UW Department of Chemistry

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Chem 142

Lab 1: Measurements and Error

Physical Measurements and Error Analysis
Introduction
In this experiment you will determine the density of a liquid and a solid by procedures involving
the determination of the mass of a sample together with its volume. Along the way, you will
evaluate the precision with which three volumetric devices can deliver a known volume to a
second container. You will judge the precision by weighing the volumes of liquid. Thus, the
more precise method of weighing will be used as the reference technique for comparison of
the volumetric devices.

One of the fundamental properties of any sample of matter is its density (ρ), which is its mass
(m) per unit of volume (V):

m
ρ= (1)
V
The density of water is exactly 1.00000 g/cm3 at 4 °C and is slightly less than one at room
temperature (0.9970 g/cm3 at 25°C). Densities of liquids and solids range from values less
than that of water to values considerably greater than that of water. Osmium metal has a
density of 22.5 g/cm3 and is probably the densest material known at ordinary pressures. It
should be noted that cm3 and mL (milliliters) are identical and are typically used
interchangeably.

In any density determination, two quantities are measured: the mass and the volume of a given
quantity of matter. The mass can easily be determined by weighing a sample of the substance
on a balance. The quantity we usually think of as "weight" is really the mass of a substance.
In the process of "weighing" we find the mass, taken from a standard set of masses, that
experiences that same gravitational force as that experienced by the given quantity of matter
we are weighing. The mass of a sample of liquid in a container can be found by taking the
difference between the mass of the container plus the liquid and the mass of the empty
container.

The volume of a liquid can easily be determined by means of a calibrated container. In the
laboratory a graduated cylinder is often used for routine measurements of volume. In titration
experiments where it is necessary to add a precise series of volumes of liquid to another
container, a buret is employed. However, the most accurate measurements of liquid volume
are made by using a pycnometer, which is simply a container having a precisely definable
volume. In the case where the pycnometer is used to deliver the volume to another vessel, we
have a pipet. These three instruments are shown in Figure 1.

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Graduated Cylinder Buret Pipet

Figure 1. Volumetric Devices

The volume of a solid can be determined by direct measurement of its dimensions if it has a
regular geometrical shape. However, many solid samples have an irregular shape. In these
cases, a convenient way to determine the volume of a solid is to measure accurately the
volume of liquid displaced when it is immersed in the liquid. The volume of the solid will equal
the volume of liquid which it displaces.

In any scientific experiment it is necessary to know how good the results are. We evaluate our
results by determining their error. The word error does not necessarily imply that one has been
careless. Even with the best technique, measured values are never perfectly well known, but
contain some uncertainty. Errors in experimental measurements may be divided into two
classes: (a) systematic errors and (b) random errors.

Systematic errors. Systematic errors are quite reproducible and arise from failure or
incompleteness of underlying theory, a shortcoming in the instrumentation or procedure, or
failure to account for an experimental variable. We characterize the magnitude of systematic
errors by specification of the accuracy. This term is defined as the difference between the
observed value and the true value of the quantity. Thus accuracy is a measure of the
correctness of the result. An accurate measurement is one in which the systematic errors have
been eliminated in so far as possible.

The ultimate goal of any analysis is to have the measured value be the same as the true value.
Of course, one of the fundamental difficulties in real scientific investigations is that the true
value is not known. However, in the student laboratory, the true value has been established
through use of independent reference methods as performed by well-trained personnel.

In the world of science, a central preoccupation is to arrive at the "true" answer by reduction of
systematic error. Often this involves repeating the experiment many times, systematically
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changing as many variables as possible: trying a different location, a different source for the
starting materials, a different instrument, etc. In practice such experimental manipulations are
difficult to carry out, but for crucial experiments, such as testing a fundamental theory of
nature, they are always done. More common, one simply analyzes the experiment carefully,
checking each step to see what 'hidden' influences might be present. This requires the
scientist to think through the entire experiment to find all the flaws in it. For example, if
temperature variations seem to be a problem, a little heat can be applied to see if any results
change.

