EXPERIM NT

Scien ri fic Meosurements

Purpose Such quantitative observations provided sup-

porting evidence for the concept that matter was
' Understand how measurements are made and the composed of atoms with definite masses. The ability
utility of basic and derived units of measurement. to determine accurately the relative masses of the
. Identify the different kinds of errors that can be elements and to systematize their chemical proper-
present in measurements. ties eventually led to the creation of the periodic
table of elements. If you look carefully at the peri-
. Display random measurement variations in a odic table, you will note that, with few exceptions,
histogram that approximates the Gaussian normal the elements are arranged in order of increasing
distribution. atomic mass.
. Calculate the standard deviation for a set of When quantitative measurements were made of
randomly distributed measurements. living things, it became apparent that the processes
of life were themselves chemical reactions subject to
. Express the uncertainty of a measured quantity the same laws as other chemical processes.
by using the appropriate number of significant
figures.
. Learn how errors propagate when quantitites are How Meosurements Are Mode
derived from measurements that are multiplied and
Most quantitative measurements are operations in
divided or added and subtracted. which two quantities are compared. For example, to
L r Present the data obtained from measurements
visually, by using graphs.
measure the length of an object, you compare it with
a ruler with calibrated marks on it. As the ruler itself

L o Practice making measurements of mass, length,

and volume and graphing the results.
was designed and manufactured, it was compared
with other standards of length that conform to the
standard unit of length agreed upon by international
L conventions.
The double-pan equal-arm analytical balance is
Pre-Lob Preporotion
L The introduction of quantitative measurement
another example of measurement by direct compari-
son. With this apparatus, the mass of an object is
brought chemistry from the magical, mystical determined by comparing it directly with a set of
\=_ alchemist's laboratory to the practical science it is masses of known value.
today. In the I600s, experimenters began to measure The single-pan analytical balance also involves a
L the properties of gases in a quantitative way; the
relationship between the pressure and volume of a
comparison of masses, using the principle of substi-
tution-an unknown mass on the pan substitutes for
{ fixed quantity of gas was discovered and published known masses on the beam above the pan. The point
by Robert Boyle. of balance occurs when the sum of the known
t It wasn't until the late 1700s, when chemists
began to measure the masses of the starting materi-
als and of the products of a reaction, that some of
masses that have been removed is exactly equal to
the unknown mass.
Figure 1-1 shows how unknown and known
the fundamental laws of chemistry were recognized masses are compared by means of double-pan, single-
and stated. These include the laws of mass conserva- pan, and electronic balances. Even a modern elec-
L tion and of definite composition (the discovery that
pure compounds have constant fixed ratios of the
tronic balance involves an indirect comparison
because standard masses are used to calibrate the
masses of their elements). force coil of the balance.
L
L l-t
t-2 Scientific Meosurements

L
Calibration 1

mass

Balance
suspensron Force coi I

Equal-arm double-pan balance with three knife edges

A
l.._l

Electronic balance
L
I
FIGURE t-t i (A) How masses are compared on an
equal-arm balance. The lever arms of the balance
*-rr must have equal lengths. (B) How masses are
compared on a substitution-type single-pan
'*** balance. Masses whose sum is equal to the
unknown mass are removed from the hanger to
keep the beam in equilibrium. (C) Calibration of
an electronic balance with a known mass. A
sensitive detector/Dc current amplifrer (not
shown) keeps the balance pan precisely at the
Substitution-type single-pan balance with only 2 knife edges rest (or null) position by adjusting the electric !
Constant load = constant sensitivity current in the force coil, The current,
Lever arm error impossible proportional to the mass on the pan, is
B transformed into a digital readout of the mass.

Time is usually measured by counting the num- burets. When measuring volume, we generally use
ber of periods of a system that oscillates at some nat- our eyes to note the position of a meniscus relative l

ural frequency. The pendulum of a grandfather clock to calibration marks and sometimes estimate the
swings at a natural frequency; an escapement mech- position of the meniscus between two marks, as
anism turns a toothed wheel that is connected by shown in Figure I-13 of the Introduction.
gears to the hands of the clock. The hands of an elec- We also make measurements of temperature
i
tric clock are driven by a synchronous electric motor using a thermometer, measurements of time using a
supplied with alternating current of a stable fre- timer or stopwatch, measurements of length using a
quency. A quartz digital watch measures time by meter stick or ruler, and measurements of voltage or
counting (and subdividing) the oscillations of a tiny current using a multimeter.
quartz crystal. The most accurate clocks, which
serve as our fundamental time standard, are based
Bosic ond Derived Units
on counting the frequency of an oscillator that is
continuously compared with the frequency associ- By an international agreement reached in 1960, cer-
ated with a transition between two energy states of tain basic metric units and units derived from them
the electrons in gaseous cesium atoms. From these are to be preferred in scientific use. The preferred
descriptions of various timekeeping devices, we see units are known as the International System units
\-
that the measurement of time is an operation in (commonly called SI units, from the French, Systdme
which the natural periods of various oscillating sys- Internationale). The basic units of the SI system are
tems are compared. given in the Appendix, Table 1.
The two most common kinds of measurements The National Institute of Standards and Technol-
made in a general chemistry laboratory are measure- ogy (NIST) Internet site (http://physics.nist.gov) pro-
ments of mass, using a balance, and measurements vides a full discussion of the fundamental physical
of volume, using graduated cylinders, pipets, and constants, including historical background informa-

