General Introduction

Quantitative Chemical • Some laboratory errors are more obvious than others, but
Analysis there is error associated with every measurement.

Seventh Edition • There is no way to measure the “true value” of anything.

The best we can do in a chemical analysis is to carefully
apply a technique that experience tells us is reliable.
Chapter 3 • Repetition of one method of measurement several times
Experimental Error tells us the precision (reproducibility) of the measurement.

• If the results of measuring the same quantity by different

methods agree with each other, then we become confident
that the results are accurate, which means they are near
the “true” value.

General Introduction Chapter OUTLINE

• Suppose that you determine the density of a mineral by 3-1 Significant Figures
measuring its mass (4.635 ± 0.002 g) and volume (1.13 ±
0.05 mL). 3-2 Significant Figures in Arithmetic
• Density is mass per unit volume:
4.635 g / 1.13 mL = 4.101 8 g/mL. 3-3 Significant Figures and Graphs

• The uncertainties in measured mass and volume are ± 3-4 Types of Error
0.002 g and ± 0.05 mL, but what is the uncertainty in the
computed density? 3-5 Propagation of Uncertainty
• And how many significant figures should be used for the
density?

• This chapter discusses the propagation of uncertainty in

lab calculations.

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3-1 Significant Figures 3-1 Significant Figures
• The number of significant figures is the minimum number of digits needed to write a • Zeros are significant when they occur (1) in the middle of a number or (2) at the
given value in scientific notation without loss of accuracy. end of a number on the right-hand side of a decimal point.

• The number 142.7 has four significant figures, because it can be written 1.427 x 102.

• If you write 1.427 0 x 102, you imply that you know the value of the digit after 7, • The last significant digit (farthest to the right) in a measured quantity always has some
which is not the case for the number 142.7. associated uncertainty.

• The number 1.427 0 x 102 has five significant figures. • The minimum uncertainty is 1 in the last digit.
• The scale of a Spectronic 20 spectrophotometer is drawn below (Figure 3-1).
• The number 6.302 x 10-6 has four significant figures, because all four digits are
necessary. You could write the same number as 0.000 006 302, which also has just four • The needle in the figure appears to be at an absorbance value of 0.234.
significant figures. The zeros to the left of the 6 are simply holding decimal places.

• The number 92 500 is ambiguous. It could mean any of the following:

• You should write one of the three numbers above, instead of 92 500, to indicate how
many figures are actually known.

3-1 Significant Figures 3-1 Significant Figures

• We say that this number has three significant figures because the numbers 2 and 3 are • When reading the scale of any apparatus, try to estimate to the nearest tenth of a
completely certain and the number 4 is an estimate. division.
• On a 50-mL buret, which is graduated to 0.1 mL, read the level to the nearest 0.01mL.
• The value might be read 0.233 or 0.235 by other people. • For a ruler calibrated in millimeters, estimate distances to the nearest 0.1 mm.
• The percent transmittance is near 58.3.
• Because the transmittance scale is smaller than the absorbance scale at this point, there • There is uncertainty in any measured quantity, even if the measuring instrument has a
is more uncertainty in the last digit of transmittance. digital readout that does not fluctuate.
• A reasonable estimate of uncertainty might be 58.3 ± 0.2.
• There are three significant figures in the number 58.3. • When a digital pH meter indicates a pH of 3.51, there is uncertainty in the digit 1 (and
maybe even in the digit 5).

• By contrast, some numbers are exact—with an infinite number of unwritten

significant digits.

• To calculate the average height of four people, you would divide the sum of heights
(which is a measured quantity with some uncertainty) by the integer 4. There are
exactly 4 people, not 4.000 ± 0.002 people!