How then do we specify accuracy? It seems obvious that by calculating the “% error” of the
measured value from the true value we can get a mathematical value for accuracy of the
measurement. This quantity is calculated as

|xmeas - xtrue|
% error = xtrue • 100 (2)

where xmeas is the measured value and xtrue is the true value. This calculation of “% error” is
used when comparing an experimental or measured value to an accepted or true value. If you
need to compare the similarity of two experimental or measured values to one another, this
calculation would be the “% difference”.

meas1 − meas2
% difference = • 100
⎛ meas1 + meas2 ⎞
⎜ ⎟
⎝ 2 ⎠

Random errors. Random errors are deviations (irreproducibilities) in observations which yield
results which differ from experiment to experiment. We characterize these irreproducibilities by
their precision. The precision of a series of measurements thus reflects how closely each
measurement in a series agrees with the others. In Figure 2, we illustrate the difference
between accuracy and precision using the analogy of firing a rifle at a target.

In many cases, precision is influenced by physical effects beyond the control of the operator.
In other cases, precision is influenced by how consistent one is in performing a technique. For
example, the precision of pipetting a volume of a liquid generally improves with practice.

Another way to define random error is as that part of the measurement that varies from
measurement to measurement. Often this is referred to as noise. As a familiar example,
consider the tape hiss in an audio cassette. This noise interferes with the determination of the
reproducible part of the measurement, often known as the signal, which in the case of an audio
tape might be Beethoven's Fifth Symphony. The only way to characterize random noise is to
repeat a measurement many times, collecting the results in a table and then summarizing
them so as to make clear any patterns that have developed.

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Low Accuracy and Low Precision

High Accuracy and Low Precision

Low Accuracy and High Precision

High Accuracy and High Precision

Figure 2. The Bullseye Analogy for Understanding the Difference between Accuracy and Precision

As an example, consider the following table of 10 successive measurements of the volume of

a pipet which is labeled as 10 mL:

9.988, 9.973, 9.986, 9.980, 9.975, 9.982, 9.986, 9.982, 9.981, 9.990

A dot diagram showing the scatter of these values is presented in Figure 3. From this diagram,
we can readily see how the measurements are distributed. In particular, there is a general
location of the observations (in this example we can see that the results are clustered near the
value of 9.982 rather than, say 9.3 or 10.3). Also, we note that the observations are spread
about the general location in a specific fashion (they extend over about .025 mL).

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9.970 9.975 9.980 9.985 9.990

Pipet Volume (mL)

Figure 3. Dot diagram for a sample of 10 observations of the volume of a sample dispensed by a pipet.

When a larger number of results is available, the dots become hard to distinguish from each
other, and we are better able to appreciate the data by constructing a histogram of the results.
Generally, this plot takes the form of a bar graph in which the data has been collected into a
series of intervals along with the number of observations that fall into that interval (many
professors post exam scores in this fashion so that you can see how you did compared to the
rest of the scores in the class). In Table I we have collected 50 measurements of the same
pipet. In Table II the data has been rearranged into groups which record the numbers of
observations that fall into a series of contiguous .003 mL bins. Figure 4 plots the data of Table
II as a histogram.

Trial Vol (mL) Trial Vol (mL) Trial Vol (mL)

1 9.988 18 9.975 35 9.976
2 9.973 19 9.980 36 9.990
3 9.986 20 9.994 37 9.998
4 9.980 21 9.992 38 9.971
5 9.975 22 9.984 39 9.986
6 9.982 23 9.981 40 9.978
7 9.986 24 9.987 41 9.986
8 9.982 25 9.978 42 9.982
9 9.981 26 9.983 43 9.977
10 9.990 27 9.982 44 9.977
11 9.980 28 9.991 45 9.986
12 9.989 29 9.981 46 9.978
13 9.978 30 9.969 47 9.983
14 9.971 31 9.985 48 9.980
15 9.982 32 9.977 49 9.983
16 9.983 33 9.976 50 9.979
17 9.988 34 9.983
Table I. Replicate data on the calibration of a 10 mL pipet.

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Volume Range (mL) Number in Range % in Range

9.969 to 9.971 3 6
9.972 to 9.974 1 2
9.975 to 9.977 7 14
9.978 to 9.980 9 18
9.981 to 9.983 13 26
9.984 to 9.986 7 14
9.987 to 9.989 5 10
9.990 to 9.992 4 8
9.993 to 9.995 1 2
Table II. Frequency distribution of data from Table I.

30
Percentage of Measurements

20

10

0 9.969 9.972 9.975 9.978 9.981 9.984 9.987 9.990 9.993

9.971 9.974 9.977 9.980 9.983 9.986 9.989 9.992 9.995

Range of Measured Values (mL)

Figure 4. Histogram showing distribution of the 50 results in Table I.