;
t_ Scientific Meosurements r-3

tion and the best values of the constants and their we do not get exactly the same value for each meas-
uncertainties. urement. There will be a dispersion (or spread) of the
Units obtained from the basic units are called measured values. The smaller the spread of values,
derived units. The volume of a cube or rectangular the more precise will be the average (or mean) value
box can be determined by measuring the lengths of of the measurements. So accuracy and precision are
its three dimensions and computing the volume as different concepts. Accuracy is a measure of how
( the product of those lengths. Thus, volume is close the measured value is to the true value. Preci-
derived from length measurements and has the sion is a measure of the reproducibility (or dispersion)
dimensions of length cubed-for example, cubic cen- of the measurements. The average of several meas-
L timeters (cm3). Cylindrical containers are easier to urements might be accurate without being very pre-
manufacture than rectangular containers, so volume cise, or a set of measurements might have good
( is more often measured in containers such as gradu- reproducibility, and therefore good precision, but
: ated cylinders and burets. The volume of a cylinder the average (or mean) value might not be very accu-
L is equal to the product of its cross-sectional area
times its length. This formula allows us to use a
rate. Good-quality measurements will be both pre-
cise and accurate. Figure 1-2 shows graphically what
length scale, often inscribed along the length of the is meant by accuracy and precision.
I cylinder, to determine volume. We've said that we determine accuracy by

t The Assessment
comparison with standards. How do we measure

of Experimentol Errors A:
,\_ ) ( High precir ion and
Every measurement involves some measurement () o high acc lracy
o( ) o
L uncertainty (often referred to as "error," but rof in
the normal sense of this term as a synonym for
"mistake"). Because many generalizations or laws of o
science are based on experimental observations oo
ooa
precision but
accuracv
involving quantitative measurements, it is important
L for a scientist (or a student of a quantitative science)
to take into account any limitations in the reliability
(
Poor precision t ut still accurate
because thr average is
close to the ( orrect value
of the data from which conclusions are drawn. In the
(_"
following section, we will discuss different kinds of o a oo
errors-systematic, random, and personal errors-
L
D:
and assess the quality of a measurement by consid- Poor precision; accuracy also
is poor because the average is
ering its accuracy and precision. not close to the correct Yalue o
o o
L Accurocy ond precision
Cor rect
( OO

L The limitations of both accuracy and precision will

contribute to uncertainty in the measurement. The
va ue

! error in a measurement, or better, the average of sev-

eral measurements, is the difference between the
1.50 1.55 1.60
Volume (mL)
r.65 r.70

measured value and the true value of the quantity

(__
measured. The smaller the error, the closer the meas- FIGURE I -2 The results of an acid-base titration
ured value is to the true value and the more qccurqte exercise are shown for four individuals. Each
t. is the result. The true value is sometimes difficult to
establish. Generally, it involves applying the same
person titrated six nominal IO-mL samples of the
same O.O4OO M acid solution with O.250 M NaOH
measurement technique to an unknown sample and (sodium hydroxide) dispensed from a 2-mL
\* to a carefully prepared or analyzed standard sample
microburet. The horizontal position of the black
dots shows the measured titration volumes. The
that resembles the unknown as much as possible. vertical columns of two or three black dots mean
Preparing these kinds of standards requires trained that those measured volumes were the same. The
specialists; standards for many kinds of measure- results of individual A were both accurate and
ments can be purchased from the National Institute precise, while those of B were precise but not
t accurate. The results of C were accurate but not
of Standards and Technology (NIST). precise, The results of D were neither accurate
L Typically, when we make a series of several meas-
urements on the same sample or replicate samples,
nor precise, (There is a systematic error
combined with substantial random errors.)
t-4 Scientific Meosurements

precision? By making several measurements and remain good. A miscalibrated scale on a ruler, for
determining the spread of the measurements. How example, would cause a systematic error in the meas
I
many measurements? Somewhere between 3 and 30. urement of length.
Three is a minimum for making a rough estimate of Similarly, in Figure t-2, the B group of measure-
the precision. Thirty measurements would give you a ments shows evidence of a systematic error, perhaps t
decent estimate. A single individual seldom has time due to a misunderstanding of how to read the posi'
in a general chemistry lab to make 30 replicate meas- tion of the meniscus in a graduated cylinder or pipet.
urements of the same quantity, but we might aggre- If the volume is read at the top rather than the bot
gate the results of all the students in a lab section or tom of the curved meniscus, the measured volume is
in the whole class in order to get a better estimate of systematically too small.
the precision. In today's world, computer-controlled
instruments can make hundreds or thousands of Random Errors qnd Stqndqrd Deviqtion lf a
repetitive measurements in a short time. measurement is made a large number of times, you
will obtain a range of values (like the distributions
Human Factors It's been observed that students
shown in Figures I-2 and 1-3) caused by the random
who are well-trained in a measurement technique
errors inherent in any measurement process (or devi-
and highly motivated will produce results with better
precision (smaller spread in the measurements) than
ations in a manufacturing process). For random
errors, small errors are more probable than large
students who lack training and motivation. Likewise,
errors and negative deviations are as likely as posi-
a single skilled and motivated student will attain bet-
tive ones.
ter precision than will a group of students in which
Figure l-3 shows the results of weighing 100 dif-
there is a range of skills and motivation. Making
ferent pennies (minted in 1983 or later). The result-
measurements in the laboratory is not unlike learn-
ing distribution of the measured masses of the pen-
ing a sport. Training, discipline, and practice pro-
nies is displayed as a bar graph called a histogram.2
duce superior performance.
(The root of the word histogram comes from the
The Mean (Average) Value and the Deviation greek ftlstos, which has several meanings, one being
Unless we have accurate standards against which we "mast," as in the mast of a sailing ship.) In the penny !
can test our measurement, we often do not know the mass histogram of Figure 1-3, the main cause of the
true value of a measured quantity. If we do not, we can
obtain only the mean, or average, value of a number of
dispersion (or spread) is not the uncertainty in meas-
uring the mass of the pennies, which is accurate to
i
measurements and measure the spread or dispersion +0.001 g, but rather the random deviations in the
of the measurements. The mean value is obtained by process for manufacturing the pennies.
adding all of the individual measurements and divid- Superimposed on the histogram is a bell-shaped
ing by the total number of measurements: curve called a Gaussian error distribution, the distri-
bution that is approached when the number of
)x, l