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3-2 Significant Figures in Arithmetic 3-2 Significant Figures in Arithmetic
• We now consider how many digits to retain in the answer after you have performed 3.3.1. Addition and Subtraction
arithmetic operations with your data.
• If the numbers being added do not have the same number of significant figures, we are
• Rounding should only be done on the final answer (not intermediate results), to avoid limited by the least certain one.
accumulating round-off errors. • For example, the molecular mass of KrF2 is known only to the second decimal place,
because we only know the atomic mass of Kr to two decimal places:
3.3.1. Addition and Subtraction
• If the numbers to be added or subtracted have equal numbers of digits, the answer The number 121.796 806 4 should be rounded
goes to the same decimal place as in any of the individual numbers: to 121.80 as the final answer.

• When rounding off, look at all the digits beyond the last place desired.
• The number of significant figures in the answer may exceed or be less than that in the • In the preceding example, the digits 6 806 4 lie beyond the last significant decimal
original data. place.
• Because this number is more than halfway to the next higher digit, we round the 9 up
to 10 (i.e., we round up to 121.80 instead of down to 121.79).

• If the insignificant figures were less than halfway, we would round down. For
example, 121.794 8 is correctly rounded to 121.79.

3-2 Significant Figures in Arithmetic 3-2 Significant Figures in Arithmetic

3.3.1. Addition and Subtraction 3.3.2. Multiplication and Division
• In the special case where the number is exactly halfway, round to the nearest even • In multiplication and division, we are normally limited to the number of digits
digit. Thus, 43.550 00 is rounded to 43.6, if we can only have three significant figures. contained in the number with the fewest significant figures:

• If we are retaining only three figures, 1.425 x 10-9 becomes 1.42 x 10-9. The number
1.425 01 x 10-9 would become 1.43 x 10-9, because 501 is more than halfway to the next
digit.
• The rationale for rounding to an even digit is to avoid systematically increasing or
decreasing results through successive round-off errors. Half the round-offs will be up The power of 10 has no influence on the number of figures that should be retained.
and half down.
• In adding or subtracting numbers expressed in scientific notation, all numbers should 3.3.3 Logarithms and Antilogarithms
first be expressed with the same exponent:
The base 10 logarithm of n is the number a, whose value is such that n = 10a.

For example, 2 is the logarithm of 100 because 100 = 102. The logarithm of 0.001 is
3 because 0.001 = 10-3. To find the logarithm of a number with your calculator,
• The sum 11.513 07 x 105 is rounded to 11.51 x 105 because the number 9.84 x 105 enter the number and press the log function.
limits us to two decimal places when all numbers are expressed as multiples of 105.

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3-2 Significant Figures in Arithmetic 3-2 Significant Figures in Arithmetic
3.3.3 Logarithms and Antilogarithms 3.3.3 Logarithms and Antilogarithms
In the above equation, the number n is said to be the antilogarithm of a. To see that the third decimal place is the last significant place, consider the following
That is, the antilogarithm of 2 is 100 because 102 = 100, and the antilogarithm of 3 is results:
0.001 because 10-3 = 0.001.
Your calculator has either a 10x key or an antilog key. To find the antilogarithm of a
number, enter it in your calculator and press 10x (or antilog).

The numbers in parentheses are the results prior to rounding to three figures. Changing
A logarithm is composed of a characteristic and a mantissa. The characteristic is
the exponent in the third decimal place changes the answer in the third place of 339.
the integer part and the mantissa is the decimal part:
In converting a logarithm to its antilogarithm, the number of significant figures in
the antilogarithm should equal the number of digits in the mantissa. Thus,

The number 339 can be written 3.39 x 102. The number of digits in the mantissa of log Here are several examples showing the proper use of significant figures:
339 should equal the number of significant figures in 339. The logarithm of 339 is
properly expressed as 2.530.

The characteristic, 2, corresponds to the exponent in 3.39 x 102.

3-2 Significant Figures in Arithmetic 3-3 Significant Figures and Graphs

3.3.3 Logarithms and Antilogarithms • When drawing a graph on a computer, consider whether the graph is meant to display
qualitative behavior of the data (Figure 3-2) or precise values.

