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# TOPIC 11

## 11.1 uncertainties in measurement

Uncertainty occurs due to the limitations of the apparatus itself and the taking of readings from
scientific apparatus. For example during a titration there are generally four separate pieces of
apparatus, each of which contributes to the uncertainty.

The error is the difference between the result obtained and the generally accepted 'correct'
result found in the data book or other literature. If the 'correct' result is available it should be
recorded and the percentage error calculated and commented upon in your conclusion. Without
the 'correct ' value no useful comment on the error can be made.

## Qualitative vs. Quantitative Data

o Qualitative = color, texture, general heat given off or absorbed
o Quantitative = specific numerical values such as change in temp, mass, absorbance that
can be measured using instrumentation.

## The idea of uncertainty in science is inherent in measurement regardless of number of decimal

places. Uncertainties are caused by limitations of the measuring apparatus and other
uncontrollable factors that are inevitable in any experiment.
o Uncertainties can be minimized by repeated trials, but can never
be eliminated.
o Random uncertainty can also be minimized by a thoughtful design
for an experiment.
 An experiment using 0.05 g of Mg with a balance
that reads to the 1/100th place gives an uncertainty
of ±0.01. This uncertainty represents( 0.01/0.05) x
100 = 20% of the mass! This would not be a good
choice for the mass of the magnesium! However, if
you increase the mass of the Mg to 1.00 grams, then
your uncertainty is greatly diminishes and is now
(0.01/1.00) x 100 = 1%. A far better percent
uncertainty that 20%! PLANNING MATTERS.
o Uncertainty is represented by a ± amount after the
measurement such as 0.27 ± 0.01 grams. The ± 0.01 is the
uncertainty in the measurement and means that the 0.27
could be + 0.01 grams more or – 0.01 grams less.

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That is referred to as the range and the acceptable values would then be 0.26 to
0.28 g.

Estimating Uncertainties
Estimating (random) uncertainties is somewhat different based on the type of measurement
tool you are using. For
o Analogue apparatus includes beakers, graduated cylinders, burets, alcohol
thermometers. The uncertainty for analogy measurements is taken to be ½ of the
smallest division. So a graduated cylinder whose smallest division is 1 mL will have an
uncertainty of ± 0.5 mL. The volume would be represented as 25.0 ± 0.5 mL. Notice how
both the volume recorded and the uncertainty have the same number of decimal
places!!! Very important!
o Digital Instruments include electronic balances and computer based technology that
determines values for you. The uncertainties are given below

## Balance reads to the… Uncertainty

0.1 g ±0.1 g
0.01 g ±0.01 g
0.001 g ±0.001 g

o Humans bring limitation and thus uncertainty to every experiment they do. These fall
under the category of random errors. For example, if you were doing an experiment that
required you to measure the time taken for a reaction mixture to change color in order
to determine the rate of the reaction you would probably use a stopwatch. You would
have to see measure your reaction time and then decide on an acceptable uncertainty. A
suitable uncertainty for this type of experiment might be ± 0.5 sec or ± 1 sec.

## Precision & Accuracy

Let’s say you’re a really great dart player. Nobody can beat
you. After throwing 10 darts, the dartboard for you looks like
the board below. All ten darts are clumped in the middle of
the board showing your significant dart throwing abilities. In
terms of two important terms: precision and accuracy. Your

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accuracy is excellent as well as your precision. Let’s take a look at these two terms in more
detail.

As you continued your evening of winning at darts to all who challenged you, it became
apparent to your very analytical mind that four different patterns of darts board emerged after a
the darter (is that a word?) finished her or her round of ten. They are shown below. You can see
that both terms, precise and accurate are included.

## Accurate Not accurate (systematic

error
Precise

1. 2.
Not precise
(reproducibility error)

3. 4.

Precision is defined in science as the reproducibility of results. Do you keep getting the
same value over and over again regardless of how you conduct your experiment? If so, then we
can say you have a high degree of precision. All of your measurements are very close together.
When this is the case, precision is high. Precision does not mean that your results are actually
“good” results. Precision only means that you are consistent for those particular results. Notice
that dartboards 1 and 2 show all of the darts bunched together in one location.