, ;'
(1) measurements becomes very large (or infinite). The
mean value of the set of measurements is the most
where I represents the operation of summation.l probable value, corresponding to the center of the
A measure of the spread of individual values
from the mean value is the deviatlon, D-defined as I
2A histogram is a bar graph that shor.vs the frequencl distribution
the difference between the measured value, x,, and
of the measurements of a variable (x) in lvhich the \,vidths of con
the arithmetic mean, x, of a number, N, of measure-
tiguous vertical bars are proportional to an interval .\x of the Vari
ments (a bar over a quantity means the average value able and the heights of the bars are proportional to the number of
of the quantity): x values that fall in the interval lx.
The process of constructing a histogram may be thought of
5i:Xi x (2)
as drarving a horizontal Iine representing the x-axis variable,
dividing the line into intervals of wjdth -\x, which r,ve rvill cali
Systematic Errors Errors are of two general types,
brns, sortrng the Nmeasurements of the variable x into the bins,
systematic (determinate) and random (indetermi- and counting the number of values that fall rn each bin. The
nate). A systematic error causes an error in the same number of x values that fall in a bin is called the frequency. \tie
direction in each measurement and diminishes accu- then plot the frequencies as contiguous bars rrsing from the hor-
racy, although the precision of the measurement may izontal x'axis. lf we sum the frequencies (bar heights) of all the
bars, they will add up to N, the total number of x values in the
sample.
ln a normalized histogram, each frequency is divided by N,
lTherefore, lx, means to calculate the sum xL + x2 + x3 + the total number of measurements, to give the frdction of the
X+i"' rneasurements that fall into that bin.
(_
Scientific Meosurements t-5

25 gives only an estimate of the standard deviation

o unless the number of measurements is large (>50).
We must recognize that, when we repeat a measure-
oa. ment only two or three times,3 we are not obtaining
EB 20
p: a very large sample of measurements, and the
=il confidence that we can place in the mean value of a

I He
9rr
OE
t5
small number of measurements is correspondingly
reduced.

L -00
oo
Although the formula may look forbiddingly com-
plex, the steps are very simple.
EL IO
f :
ES
>o
. First, calculate the arithmetic mean or average
value, x, of the measurements.

\- o5 . Then subtract the mean value, x, from each one

5
=tA of the individual values, x,, to obtain the deviation.
o
f lJr
There will be both positive and negative deviations
. Square each deviation, and add all of the squares
t 0
S^
rP^
^VVVVVVVV F6^ ooo^ p"^+u^..f
^f"
. Divide the total by N- 1, where Nis the total
number of measurements.
I Penny mass (grams)
\ . Finally, take the square root of the result to
al

FTGURE I -3 i ftre measured mass distribution of obtain the estimate of the standard deviation.
L l0O different pennies minted in the year 1983 or
later is plotted as a bar graph (called a The procedure for the calculation of the standard
histogram). The mean (average) mass of the deviation is illustrated in Table 1-1.
sample of pennies is 2.499 g with a standard We said that the maximum of the smooth bell-
deviation of O.Ol9 g. Think of the process of
shaped curve (Gaussian error curve) shown in Figure
L': constructing the bar graph as dividing the
horizontal mass axis into bins of arbitrary width
and sorting pennies into the bins according to
1-3 corresponds to the average (or mean) penny
mass (2.499 g). The spread (or dispersion) of the
t- their masses and counting the number of pennies
in each bin. The width of each bin, represented
curve is determined by the standard deviation
(0.019 g). The standard deviation can be related to
by the bar width, is arbitrarily made equal to one-
L half standard deviation (O.OO95 g). On the
horizontal mass axis, the mass value labels are
the confidence interval, or the range about the mean
value in which one of a group of measurements may
the values in the center of each bin. For each bin, be expected to fall. If we recognize that the Gaussian
L the bar height, called the frequency, is equal to
the number of pennies having masses that fall
error distribution is a distribution of the probabili-
ties of obtaining a particular measurement, we see
within the bin boundaries.
L The smooth bell-shaped curve is the Gaussian
distribution for a large number of pennies whose
that the probability of measurements occurring close
to the mean will be greater than the probability of a
masses are randomly distributed about a mean measurement occurring far away from the mean. In
\_ value of 2.499 g with a standard deviation of fact, there is a 0.68, or 68%, probability that a given
O.Of 9 g. As the total number of pennies in the measurement will fall within plus or minus one stan-
sample increases, the bar graph approaches a
Gaussian distribution.
dard deviation of the mean value. There is a 0.95
(95%) probability that a measurement will fall within