• If someone will use the graph (such as Figure 3-3) to read points, it should at least
have tic marks on both sides of the horizontal and vertical scales.
Better still is a fine grid superimposed on the graph.

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3-3 Significant Figures and Graphs 3-4 Types of Error
• Rulings on a graph should be compatible with the number of significant figures of • Every measurement has some uncertainty, which is called experimental error.
the coordinates.
• The graph in Figure 3-4a has reasonable rulings for the points (0.53, 0.63) and (1.08, • Conclusions can be expressed with a high or a low degree of confidence, but never
1.47). Rulings correspond to every 0.1 unit, so you can estimate the position of the 0.01 with complete certainty.
unit.
• The graph in Figure 3-4b is the same size but is not ruled fine enough to estimate the • Experimental error is classified as either systematic or random.
position of the 0.01 unit. Plan the axes of a graph so that data are spread over as much
of the sheet of paper as possible. 3.4.1 Systematic Error
• Systematic error, also called determinate error, arises from a flaw (defect) in
equipment or the design of an experiment.

Figure 3-4 Graphs demonstrating • If you conduct the experiment again in exactly the same manner, the error is
choice of rulings in relation to significant
reproducible.
figures in the data. Graph (b) does not
have divisions fine enough to allow you
to plot data that are accurate to the • In principle, systematic error can be discovered and corrected, although this may not
hundredths place. be easy.

3-4 Types of Error 3-4 Types of Error

3.4.1 Systematic Error 3.4.1 Systematic Error
• For example, using a pH meter that has been standardized incorrectly produces • To do this, deliver distilled
a systematic error. water from the buret into a
flask and weigh it.
• Suppose you think that the pH of the buffer used to standardize the meter is 7.00, but
it is really 7.08. Then all your pH readings will be 0.08 pH unit too low. • Determine the volume of
water from its mass by using
• When you read a pH of 5.60, the actual pH of the sample is 5.68. Table 2-7.

• This systematic error could be discovered by using a second buffer of known pH to • Figure 3-3 tells us to apply a
test the meter. correction factor of - 0.03 mL
to the measured value of
• Another systematic error arises when you use an uncalibrated buret. The 29.43 mL.
manufacturer’s tolerance for a Class A 50-mL buret is 0.05 mL. When you think you
have delivered 29.43 mL, the real volume could be anywhere from 29.38 to 29.48 mL • The actual volume delivered
and still be within tolerance. is 29.43 - 0.03 = 29.40 mL.
A key feature of systematic error is that it is reproducible. For the buret just discussed, the error is always
• One way to correct for an error of this type is to construct a calibration curve, such as 0.03 mL when the buret reading is 29.43 mL. Systematic error may always be positive in some regions and
that in Figure 3-3, by the procedure on page 38. always negative in others. With care and cleverness, you can detect and correct a systematic error.

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3-4 Types of Error 3-4 Types of Error
Ways to detect Systematic Error: 3.4.2 Random Error
1. Analyze samples of known composition, such as a Standard Reference Material. • Random error, also called indeterminate error, arises from the effects of
Your method should reproduce the known answer. uncontrolled (and maybe uncontrollable) variables in the measurement.

• Random error has an equal chance of being positive or negative. It is always present
2. Analyze “blank” samples containing none of the analyte being sought. If you observe and cannot be corrected.
a nonzero result, your method responds to more than you intend. Section 29-3 discusses
different kinds of blanks (Quality Assessment). • There is random error associated with reading a scale. Different people reading the
scale in Figure 3-1 report a range of values representing their subjective interpolation
between the markings.
3. Use different analytical methods to measure the same quantity. If the results do not
agree, there is error in one (or more) of the methods.

• One person reading the same instrument several times might report several different
4. Round robin experiment: Assign different people in several laboratories to analyze readings.
identical samples by the same or different methods. Disagreement beyond the estimated
random error is systematic error. • Another indeterminate error results from random electrical noise in an instrument.
Positive and negative fluctuations occur with approximately equal frequency and cannot
be completely eliminated.