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The table below shows temperatures taken for the 6 readings. The values are very close
together and the average is also close to each of the individual measurements. This collection of
data represents, once again, high precision.

## Precision of a Single Measurement

We can talk about the precision of a
single measurement, which is dependent
only on the number of significant figures.
For example, a temperature reading of
21.33 ± 0.01OC is more precise than a
temperature reading of 21.2 ± 0.1 OC

## Accuracy, on the other hand,

refers to how close a
measurement is to the actual value of a particular quantity. You may remember back to T1
chemistry when you determined the density of pennies. I asked you to compare your
experimental result for the density of copper with the literature value. If your experimental
value (the average of al your trials) was close to the actual value for the density of copper (8.96
g/mL), thenyour accuracy was very high.

## If you look back to the dartboard above, all 4 possibilities in

terms of precision and accuracy are shown. Random errors
1: High precision and high accurancy A random error, is an error which affects a reading
2: High precision and low accuracy at random.
Sources of random errors include:
3: Low precision and fairly high accurancy
4: Neither precision nor accuracy.  The observer being less than perfect

## Random errors  The readability of the equipment

The random error in experimental results is due to the
inabilitiy of experimenter’s to consistently read an analogue  External effects on the observed item

Systematic errors
A systematic error, is an error which occurs at each
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Sources of systematic errors include:
instrument (graduated cylinder or beaker) in consistently the same way. This will result in a
spread of results, even in the most carefully designed of experiments. Due to the random
nature of these errors, there is an equal chance that they will be above or below the ‘true’
value. To minimize such errors, it is good practice to take many readings and find the mean,
even in the simplest of experiments. Because it is impossible to know the ‘true’ value, the best
estimate is the mean of repeat readings.

Systematic Errors
Systematic errors arise in an experiment as a result of the apparatus used or the procedure
followed. Systematic errors result in a loss of accuracy. A systematic error cannot be diminished
by repeated trials. For example, you use an electronic balance to take the masses of the various
substances you are using in your experiment. It turns out the balance is not properly calibrated.
Your measurement of 23.25 grams is actually 24.25 g. No matter how many times you repeat
taking the mass of this object, it will be 1.00 g heavier than it should be.

## Systematic errors can be identified by comparing an experimental value to an accepted

literature value. In terms of the density experiment you did 2 years ago in 9 th grade, the actual
value for the density of copper is 8.96 ± 0.5 g/ml and let’s say your experimental value is 7.96 ±
0.5 g/ml. Since your experimental value is not particularly close to your actual (theoretical
value), one could propose systematic errors may be one of reasons. We can use percent error to
compare an experimental value with the accepted literature value:
ABSOLUTE VALUE
|value| means you take the
% E = percent error = |experimental value – literature value| x 100 positive value
accepted value

Recall that we take the absolute value of the difference between the
experimental and literature values. Percent error is always given as a positive value.
%E>%U
If % error > % uncertainty,
For the above density example, the percent error would be:
systematic errors need to be
considered. |7.96 – 8.96| x 100 = |-1.00| = 1.00 x 100 = 11.1%
8.96 8.96 8.96

We can calculate a value called the percent uncertainty, which is due to random error.

## percent uncertainty = uncertainty of the measurement x 100 = 0.5 x 100 = 6%

experimental value 7.96

You may need to compare the percent error and the percent uncertainty when you are
completing your research project at the beginning of your T4 year. If the percent error is greater
than the percent uncertainty, we can reasonably assume the experiment involves some
systematic errors. For any density experiment where water displacement is involved, one
primary systematic error is the unreliability of the graduated cylinder. Also, the pennies were

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not completely copper metal and thus another error. Remember, systematic errors can be
reduced by changing the way in which the experiment is carried out in this case. You could
actually find the volume of the penny by using a ruler to measure the
height of the penny and the diameter and then use the volume of a % E< % U
cube equation to determine the volume. This would give a more If % error < % uncertainty, you
precise volume measurement that could be used with the mass of the have designed a very good
pennies to determine the density. procedure and your
experiment has worked well as
a way of obtaining a particular
When the percent error < percent uncertainty, then the experiment value.
has worked well as a way of obtaining a value for this particular
quantity.