L Gaussian distribution curve. The spread, or disper-

plus or minus fr.yo standard deviations of the mean
value. This means that, for the curve of Figure 1-3,
sion, of the results is expressed by the standard we can expect thal 95% of the measurements will fall
(,_
deviation, s: between 2.461 and 2.537 g. If we were to measure the
total area under the curve, we would also see that
>( il2 l2
( (3)
.s
N-1 )'
3lf only two or three measurements are made, the standard
t.- This formula says: Sum the squares of the deviations,
deviation may be approximated by the average deviation,
divide by N - 1, and take the square root of the
which is the mean value of the absolute values of the devia
result. So the standard deviation could also be called
(- the root-mean-square deviation. This formula actually d= )x,
tlons,br: =
lJ
x
 I

l-6 Scientific Meosurements

|

I[f[fiEI The Procedure for Calculating Significonf Figures

the Standard Deviation
The limited precision of any measurement must be
Measured Square of considered whenever that measurement is to be
Valueo Deviation Deviation used, whether that use is to report the value of the
(x) (xi - x) (x; - x)2
quantity, to constitute one of a series of measure-
ments, or to be combined in a calculation with other
4.28 0.01 0.000r
measured quantities. The limited precision creates
4.21 0.08 0.0064
uncertainty, which limits the conclusions that can be
4.30 0.01 0.000i
drawn from a measurement.
4.36 0.07 0.0049
Keeping track of this uncertainty would be rather
4.26 0.03 0.0009
cumbersome if the uncertainty needed to be
4.33 0.04 0.00 r 6
reported each time the measurement itself were
) : zs.z+ >:o.oo ) -o.or+o reported or used in a calculation. Introducing the
concept of significant figures allows us lo imply lhe
precision of a measurement without having to state
* )*,
'' 25 74
The mean, -r - 4.29 g explicitly the uncertainty. Significant figures also
allow us to easily estimate the precision of a value
rhe srandard deviation, r - (+=+)'" : o.or, * that is calculated from a combination of different
measured quantities.
The best value of the measurement is written as
4.29 + 0.05 g.
For example, when the mass of an object is
reported as 56.78 g, it is implied that the object was
'The measured values are those obtained from a series of six
weighed in such a way that there is no question that
replicate measurements of the weight of a sample on a triple- the mass is at least 56.7 g and that the value of the
beam balance.
hundredths place is thought to be 8, but that some
judgment was required in deciding this last digit. We
should infer that there is an uncertainty of at least
0.01 g in the value 56.78 g.
this interval of 4s 1*2r about the mean value) corre- The number 56.78 has four significant figures
sponds to 95% of the area under the Gaussian error (that is, digits); three are completely certain (56.7),
curve. Note that we cannot make a definite predic- and one has some uncertainty in it (the 8), but all
tion about any single measurement. We can only say four digits contain useful information. When the sig-
that if we make a measurement a large number of nificant figure convention is used, the last digit writ-
times, we can expect that 95% of the values obtained ten is assumed to have an uncertainty of at least I.
will fall within plus or minus two standard devia- Note that although the use of significant figures to
tions of the mean. imply the uncertainty is practical, the convention
Personql Errors To the types of errors already i

described-systematic and random-we might add a

third category, the personal error, or blunder. Such
errors are all too common in student work. Thus, if
sflffp Typicat Instrument uncertainties i

the numbers on a scale are misread and recorded Typical

incorrectly, or if part of a solution is spilled in a titra- Instrument Uncertainty
tion, the result will contain an error. Careful work *0.50
will not contain any blunders, and any work sus- Platform balance g
Triple-beam (centigram) balance +0.01 g
pected of containing one should be repeated, and the
Top-loading semimicro balance *0.00I g
nature of the error should be recorded in the lab
Analytical balance *0.0001 g I
notebook.
100-mL graduated cylinder +0.2 mL
I 0-mL graduated cylinder +0.1 mL
Precision of Ioborotory operotions 50-mL buret +0.02 mL
25-mL pipet *0.02 mL
The precision associated with various pieces of 10-mL pipet +0.01 mL
equipment you may use in the laboratory is summa- Thermometer (10 "C to I 10 'C, +0"2 "c
rized in Table I-2. These uncertainties express limi- graduated to I "C)
tations in the reading of the instruments and do not Barometer (mercury) +0.5 torr
reflect systematic errors.
 Scientific Meosurements t-7