3-4 Types of Error 3-4 Types of Error

3.4.3 Precision and Accuracy 3.4.3 Precision and Accuracy
nPnA AnP A&P PnA
Precision describes the reproducibility of a result. If you measure a
quantity several times and the values agree closely with one another, • A measurement might be reproducible, but wrong.
your measurement is precise.
• For example, if you made a mistake while preparing a solution for a titration, the
solution would not have the desired concentration.
If the values vary widely, your measurement is not very precise.
• You might then do a series of reproducible titrations but report an incorrect result
because the concentration of the titrating solution was not what you intended.
Accuracy describes how close a measured value is to the “true” value. If
• In this case, the precision is good but the accuracy is poor (PnA).
a known standard is available (such as a Standard Reference Material,
described in Box 3-1), accuracy is how close your value is to the known • Conversely, it is possible to make poorly reproducible measurements clustered around
value. the correct value.

• In this case, the precision is poor but the accuracy is good (AnP).

• An ideal procedure is both precise and accurate (A&P).

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3-4 Types of Error 3-4 Types of Error
3.4.4 Absolute and Relative Uncertainty
3.4.3 Precision and Accuracy
Absolute Uncertainty expresses the margin of uncertainty associated with a
nPnA AnP A&P PnA
measurement.
• Accuracy is defined as nearness to the “true” value.
• If the estimated uncertainty in reading a calibrated buret is ± 0.02 mL, we say
that ± 0.02 mL is the absolute uncertainty associated with the reading.
• The word true is in quotes because somebody must measure the “true” value, and
there is error associated with every measurement.
Relative Uncertainty compares the size of the absolute uncertainty with the size of its
associated measurement. The relative uncertainty of a buret reading of 12.35 ± 0.02 mL
• The “true” value is best obtained by an experienced person using a well-tested
is a dimensionless quotient:
procedure.

• It is desirable to test the result by using different procedures, because, even though
each method might be precise, systematic error could lead to poor agreement between
methods.

• Good agreement among several methods affords us confidence, but never proof, that
results are accurate.

3-4 Types of Error 3-5 Propagation of Uncertainty

3.4.4 Absolute and Relative Uncertainty Introduction

If the absolute uncertainty in reading a buret is constant at 0.02 mL, the percent relative We can usually estimate or measure the random error associated with a measurement,
uncertainty is 0.2% for a volume of 10 mL and 0.1% for a volume of 20 mL. such as the length of an object or the temperature of a solution.
(0.02/10) = 0.002 = 0.2/100 = 0.2 % or (0.02/20) = 0.001 = 0.1/100 = 0.1 %
The uncertainty might be based on how well we can read an instrument or on our
If you use a 50-mL buret, design your titration to require 20–40 mL of reagent to experience with a particular method.
produce a small relative uncertainty of 0.1–0.05%.
If possible, uncertainty is expressed as the standard deviation or as a confidence
interval; these parameters are based on a series of replicate measurements.
In a gravimetric analysis, plan to have enough precipitate for a low relative uncertainty.
If weighing precision is ± 0.3 mg, a 100-mg precipitate has a relative weighing error of The following discussion applies only to random error. We assume that systematic error
0.3% and a 300-mg precipitate has an uncertainty of 0.1%. has been detected and corrected.

In most experiments, it is necessary to perform arithmetic operations on several

numbers, each of which has an associated random error.

The most likely uncertainty in the result is not simply the sum of the individual errors,
because some of these are likely to be positive and some negative. We expect some
cancellation of errors.