We notice that as the number of measurements grows larger, the histogram becomes more
and more certain. In the limit where the number of measurements becomes infinite, we have a
sample of all possible values of the measurement. At this point we realize that the histogram
represents a probability distribution function, which specifies the probability of obtaining a
measurement of a specific value as a function of that value. Probability distribution functions
are conveniently described in terms of two parameters of the histogram of measurements: the
mean and standard deviation.
—
The mean or average of all the measurements is represented by x . It is calculated as the
sum of all the measurements divided by the number of measurements:

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1 N
x = ∑ xi (3)
N i=1
where we assume that a total of N measurements have been made and identified by the
subscript i which ranges from 1 to N.

There are several ways to express the degree of precision in a series of measurements. For
this course, you will calculate the standard deviation as the measure of precision. The
standard deviation, s, is a measure of the size of the random errors in a set of repeated
—
measurements. It is computed by taking the difference between the mean, x , and each
individual measurement, xi, squaring this value, adding all these numbers together, dividing by
the number of measurements minus one (N-1) and then taking the square root.

1 N
s= ∑ ( xi − x )
2
(4)
N − 1 i=1

The value of the standard deviation is commonly used to indicate the amount of uncertainty in
one's experimental values. As an example one might report the results of three experimental
measurements of a pipet's volume as 9.96 ± 0.03 mL, where 9.96 is the mean of the
measurements as calculated from Equation 3 and 0.03 mL is the standard deviation as
calculated from Equation 4.

For many types of measurements, the distribution curves are found to be satisfactorily
described by the Gaussian function:

1 ⎛ x −μ ⎞ 2
1 ⎞ − 2 ⎜⎝ ⎟
P(x) = ⎛ e σ ⎠
(5)
⎝ σ 2π ⎠

where σ is the standard deviation and μ is the mean. We have used the Greek notation for the
mean and standard deviation, to indicate that these quantities are the "true" values rather than
the estimates obtained by doing a limited number of experiments, as implied by equations 3
and 4. The Gaussian distribution function is particularly advantageous because: (a) it is
described by only two parameters, σ and μ, and (b) it is symmetric about μ.

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In Figure 5 we have superimposed a Gaussian function of μ = 9.982 mL and σ = 0.0056 mL on

the histogram. The correspondence between the histogram and the Gaussian function is good,
and generally improves as the number of experiments increases.

30
Percentage of Measurements

20

10

0 9.969 9.972 9.975 9.978 9.981 9.984 9.987 9.990 9.993

9.971 9.974 9.977 9.980 9.983 9.986 9.989 9.992 9.995
Range of Meas ured Values ( mL)
Figure 5. Histogram of Figure 4, with Gaussian curve superimposed.

The prelab assignment on WebAssign addresses the following:

• Calculating the average and standard deviation for replicate volume measurements.

• Calculating the volume of water to use in order to make a solution of sucrose that is
25% sucrose by weight.

• Calculating the actual % sucrose in the prepared solution (using the exact mass of
water added to a specific mass of sucrose) and determining the solution’s density.

• Determining the volume of a piece of metal, given its mass and density.

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Helpful information

• Unit conversions and dimensional analysis are covered in Appendix Two (section A2.2)
in Zumdahl. This section may be helpful when figuring out how to convert between
mass, density, and volume.

• When measuring volumes in these types of glassware, you will notice that the top of the
liquid looks bowl-shaped. This curvature is called the meniscus. When determining the
volume in a graduated cylinder or buret, read the markings on the glassware next to the
bottom of the meniscus. Class A pipets, like the one you will check out from the
stockroom, will deliver the volume marked on the pipet when the bottom of the
meniscus falls on the line etched on the neck of the pipet just above the large ballooned
portion.

• Percent weight by mass, or mass percent, is calculated according to the following

equation:

grams of solute
Mass percent = X 100%
grams of solution
where “solute” is the substance being dissolved (sucrose) and the “solution” is the
solute plus solvent (sucrose plus the water, in this case).

Safety Considerations

In part B, when determining the volume of the metal sample, be careful when you add the
metal to the graduated cylinder containing water. Dropping the metal pieces into the cylinder
haphazardly can result in the glass cylinder breaking or water splashing out of the cylinder or
up the sides, which will affect the accuracy of the volume readings.

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