has limitations. The values 35.4 + 0.1 and 35.4 + 0.4, quantity shown in Table 1-3. To specify 62,000 as
for instance, would both be expressed as 35.4 to the having three significant figures, it would be necessary
correct number of significant figures. Nevertheless, to write it in scientific notation as 6.20 x 104.
the convention provides a convenient way of stating
the approximate uncertainty in a number, and signifi-
cant figures are especially helpful in estimating the
Propogotion of Error in Colculotions
uncertainty in a value calculated from a series of The limitations of each measurement must be rec-
uncertain quantities. ognized whenever that measurement is to be used
Other examples of the number of significant fig- or reported. When the value of a measurement is
ures in quantities are given in Table I-3. used to calculate another quantity, the uncertainty
Zeros require special attention in order to deter- in the measurement limits the certainty of the calcu-
mine whether or not they are significant figures in a lated value. This uncertainty must be recognized,
number. The general rule is that zeros used to hold a but the relationship between the uncertainty of the
decimal place are not significant. The implications of measurement and that of the calculated quantity is
this statement are as follows: not always easy to predict. Significant figures are
useful because they enable us to estimate the error
l. Zeros in front of a number are not significant. In in calculated quantities. Two simple rules allow us
Table I-3, the examples 0.0862 (with three signifi- to produce this estimate for the basic mathematical
cant figures) and 0.001740 (with four, the last zero operations.
being significant) illustrate this.
2. Terminal zeros are significant if they are to the
l. For multiplication and division, the answer is
rounded to the same number of significant figures as
right of the decimal point. Thus, the terminal zeros
in 0.001740, 1.6300, 14.00, and 250.00 are signifi- that of lhe least significant factor in the calculation.
Examples include:
cant digits. This also means that, if a measurement
was not made precisely, the terminal zeros must not 1.48 x 3.2887:4.87
be written. For instance, 14.00 implies a measure-
)A)
ment made to +0.01. If the measurement is only pre-
L) cise to +1, only "I4" should be reported.
8.t47
0.023
3

x 1.482 x 13.25:0.45 (4)

3. Zeros as digits between other significant digits are
q- significant (note 12.0004 with six significant figures).
::71I - 23.ooo or 2.3
U.OUU 5
ro4
4. By convention, terminal zeros are not significant
L if there is no decimal point, but a decimal point 1.918 0.47523 81.96 1r t
'+
implies that all digits to the left of it are significant. 53--
(_ This is the origin of the implied four significant fig-
In each case, the least significant factor determines
ures in the quantity 1500., but only two in the 62,000
the significance of the answer, no matter how signifi-
L cant the other factors are. If you perform the forego-
ing calculations on a calculator, you will notice that
calculators are unaware of the significant-figure rules
I[f[f@ Number of Significant Figures and are more than happy to create an abundance of
Number of nonsignificant digits. You must decide which of the
Quantity Signiflcant Figures digits are to be retained as significant and which are
to be discarded.
L 857.29
435
5

3 2. For addition or subtraction, the last significant

I 6.02 x I023 digit in the answer is the right-most common digit of
L 0.0862
5
3 all the terms in the sum. This rule is more easily seen
0.00 r 740 4 and rationalized by considering an example, such as
t2.0004 6 adding these two numbers:
1.6300 5
t2.34 addend
62,000 2
+ 5.6 addend (s)
14.00 4
17.94
t 1 500.
25 0.00
4
5
1
sum

not significant
l
r-8 Scientific Meosurements

The digit "4" in the sum is not significant because Then only numbers need to appear along each axis,
the addend 5.6 does not have a significant digit in and the axes are not cluttered with the units of each
the hundredths place. This rule can be understood variable.
by realizing that the hundredths digit of 5.6 is
unknown and could have any value. When this 3. Scales The scale on each axis should be chosen
unknown value is added to the "4" of 12.34, the carefully so that the entire range of values can be plot-
result is also an unknown (nonsignificant) digit. ted on the graph. For practical reasons,2,4,5, or 10
Other examples of significant figure determina- divisions on the graph paper should represent a deci-
tions in addition and subtraction are mal unit in the variable. This equivalence will make it
easy to estimate values that lie between the scale divi-
73.2r3 1.00257 8.5672
sions. For greatest accuracy and pleasing proportions,
+ t4.84 + 0.0013 + I53
the scales selected should be chosen so that the graph
88.05 1.0039 t62
(6) nearly fills the page. Be sure, however, that no plotted
points fall outside the borders of the graph.
6.02 x1023:6.02 x 1023 L.76541
Note that the lower left corner of the graph does
+5.2 x1022: .52 x 1023 * r.75893
noir have to represent zero on either axis. If the range
6.54 x 1023 0.00648
of measured values extends to zero, the latter may
be a good choice; but if not, there will be much
Grophing wasted space on the graph.
In many instances, the goal of making measurements
4. Data Points It is good practice to mark the loca-
is to discover or study the relationship that exists tion of each data point with a very small dot and then
between two variables. The pressure and the volume
draw a small circle around the dot to make the point
of a gas, the volume and the temperature of a sub-
more visible.
stance, or the color of a solution and the intensity of
that color are examples of sets of variables that are
5. The Curve A smooth curve should be drawn
related. As one variable changes, so does the other.
through the points. The curve should pass as close
We often use graphs to visualize the relationship
as possible to each of the points but should not be
between two variables. If there are two variables, the
graph will be a two-dimensional plot of the points
connected point to point with short line segments. If
the relationship appears to be linear, the smooth curve
I
)

that represent pairs of values of the two variables. An

should be a straight line. If the line is extended past the
example of a well-drawn graph is shown in Figure 1-4.
range of the measured values, this extension should be
Notice that the graph has several features that help
indicated by a dashed rather than a solid line. I
clarify the meaning of the graph.

