Lab 1A:

ACCURACY, PRECISION, AND UNCERTAINTY

Introduction

Any measurement students make is only an approximation of the “true” value of the measured property.

• Accuracy is the difference between the measured value of a property and its true value.
• Precision is the range of a repeated set of measurements of a property.

If students make repeated measurements of a single property, and they agree well, the average of the measure-
ments is said to be highly precise. If repeated measurements scatter widely, the average of the measurements is
said to be imprecise.

The accuracy obtained with a thermometer or a graduated cylinder might be far less than it seems just from read-
ing of the scale. If the scale was marked incorrectly (miscalibrated), it does not matter how carefully a student
measures; there will be a systematic uncertainty (often called systematic error). Systematic uncertainty has a
definite cause and causes the results of a series of measurements to be all high or all low. However, even with a
well-calibrated scale, repeating any measurement many times will obtain a range of values; this range is called
random uncertainty (often called random error). Random uncertainty affects the precision of the measurement
by causing the data to be scattered around a mean value. Random uncertainty is caused by many uncontrollable
variables that are part of every measurement. Systematic uncertainty combined with random uncertainty equals
experimental uncertainty. Both individual measurements and final results are subject to experimental uncer-
tainty. Uncertainties in final results are often called experimental error.

Experimental uncertainty is a concern of every chemist. Minimizing experimental uncertainty requires using
available equipment and apparatus to the limit of its performance. Anyone who makes a measurement and
reports a value has a responsibility to specify the uncertainty of that value. Uncertainty is controlled by the nature
of the measuring device and the care with which it is used. When a chemist reports a result, they can use one
of two methods to specify its uncertainty. The two methods are significant figures and standard deviations.
Both significant figures and standard deviations will be introduced in this experiment.

The term, experimental uncertainty, indicates whether a measurement or calculated experimental result is “good”
or “bad.” Good measurements and results have a low experimental uncertainty; bad measurements have a high
experimental uncertainty. Anyone who reports a value has a responsibility to specify the uncertainty of that value
and thereby advertise the quality of the value.

In practice, the main uncertainty of an experimental result for a single measurement stems from the limitations
of the used measuring device or devices. Regardless of its design and construction, every measuring instrument
gives uncertain results. Generally speaking, well-made, high-quality instruments provide relatively more certain

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 1A.1
Department of Chemistry.
 ACCURACY, PRECISION, AND UNCERTAINTY

results than poorly made, low-quality ones.

Significant figures show uncertainty according to standard, conventional rules. Generally speaking, digits that
have been measured are significant: zeros that have not been measured are not significant. Standard deviation
is a statistically based estimate of uncertainty that can be interpreted in terms of a statistical frequency (chance)
that the best possible measured value will lie between specified limits.

SIGNIFICANT FIGURES

Significant figures are assigned according to widely accepted, but not unique, rules. In the absence of other
information, the uncertainty of a reported value may be estimated as ±1 in the rightmost significant digit. When
measured values are combined (added, subtracted, multiplied, or divided), the uncertainty of the result depends
on the uncertainty of each of the individual measurements and how they are arithmetically combined. Because
an experimental result is almost never just a single measurement, it is necessary to know the rules for combining
the uncertainty of the separate measurements to obtain an estimate of the uncertainty of the final, reported value.

The least significant digit in the value of a single measurement will normally be the digit obtained by judging
the measurement to one-tenth of the smallest scale division of the measuring device. Thus, if a thermometer is
marked in degrees, a temperature measured with it would normally be reported to the nearest one-tenth degree.
The actual number of significant figures to be reported depends on the value of the temperature and the mea-
surement scale. For example, on the Celsius scale, 25.6 °C has three significant figures, 9.8 °C has two, and 0.3
°C has one. Converted to the Kelvin scale (K = °C + 273.15), each of these would be reported to four significant
figures: 298.8 K, 283.0 K, and 273.5 K.

RULES FOR SIGNIFICANT FIGURES

1. Whole number conversion factors and certain defined quantities are exact and have an infinite number
of significant figures. The atomic number of boron is exactly 5; there are exactly 1000 milligrams in a
gram, and exactly 4.184 joules per calorie. In each of these, as many trailing zeros as desired may be
added behind the decimal point.
2. Any non-zero digit is significant. For example, 1543 has four significant digits; 137.33 has five significant
digits.
3. Zeros that lie between non-zero digits are significant. Thus in 8507 J, since the 7 is significant (rule 2)
the zero must also be significant. Likewise, all zeros in each of the following numbers are significant:
.707, 909.08, and 40.7.
4. Place-holding zeros on the left of the first non-zero digit are not significant; neither is the leading zero
in a number less than one. Thus, 0.222 has three significant digits and 0.004678 has four significant
digits.
5. Trailing zeros following a decimal point are significant. The number 58.70 amu has four significant

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 1A.2
Department of Chemistry.
 ACCURACY, PRECISION, AND UNCERTAINTY

digits; 0.30000 L has five significant digits—the 3 and the four trailing zeros. In 0.0001900 g there are
four significant digits: the 1, 9, and the two trailing zeros.
6. Trailing zeros in a number without a decimal point are presumed to be placeholders and not significant.
Thus, 2380 has three significant digits, 1500 has two significant digits, and 800 has only one significant
digit. To specify 800 to two significant figures requires that it be written in exponential notation as
8.0 × 102. To specify 800 to three significant figures one may write it as 8.00 × 102, or write it as 800,
alternatively.

