3): 8.5 ± 0.1 cm3 (the first digit
is known but the second one is estimated. Notice the variation in the second digit
is much less)
 Burette (has divisions in 0.1 cm3): 8.50 ± 0.05 cm3 (it is the third digit that is
estimated)

(3) If using a pipette or a volumetric flask, as you are not reading a scale, you record the
precision uncertainty given by the manufacturer. In fact all measuring instruments
have a manufacturers error associated with them. However, in most cases this is
ignored.

(4) You might decide that the precision uncertainty is in fact larger than it is suggested by
following the rules above. For example, reaction time might add to the precision
uncertainty when using a stop clock or if taking rapid readings on a thermometer;
random fluctuations might add to the uncertainty when reading a balance or
voltmeter.

There must be agreement between the number of significant figures included in a

measurement and the precision uncertainty. DO NOT DROP OFF FINAL ZEROS.

Thus measuring 10 cm3 of water in a pipette should be recorded as 10.00 ± 0.03 cm3 and
not 10 ± 0.03 cm3.

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Dealing with uncertainties in calculations

The uncertainty attached to a reading is usually expressed in the same units as the reading.
This is then called the absolute uncertainty.

e.g. 15.3 ± 0.1 s

The absolute uncertainty is often converted to show a percentage uncertainty. For the
above example, this would be:

15.3 ± 0.65% [(0.1/15.3) x 100]

Adding or subtracting:

If more than one reading of a measurement is made, then the uncertainty increases with
each reading. For example: 10.0 ± 0.1cm3 of acid is delivered from a 10 cm3 measuring
cylinder repeated 3 times. The total volume delivered is

Total volume delivered = (10.0 ± 0.1 cm3) + (10.0 ± 0.1 cm3) + (10.0 ± 0.1 cm3)
= 30.0 ± 0.3 cm3

A second example: when using a burette (± 0.05 cm3), you subtract the initial volume
(even if it is zero, it is 0.00 ± 0.05) from the final volume. The volume delivered is:

Final volume = 38.40 ± 0.05 cm3

Initial volume = 12.10 ± 0.05 cm3
Total volume delivered = 26.30 ± 0.10 cm3

WHEN ADDING OR SUBTRACTING UNCERTAIN VALUES, ADD THE

ABSOLUTE UNCERTAINTIES

Multiplying and dividing:

Convert the absolute uncertainties to percentage uncertainties and add them together.
When finished, convert the total percentage uncertainty back to an absolute uncertainty:

e.g. number of moles = concentration x volume

= (0.53 ± 0.05 mol.dm-3) x (0.50 ± 0.01 dm3).
= (0.53 ± 9.4% mol.dm-3) x (0.50 ± 2.0% dm3)
= 0.265 ± 11.4% mol
= 0.265 ± 0.030 mol
= 0.27 ± 0.03 mol round the uncertainty up to dp

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WHEN MULTIPLYING OR DIVIDING, ADD THE PERCENTAGE

UNCERTAINTIES
&
CONVERT THE TOTAL % UNCERTAINTY BACK TO AN ABSOLUTE
UNCERTAINTY

Notice that in the above example the final result has been adjusted to the correct number
of decimal places and that the final absolute uncertainty is given to one significant
figure.

Average values:

When a number of readings are taken and an average value needs be calculated, what are
the uncertainties associated with this value?

For example, in a titration three values were obtained for the volume added: 24.50, 25.20
and 24.80 cm3. The precision uncertainty of each volume would be twice the error of the
burette readings, i.e. 0.05 cm3 x 2 = 0.10 cm3. Thus the average volume added would be:

(24.50 + 25.20 + 24.80)/3 ± (0.10+ 0.10 + 0.10)/3 cm3 = 24.83 ± 0.10 cm3

BUT if the spread of values that you are averaging is greater than 0.10 cm3, then the errors
of your titration technique are greater than the random errors of the equipment. In this
case, the uncertainty in the mean value can be calculated as range of the result (i.e. greatest
- smallest value) divided by twice the square root of the number of readings used (N):

X max  X min
X 
2 N

In this case: X = 25.20-24.50/23 = 0.2. In reporting your final answer, use whichever
value (the one calculated by this formula or the uncertainty of an individual reading) is
greater but you do not need to add these errors. In the example above, the answer would
be given as: 24.8 ± 0.2 cm3.

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11.2 Graphical techniques

Graphing in science

Most scientific graphs are made as line graphs. There may be times when other types
would be appropriate, but they are rare.

The lines on scientific graphs are usually drawn either straight or curved. These
"smoothed" lines do not have to touch all the data points, but they should at least get close
to most of them. They are called best-fit lines.

In general, scientific graphs are not drawn in connect-the-dot fashion.

Here are two examples of best-fit graph lines. One is drawn correctly, the other is not.

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What is a graph?

A graph is a visual representation of a relationship between two variables, x and y.

A graph consists of two axes called the x (horizontal) and y (vertical) axes. These axes
correspond to the variables we are relating. In chemistry we will usually give the axes
different names, such as Temperature and Time.

The point where the two axes intersect is called the origin. The origin is also identified as
the point (0, 0).

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Graphing practice 1

Graphing practice 2

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