Lineor relotionships
Feotures

l. A Title The title on a graph should be a brief but Although many variables in chemical systems may
be related in a complex nonlinear way, some of the
clear description of the relationship under study.
Titles such as "Lab Number 1" or "Volume and
Temperature" are not good practice because their The vapor pressure of water
between 110'Cand 150"C
meaning is clear only to those familiar with the
experiment and because the meaning will be lost as P 3000
memory fades with the passage of time. OJ

2. Labeled Axes Each axis of the graph should be o 2000

o-
clearly labeled to show the quantity it represents and
the units that have been used to measure the quan-
tity. You should recognize the distinction between t20 i30 140 150
i

the quantity measured (pressure, volume, tempera- Temperature ("C)

ture, time, etc.) and the units that have been used to j
measure that quantity (atmospheres, liters, degrees FIGURE I -4 i This is an example of a well-made
Celsius, seconds, etc.). graph. Notice the clear title, the properly labeled
axes with variable names and units, the clearly
It is convenient to label each axis with the name of
marked data points, and the smooth curve
the measured quantity followed by the unit (usually showing the observed trend and the extrapolated
abbreviated) in parentheses-for example, Volume (L). trend.
t_ Scientific Meosurements t-9

relationships turn out to be direct proportions; that interpolation For example, from Figure 1-4 we can
is, the value of one variable is a constant factor determine by interpolation that at 125 'C the vapor
times the value of the other variable plus or minus pressure of water is about 1800 torr.
a second constant. When this proportional rela- If the estimation is made beyond the measured
tionship exists, the graph of the two variables will range, the process is called extrapolation. From Fig-
be a straight line. An example of a linear graph is ure 1-4 we can see that the vapor pressure ofwater at
shown in Figure 1-5, which illustrates the volume 155 "C is estimated by extrapolation to be about
L of a sample of gas versus the temperature of the 4000 torr.
gas. Interpolation and extrapolation are useful tech-
L The slope of the line is the constant factor relat- niques, but both are estimates and assume that the
ing the two variables. It can be determined by using graph is accurate or that it extends beyond the meas-
a any two points on the line, as shown in Figure 1-5.
Note that the slope is calculated in the units of the
ured values. For extrapolation, especially, this
assumption may lead to incorrect conclusions.
two variables.
\- In Figure 1-5, the point on the line where the
Exercises in Meosurement
value of the volume is zero (which is where the line
!- crosses the temperature axis) is called the tempera- Materials and Supplies: Sets of four pennies dated
1981 and earlier and sets of four pennies dated 1983
ture intercept.
L If a relationship exists between two variables, it
is possible to estimate what the value of one variable
and later (plus some extra ones if you plan to do experi-
ments on the pennies as described in Consider This);
i
would be for any value of the other variable by using meter sticks; 30-cm metric rulers; cardboard milk car-
'\- the graph. If the point of interest lies within the tons (quart or half-gallon size); beakers of five or six
range of measured values, this estimation is called sizes; 60-cm lengths of string; fine-tipped marking pens.
L
70

ri
L 60 -:*j-r*
:lli

50

t
ll
t1: 'r
itl
:1:

L o
40

t o 30

20

L 10

t
\_"
0
1,
-300 -250 -200 -l 50 -l 00 -50 0 50 100
Temperature ("C)

!
FIGURE I -5 i The relation between the temperature and the corresponding volume of a sample of
hydrogen gas. Volume is directly proportional to the Kelvin temperature, as represented by Charles's law,
L V = kT = k(t'C + 273), where k is the slope of the straight line. (The figure was created using a
spreadsheet, plotting the data points as an (XY) scatterplot and adding a trendline that gives the slope of
the straight line plot.)
r-ro Scientific Meosurements

l. Mass Measurement Pennies minted in the tice you can learn how to use Excel spreadsheets to
United States in I98l and earlier years are signifi- do data calculations like those in Table 1-1 and pro-
cantly different from pennies minted in 1983 or duce (XY) scatterplots and histograms like those l*.
later. Is it possible to tell the difference between shown in Figures I-2, l-3 (a histogram), 1-4, and 1-5
these two kinds of pennies by weighing them?
Work in pairs. One student will receive from the
that were produced using an Excel spreadsheet.
Some guidance in using Excel is provided in Table 13,
L
instructor four pennies dated 1981 and earlier, and the last table of the Appendix.
the other student will receive four pennies dated
1983 and later. Carefully check the zero on the ana-
lal Circumference versus diameter of different
size beakers. Measure the diameter of each of four
lytical balance. Weigh and record the mass of each of
different sizes of beakers. An easy way to do this
the four pennies to the nearest milligram as well as is to place the edges of two books or blocks of
the year in which each penny was minted. Then put
all four pennies on the pan and weigh and record the
wood against the beaker on opposite sides. Then \*
carefully remove the beaker and measure the dis-
total mass of the four pennies. Finally, record the tance across the gap with a metric ruler or meter
masses and dates of the four pennies weighed by
stick. Record each diarneter measurement.
your partner.
Now measure the circumferences using a
In your report, calculate the mean (average) value
length of string. Draw the string snugly around \-
and standard deviation for the masses of the pennies
the beaker and mark the overlapped ends of the
that you and your partner weighed. Can you tell from
string with a fine-tipped marking pen. Measure
these data if there is a significant difference in the
the distance between the marks on the string with
average mass of the two groups of pennies? If there
a meter stick to get the circumference of each of
is a significant difference, what hypothesis could you
the four beakers.
offer to explain the difference?
In part 3, your instructor may also ask you to plot Making a graph. In your report, make a graph of
the data (penny mass versus year in which the penny the circumferences of the beakers versus their
was minted) for the class data. This can be conve- diameters. If your instructor so directs, make the
niently done using a spreadsheet program on a com- graph using graphing software (such as an Excel \-
puter, if one is available, or it can be done by hand. spreadsheet) to make an (XY) scatterplot of the