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3-5 Propagation of Uncertainty 3-5 Propagation of Uncertainty
3.5.1. Addition and subtraction 3.5.1. Addition and Subtraction
Suppose you wish to perform the following arithmetic, in which the experimental The absolute uncertainty e4 is 0.04, and we can write the answer as 3.06 ± 0.04.
uncertainties, designated e1, e2, and e3, are given in parentheses.
Although there is only one significant figure in the uncertainty, we wrote it initially as
0.041, with the first insignificant figure subscripted.
Equation 3-4
We retain one or more insignificant figures to avoid introducing round-off errors into
later calculations through the number 0.041.
The arithmetic answer is 3.06. But what is the uncertainty associated with this result? The insignificant figure was subscripted to remind us where the last significant figure
should be at the conclusion of the calculations.
For addition and subtraction, the uncertainty in the answer is obtained from the
absolute uncertainties of the individual terms as follows: To find the percent relative uncertainty in the sum of Equation 3-4, we write

The uncertainty, 0.041, is 1.3% of the result, 3.06. The subscript 3 in 1.3% is not
significant. It is sensible to drop the insignificant figures now and express the final
result as

3-5 Propagation of Uncertainty

3.5.2. Multiplication and Division
For multiplication and division, first convert all uncertainties to percent relative
uncertainties. Then calculate the error of the product or quotient as follows:

For example, consider the following operations: 0.03/1.76=0.017045

First convert absolute uncertainties to percent relative uncertainties.

For addition and subtraction, use absolute uncertainty. Relative

uncertainty can be found at the end of the calculation. For multiplication and division, use percent relative uncertainty.
uncertainty. Absolute uncertainty can be
found at the end of the calculation.

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3-5 Propagation of Uncertainty 3-5 Propagation of Uncertainty
3.5.2. Multiplication and Division 3.5.3. Mixed Operations
Then find the percent relative uncertainty of the answer by using Equation 3-6. Now consider a computation containing subtraction and division:

The answer is 5.64 ± (4.0%).

To convert relative uncertainty to absolute uncertainty, find 4.0% of the answer. First work out the difference in the numerator, using absolute uncertainties. Thus,

The answer is 5.64 ± (0.23). Finally, drop the insignificant digits.

Then convert to percent relative uncertainties. Thus,

The denominator of the original problem,

0.59, limits the answer to two digits.

Advice : Retain one or more extra insignificant figures until you have finished
finished your entire The percent relative uncertainty is 3.3%, so the absolute uncertainty is
calculation. Then round to the correct number of digits. 0.033 x 0.6190 = 0.020. The final answer can be written as
When storing intermediate results in a calculator, keep all digits
digits without rounding.

3-5 Propagation of Uncertainty 3-5 Propagation of Uncertainty

3.5.3. Mixed Operations 3.5.4. The Real Rule for Significant Figures
The percent relative uncertainty is 3.3%, so the absolute uncertainty is The first uncertain figure of the answer is the last significant figure. For example, in the
0.033 x 0.6190 = 0.020. quotient

The final answer can be written as

the uncertainty (± 0.000 2) occurs in the fourth decimal place. Therefore, the answer is
properly expressed with three significant figures, even though the original data have
four figures. The first uncertain figure of the answer is the last significant figure.
Because the uncertainty begins in the 0.01 decimal place, it is reasonable to round the
result to the 0.01 decimal place: The quotient

is expressed with four significant figures because the uncertainty occurs in the fourth
place.

The result of a calculation ought to be written in a manner consistent with The quotient
its uncertainty.
is expressed with four figures even though the dividend and divisor each have three
figures.

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3-5 Propagation of Uncertainty 3-5 Propagation of Uncertainty
3.5.5. Exponents and Logarithms 3.5.5. Exponents and Logarithms
For the function y = xa ,the percent relative uncertainty in y(%ey) is equal to a times the The natural logarithm (ln) of x is the number y, whose value is such that x = ey,
percent relative uncertainty in x(%ex): where e ( 2.718 28 . . . ) is called the base of the natural logarithm. The absolute
uncertainty in y is equal to the relative uncertainty in x.

Now consider y = antilog x, which is the same as saying y = 10x. In this case, the
relative uncertainty in y is proportional to the absolute uncertainty in x.