COMBINING UNCERTAINTIES USING SIGNIFICANT FIGURES

When numbers from different measurements are combined using arithmetic operations, specific rules must be
followed to obtain the correct number of significant figures in the result. The logic of these rules for handling
significant figures derives from the fact that no arithmetic operation can conceivably improve (lower) the uncer-
tainty of any measurement.

The following statement summarizes uncertainty estimates of the results of addition and subtraction using the
rules of significant figures:

As a result of addition or subtraction, the answer has the same number of decimal places as there are in the
measurement with the fewest decimal places.

Example 1A.1

Add the following numbers, rounding the answer to the correct number of significant figures:

95.4

58.54

110.5

264.4

The final answer is 264.4. When rounding, a common rule is as follows: 0, 1, 2, 3, 4 round down,
and 5, 6, 7, 8, 9 round up. In this example, the figure 4 in the result comes from rounding down
a non-significant 4.

The following statement summarizes uncertainty estimates of the results of multiplication and division using the
rules of significant figures:

The uncertainty of the result of multiplication or division is estimated by its number of significant figures; the
number of significant digits in the result is the same as that in the multiplicand or divisor or dividend with the

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 1A.3
Department of Chemistry.
 ACCURACY, PRECISION, AND UNCERTAINTY

least number of significant digits.

Example 1A.2

How many significant figures are in the correct answer for the following multiplication?

2.8770 × 3.4 × 0.01224 = 0.12

Significant figures: 5 2 4 2

The measurement with the fewest significant figures, 3.4 has two significant figures. Thus, the
final answer, 0.12, has only two significant figures.

STANDARD DEVIATION

The standard deviation of a value is the ± that follows it. The standard deviation of a reported value is a math-
ematical expression of the value’s uncertainty. There is a high probability that the “true” value of a measurement
lies within the specified ± range. For a series of 𝑁 repeated measurements 𝑥1 , 𝑥2 , 𝑥2 ... 𝑥n the average value is 𝑥av
(Equation 1A.1).
𝑥1 + 𝑥2 + 𝑥3 + ... + 𝑥n
𝑥av = (Equation 1A.1)
𝑁

The deviation of the 𝑖-ith value from the average is 𝑥𝑖 –𝑥av .

The estimated standard deviation (𝑆) of the average value is given by Equation 1A.2:

𝑖=𝑛
∑ (𝑥𝑖 –𝑥av )
𝑆 = √ 𝑖=1 (Equation 1A.2)
𝑁−1

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 1A.4
Department of Chemistry.
 ACCURACY, PRECISION, AND UNCERTAINTY

Example 1A.3

Four (N = 4) repeated measurements of a mass are 1.34, 1.23, 1.28, and 1.31 g. Calculate the
average mass to be reported and the estimated standard deviation (S) of the average to be reported.
Start by calculating 𝑥av :

𝑥av = (1.34 + 1.23 + 1.28 + 1.31)/4 = 5.16/4 = 1.29 g

Next, calculate the deviation (𝑥𝑖 –𝑥av ) for each value and square it.

Measurement (𝑖) Value (𝑥𝑖 ) Deviation ((𝑥𝑖 –𝑥av )) Square Deviation ((𝑥𝑖 –𝑥av )2 )
1 1.34 +0.05 0.0025
2 1.23 -0.06 0.0036
3 1.28 -0.01 0.0001
4 1.31 +0.02 0.0004
sum= 0.066

Finally, calculate the standard deviation and give the reported value:

0.0066
𝑆= = 0.047
√ (4 − 1)

Reported value = 1.29 ± 0.05(𝑔).

The statistical interpretation of the standard deviation is that for a large set of repeated measurements of a single
value: 68% will lie within ±1 standard deviation 95% will lie within ±2 standard deviations 99.7% will lie within
±3 standard deviations The standard deviation of the result of an addition or subtraction is given by the following
rule: The standard deviation of the result (𝑆r ) of addition or subtraction is the square root of the sum of the squares
of the standard deviations of the components (𝑆a and 𝑆b ).

𝑆r = √𝑠2a + 𝑠2b (Equation 1A.3)

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 1A.5
Department of Chemistry.
 ACCURACY, PRECISION, AND UNCERTAINTY

Example 1A.4

Calculate the result and estimated standard deviation of (2.3 ± 0.2) + (5.7 ± 0.3).

(2.3 ± 0.2) + (5.7 ± 0.3) = 8.0 ± √0.022 + 0.32

The reported value is 8.0 ± 0.4.

The standard deviation of the result of a multiplication or division is given by the following rule: The standard
deviation of the result (𝑅 ± 𝑆r )) of a multiplication or division of 𝐴 ± 𝑆a by 𝐵 ± 𝑆b is obtained using the formula:

𝑆r 2 𝑆 2 𝑆 2
( ) = ( a) + ( b) (Equation 1A.4)
𝑅 𝐴 𝐵

Example 1A.5

Calculate the result and estimated standard deviation of 3.67 ± 0.02 × 4.50 ± 0.04.
Solve for 𝑆r using Equation 1A.4:

𝑆r 2 0.02
2
0.04
2
( ) =( ) +( )
16.5 3.67 4.50
𝑆r = 0.17

Therefore, the reported value is 16.5 ± 0.2.

Laboratory Manual Prepared by Catalyst Education, LLC for Virginia Polytechnic Institute and State University 1A.6
Department of Chemistry.