The table below summarizes the relationship between percent error and percent uncertainty
and how one’s experiment may be impacted.

Percent error << percent random uncertainty Experiment has worked well as a way of
obtaining a value for a particular quantity when
compare to an accepted literature value.
Percent error < percent uncertainty Experiment should be further refined by using
more precise measuring apparatus and/or taking
Percent error > percent uncertainty Systemic errors exist and these must be
eliminated as far as is possible.

## Self Test 11.1a

Do Problems 1,2

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11.2 Significant figures
In order to do calculations using measurements you have collected, you first have to be able to
determine the number of significant figures in any measurement. In science, we talk about “the
number of significant figures” in a measurement and counting them correctly means your

## Counting the number of Significant Figures in a

Measurement
Two situations when zeros Definition Example # of sig figs
are NOT significant
RULE 1 Numbers Trailing zeros are not significant and 50 km 1
greater than 1. are therefore not counted. A trailing 500 km 1
zero appears at the end of a 25,000 m 2
measurement. Notice there are no 100 mL 1
decimal points.
RULE 2 Numbers less Sandwiched zeros are not 0.0056 dg 2
than 1 significant. A sandwiched zeros 0.005 pm 1
appears between the decimal point 0.000124 ng 3
and the first non-zero digit 0.0100 L 3
1) All non-zero digits are significant. 1,2,3,4,5,6,7,8,9
2) Zeros are sometimes significant and sometimes not so they are the trickiest.
Remember the two times when zeros ARE NOT significant and all other they are
counted.

## i. For number greater than 1, trailing zeros are not significant

Examples: 50 kg, 1 SF
50,000 km, 1 SF
320 liters 2 SF

ii. For number less than one, zeros that appear between the decimal and
the first digit are not significant
Examples: 0.0025 g 1 SF
0.00160 cm 3 SF
the zeros between the decimal and number 1 are not significant, but the
zero at the end is! I know, tricky.)
0.0065 mm 2 SF

We say that all non-zero digits are significant. They count in terms of expressing the specificity
or precision of a measurement. For example, 12.5 mL has 3 sig figs and 25.55 mL has 4 sig figs.

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This must mean that the measuring tool I am using in the first measurement above is not as
good a measurement device as the second measurement.

## A Measurement and its Uncertainty must Match

Very often we do not include uncertainty in our measurements. In your recent water
crystallization lab, you may recall you were asked for the uncertainty. When you
recorded the mass of your crucible, you also took note of whether it was a balance that
recorded to the 1/10th , 100th, or 1/100th place. For example, a crucible mass of 44.316 g
would, with uncertainty include the uncertainty for the balance. For all electronic
balances, the uncertainty of ±0.01, ±0.01 or ± 0.001 grams depending on the balance
used. Going back to our mass, the complete measurement with uncertainty would be
written as 44.316 ± 0.001 grams. Notice that the measurement value goes to the
1/1000th place. This means that the uncertainty must match the measurement and also
have the same degree of precision. It would not be correct to write a measurement with
the following uncertainty in the following way:
363.2 ± 100 kg. The measurement is too precise for the uncertainty or the uncertainty is
not
Correct measurement and uncertainty Range precise
362.2 ± 0.1 mL 362.1362.3 mL enough
362 ± 5 mL 358  367 mL for the
360 ± 10 mL 350  370 mL
400 ± 100 kg 300  500 kg
measurement. Only you know the measuring device you used. Let’s say the balance you
used was very simple and not precise—a balance you might use at a warehouse that
measured large masses. The correct adjustment for this measurement would be 400 ±
100 kg. Listed below are all the possibilities of how the measurement precision could be
adjusted and the corresponding uncertainty that would need to be used.