If y is the base 10 logarithm of x, then the absolute uncertainty in y (ey) is proportional

to the relative uncertainty in x times (ex/x):
If y = ex, the relative uncertainty in y equals the absolute uncertainty in x.
Equation 3-8

You should not work with percent relative uncertainty [100 (ex /x)] in calculations
with logs and antilogs, because one side of Equation 3-8 has relative uncertainty and Table 3-1 summarizes rules for propagation of uncertainty. You need not memorize the
the other has absolute uncertainty. rules for exponents, logs, and antilogs, but you should be able to use them.

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Table 3-1 summarizes rules for propagation of uncertainty. You need not memorize the
rules for exponents, logs, and antilogs, but you should be able to use them.

3-5 Propagation of Uncertainty 3-5 Propagation of Uncertainty

O = 15.999 4 ± 0.0003
3.5.6. Uncertainty in Molecular Mass 3.5.6. Uncertainty in Molecular Mass
What is the uncertainty in the molecular mass of O2? On the inside cover of this book, What is the true mass of a mole of oxygen ? Every mole of oxygen has the same mass ?
we find that the atomic mass of oxygen is 15.999 4 ± 0.000 3 g/mol. Without thinking,
I always used Equation 3-5 for the uncertainty of a sum: The uncertainty of 0.000 3 means that the true mass is in the range 15.999 1 to 15.999 7.

If the true mass were 15.999 7, then the mass of O2 is 2 x 15.999 7 = 31.999 4 g/mol.
If the true mass is 15.999 1, then the mass of O2 is 2 x 15.999 1 = 31.998 2 g/mol.
(3-5)
The mass of O2 is somewhere in the range 31.998 8 ± 0.000 6. The uncertainty is not

Equation is appropriate when the errors in each term are random.

random One might be
positive and one might be negative. In most cases, the uncertainty in the sum is less
than 0.000 3 + 0.000 3 = 0.000 6. Let’s apply this reasoning to find the molecular mass of C2H4:

(3-5)

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3-5 Propagation of Uncertainty 3-5 Propagation of Uncertainty
3.5.6. Uncertainty in Molecular Mass 3.5.7. Multiple Deliveries from a Pipet

To find the uncertainty in the sum of the masses of 2C + 4H, we do use Equation 3-5 A 25-mL Class A volumetric pipet is certified by the manufacturer to deliver 25.00 ±
because the uncertainties in the masses of C and H are independent of each other. 0.03 mL.

One might be positive and one might be negative. The volume delivered by a given pipet is reproducible, but can be anywhere in the
range 24.97 to 25.03 mL.
So the molecular mass of C2H4 is
The difference between 25.00 mL and the actual volume delivered by a particular pipet
is a systematic error. It is always the same, within a small random error.

You could calibrate a pipet by weighing the water it delivers, as in Section 2-9.

Calibration eliminates systematic error, because we would know that the pipet always
delivers, say, 24.991 ± 0.006 mL.

The remaining uncertainty (± 0.006 mL) is random error.

3-5 Propagation of Uncertainty

3.5.7. Multiple Deliveries from a Pipet

If you use an uncalibrated 25-mL Class A volumetric pipet four times to deliver a total
of 100 mL, what is the uncertainty in 100 mL?

Because the uncertainty is a systematic error, the uncertainty in four pipet volumes is
like the uncertainty in the mass of 4 moles of oxygen:

The uncertainty is ± 4 × 0.03 = ± 0.12 mL, not

Calibration improves accuracy. Suppose that a calibrated pipet delivers a mean volume
of 24.991 mL with a standard deviation (a random variation) of ± 0.006 mL.

If you deliver four aliquots from this pipet, the volume delivered is 4 × 24.991 = 99.964
mL and the uncertainty is

By calibrating the pipet, we reduce the uncertainty from ± 0.12 mL to ± 0.012 mL.

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