2. Volume Measurement
data points, adding a linear trendline and check- L
ing the trendline options boxes to display the
i
(a) Using a metric ruler or meter stick, measure trendline equation and R2 value. (R2 is a measure
the length of each of the three edges of a quart or of the correlation or goodness of fit.)
half gallon cardboard milk carton to the nearest If your instructor directs you to make a hand-
0.5 mm. (lgnore the irregular portion of the car- drawn graph, first plot the points choosing an
ton at the top.) Record these values. In your appropriate scale. Then draw a straight line
report, calculate the volume of the milk carton in through the plotted points that gives a good fit to
units of cubic centimeters, liters, and quarts. the data points. Pick two points on the line
(located near the ends of the line) and determine
(b) Read the volumes of partially filled l0-mL and
the slope of the line, where
50-mL graduated cylinders provided by the
instructor. Take care to avoid parallax error and
note the position of the bottom of each meniscus
,
slope = change in circumference
change in diameter
\7 )
I
as described in the Introduction. Read the value Is the numerical value of the slope, the ratio of
of the smaller cylinder to the nearest 0.02 mL, the circumference to the diameter of a circle,
and read the larger one to the nearest 0.2 mL. what you expected it to be?
Record these values. Report the two values to the
instructor. If they are not correct, the instructor (bl Penny mass versus year of minting. If your
will show you how to read the meniscus instructor so directs, use the accumulated data \.-
correctly. for the class to make a graph of the average mass
of your pennies versus the year in which they \
3. Graphing In the report form, graph paper is were minted. The class data can be entered and
provided for making hand-drawn graphs. However, if plotted by hand or by using a computer and
your instructor approves, we suggest that you build spreadsheet program. If you have several pennies
your computer skills by making the graphs called for minted in the same year, you can enter a data
in Part 3(a) and 3(b) using a Microsoft spreadsheet or point for each penny or plot the average mass
other graphing software. With some study and prac- for that year. From looking at your graph, is it
(_
Scienti[ic Meosurements I-l t

possible to see evidence of any change in the Bibliogrophy

average mass of pennies over time? what year(s)
does it appear that this change took place? What The National Institute of Standards and Technology
hypothesis would you suggest to explain your (NIST) Internet site (http:,//physics.nist.gov)
findings? Was there a change in size of the pen- provides a full discussion of the physical
nies? If not, how could they be the same size, but constants, including historical information and the
have different masses? best values of the constants and their
uncertainties.

L CONSIDER THIS
Mauldin, R. R., "lntroducing Scientific Reasoning with
the Penny Lab," J. Chem. Educ. L997, 74,952-955.
Miller, J. A. "Analysis of I9B2 Pennies," J. Chem. Educ.
To get to the bottom of the question of how pennies 1983, 60, r42.
could be different without looking much different to
Ricci, R. W.; Ditzler, M. A., "Discovery Chemistry: A
\_ casual observation, some further experimentation is
Laboratory-Centered Approach to Teaching General
called for. Here are some experiments you can try.
Chemistry," J. Chem. Educ. L991,6B, 229. The
L Take a penny from each group (1981 or earlier and
1983 or later) and use a triangular file to file four
authors describe a measurements experiment they
call the Pennies Lab.
L equally spaced notches on the edge of the penny.
First, carefully observe the notches you have filed. Sardella, D. J., "An Experiment in Thinking Scientifically:
Using Pennies and Good Sense," J. Chem. Educ.
Are there any obvious differences? Then, working in
1992, 69,933.
\_
t
a fume hood, put two notched pennies in a small
beaker and cover them with 10 mL of 6 M HCl. Stolzberg, R. J., "Do New Pennies Lose Their Shells?

L Observe the pennies for a few minutes and after

standing for an hour or two. Do you see any differ-
Hypothesis Testing in the Sophomore Analytical
Chemistry Laboratory," J. Chem. Educ. L998, 75,
ence in the way the pennies behave in HCI? 1453*1455.
Or try this. First, file notches on the edges of the
pennies. Then, using a pair of steel tongs to hold the
L pennies, try heating the pennies in the flame of a
Bunsen burner. Be careful to tilt the burner so that, if
the penny melts, the molten metal won't fall into the
{...-
burner and clog it, or worse, fall on your hand. Is
there a difference in the way the pennies behave in
(- the flame of a Bunsen burner? Now try to put these
observations together to explain any differences you
(-- have found in the pennies.

L
t
L
L
 {

L
l

t
 T
.,'-\
RE PORT I
.
Scientific Measurements Name
b*,,
:: -r
L. Date Section

rt.--
i
Locker Instructor_
\_

Exercises
L l. Determine the number of significant figures in each of the following quantities

( 45.8736 t.70 t0 1

0.00239 0.00 s 90
a 48,000 1.00040
93.00 4.0000
\_
3.982 x 106 3 800

L 2. Express each of the following quantities using significant figures to imply the stated error. For instance, 236
with an error of +0.1 would be written as 236.0, but if the error was +0.01, it should be reported as 236.00.
\- 2.3 + 0.001 1.77 + 0.06
I.989 + 0.0003 22,500 + I0
1.77 + 0.01 0.0043 + 0.000007

3. Round each of the following to three significant figures.

L r367
0.0037421
r2.85
t.6683 x I0-a
L 1.5587 t.632257

4. Perform each of the indicated operations and report the answer to the proper number of significant figures
32.27 x 1.54
(- 3.68 / 0,0792s
1.750 x 0.0342
L 0.009s7 / 2.9465

a (3.2650 x 1024) x (4.85 x 103)

7.56 + 0.153

8.2I98 - 5.32
L 10.052 - 9.8742

6.75xI08+5.43x107
\,-- 0.01953 + (7.32 x 10 3)
(8.52 + 4.rs86) x (18.73 + r53.2)

\,'/8iz x lo-3
(3.84 x Io 2)3
(0.000738 8.3 x l0-s) / (6.298 x r0 8)

L
r -r3
5. To demonstrate that the rules for significant-figure propagation in multiplication do provide an estimate of
the uncertainty in the answer, consider a block with rectangular sides whose dimensions have been measured
with a millimeter ruler.
Height: 254.7 mm Width: 136.8 mm Depth: 25.3 mm
(a) Determine the volume of the block in cubic millimeters. Report your answer to as many digits as your
calculator displays.

(b) Determine the volume of the block if you assume that each of the foregoing measurements is actually
0.1 mm too low.

\*

(c) With which digit do the answers to parts (a) and (b) begin to differ? If you report the volume using all of
the digits that are the same in parts (a) and (b) plus one more digit where the two values do not agree, how
many digits should you report? \-

(d) How many digits would you report according to the rules for significant figures? Is this the same as in
part (c)?
\-

\
6. The density of water is determined by measuring the mass of a known volume of water. If you determined the
density of a 25-mL sample of water, how many significant figures should you report if you used the following
l.
instruments? (Refer to Table l-2 for the instrument uncertainties.)
(a) An analytical balance for measuring mass and a 25-mL pipet for the volume measurement

(b) A centigram balance and a pipet

(c) An analytical balance and a graduated cylinder

L
(d) A centigram balance and a graduated cylinder

I -t4
 REPORT T SHEET 2
1r:
t:
ti
lil Name Date
Il
L

L I
L

I
I

I Doto ond Colculotions

l.
I Mass measurement
(a) Your data for the weighing of four pennies
L Square of
Mass of the Penny Deviation Deviation
Date of the Penny (x) (xi t) (xi - x)2

L o o
o o

L o o
o

C Calculate the sum: ) : g od

Mass of your four

pennies weighed together
L Calculate the average (mean)
o

mass of the four pennies.

L Average mass: x : o

Now calculate the deviations, the deviations Calculate the standard deviation for the four pen
squared, and their sums at the top of the nies following the example shown in Table l-I.
next column.
L Standard deviation
alf there are no errors in your calculation, the sum of the deviations should be 0.
s: o

l._
(b) Your partner's data for the weighing of four pennies:
(_-
Square of
L Date of the Penny
Mass of the Pentry
(xi)
Deviation
(xi - x)
Deviation
(xi - x)2

L 6 g
o o

L g
c
o
o
Calculate the sum: ) : 6 oa
b
Mass of your four

L pennies weighed together

Calculate the average (mean)
g

mass of the four pennies.

L Average mass: x : o

\ Now calculate the deviations, the deviations Calculate the standard deviation for the four pen-
squared, and their sums at the top of the nies following the example shown in Table I-I.
next column,
-
(

Standard deviation s: o

'lf there are no errors in your calculation, the sum of the deviations should be 0
L
I r -I5
 t
(c) Summarize the results of the calculations for your data and your partner's data.

Your Data Your Partner's Data

Average mass, x g
L
Standard deviation, s g o

Sum of individual masses o

Mass of the four pennies weighed together o

Do the data indicate that there is a significant difference between the masses of pennies minted in 1981 and
earlier and those minted in 1983 and later years? Explain, using the averages and standard deviations. L

\-

Suggest a hypothesis for the difference in masses

\-

2. Volume measurement
(a) Milk carton dimensions:

Height: CM width: cm Depth CITl

Calculate the volume of the milk carton in units of cubic centimeters: y: cm3

Convert this volume to units of liters: V: L

Convert this volume to quarts: Y: qt

T

Does the calculated volume agree with the value printed on the milk carton?

(b) Volume of liquid in 10-mL cylinder: mL

Volume of liquid in 50-mL cylinder: mL

(Show your values to your instructor.)

l-16
 REPORT I SHEET 3

Name Date

L
3. Graphing
(a) Circumference versus diameter for different size beakers

Circumference
L Beaker Size
(mL)
Diameter
(cm) (cm)

L
L
L On the graph paper provided, plot the circumference along the vertical axis and the diameter along the hor-
izontal axis. Ensure that your graph has all of the features discussed on page 1-8.

\-
L
L
L
I

L
L
Calculate the slope of your graph, following the example shown in Figure 1-5, and discuss the significance
of the numerical value of the slope.
, A circumference
l
' A diameter

L
t-17
 t
(b) Penny mass versus year of minting
Make a plot of the average mass of the pennies versus the year in which they were minted for each year for
which you have data. Expand the mass scale (a range of 2.3 to 3.3 g is suggested) so that you can easily see
any trends. The horizontal axis should range over the years from your oldest to newest penny (there may
be gaps in your plot if you have no data for a particular year).
L

\-

From looking at your graph, is it possible to see any evidence of a change in the average mass of pennies
over time?

In what year(s) does it appear that this change took place?

Was there a change

masses?
in the size of the pennies? If not, how could they be the same size but have different L

WffiffitrWrffil* coNslDER THIs liilll._ .....

If you tried any of the experiments, briefly summarize your observations and what you concluded from them i

r-r8