## Uncertainty of a Mean (Average) Value

In the table to the right, we have 6 different readings of
volumes. No uncertainty is given. We also see a calculated Reading Volume Deviation from
mean (average). If we want to include the uncertainty with (cm3) the mean
an calculated average value, we can do the following:
1 21.0 0.4
2 21.9 0.5
1. Find the largest deviation from the mean, which is
3 22.1 0.7
represented in column 3. Each of the six measurements were 4 21.2 0.2
subtracted from the mean value of 21.4 cm3 to arrive at the 5 20.7 0.7
deviation (difference) from the mean value. We can see that 6 21.5 0.1
0.7 cm3 is the largest deviation. mean 21.4
value

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2. Multiply this deviation by 2/3. Thus we have 0.7 cm 3 (2/3) = 0.46 cm3. Our measurement are
all to the 1/10th place so we
round 0.46 to 0.5 cm3. Now we can write our mean value for volume with an uncertainty, 21.4
± 0.5 cm3 and be reasonable sure that the range of values will fall 20.9  21.9 cm3.

Do problems 3,4

## How many significant figures do I keep in my answer?

Mathematical Operations How do determine Example Answer
and Significant Figures number of SF.
Adding and Subtracting Least place holder 4.5 g 10.6 g
4.55 g Least place holder is the tenths in the
4.547 g first number
10.597 g
Multiplying and Dividing The measurement will 4.55 g = 0.318 g/mL
have the same number of 14.30 mL Numerator has 3 sig figs and
sig figs. as the denominator has 4 sig figs so the
measurement with the answer will have 3.
least number of SF. 55.82 m = 27.91 m
2 2 is not a measurement so don’t
include in determining number of SF

The above table is a review of how to handle significant figures when you begin calculating
values based on the measurements you obtain from a particular experiment. Adding and
subtracting are handled differently than multiplication/division. You should be able to see that
for add/subtract, the number of sig figs in your calculation is based on the decimal place of the
measurements. If all measurements end in the 1/100th place, but one ends in tne 1/10th place,
when you are determining the percent error of a measurement.

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For example, the literature value for the heat released when 50 mL of 0.1 M NaOH reacts with
50 mL of 0.1 M HCl is -57.3 kJ/mol. The experimental value obtained was recorded as
-55.80 kJ/mol. Recall that percent error is:

## % E = percent error = |experimental value – literature value| x 100

accepted value

The literature value is given to the 1/10th place but the experimental value is given to the
1/100th place. Thus the difference of these two values will be only to the 1/10 th place or 1.5
kJ/mol not 1.50 kJ/mol.

When we multiply or divide, our calculated answer is based on our least significant
measurement. To complete the percent error for the heat released, we take the difference
calculated and divide by our literature value. Thus,
When to Round?
|-57.3-(-55.80)| x 100 = 2.6% In general, when you have a
|-57.3| calculation that involves many
steps, wait until you arrive at your
final answer. Round that value to
1.5 has two sig figs and the literature value has three sig figs, the correct number of significant
therefore we report our answer with two sig figs. figures.

Do problems 1-4

## 1. Determine the number of significant figures in each of the following measurements:

a. 140. 74 mL _____5_______
b. 0.0041 g ______2______
c. 4 aardvarks _____1 _______
d. 450 nm ______2______
e. 3.700 x 1014 pg ______4______
f. 31.000 mg ______5______
g. 1300 nm ______2______
h. 847.050 mg ______5______
i. 2,495 km ______4______
j. 0.00410 µL _______3_____

2. Round each measurement to the number of correct number of significant figures indicated in
parentheses.

## a. 3.741 mg (3 SF) ______3.74mg______

b. 0.0041198 g (2 SF) ______0.0041g_____
c. 81.67 mL (2 SF) ______82mL______

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d. 191,000 km (1 SF) ______200,000km______
e. 150.6142 g (3 SF) _______151g_____
f. 2.0097 x 10-12 pL (4 SF) _______2.001x10^-12pL_____
g. 0.0115 dg (2 SF) _____0.012dg_______
h. 89.69 mL (3 SF) _______89.7mL_____

3. Perform the following calculations and give your answer to the correct number of significant
figures.
a. 18.7644 g – 3.472 g + 0.4101 g = _____15.70g_______
b. 17.441 g/mL ÷ 3 = __5.8137mL_ (3 not a meas; finding average)
c. 14.044 mL + 8.11 mL + 3.4 mL = _____25mL_______
d. 3.41 g – 0.086652 g = ______3.32g______
e. 0.87 mm x 4.061 x 10.4 = _____37mm_______
f. 21.01 m x 2 m ______40m______
g. Calculate the average of the following set of density values (g/cm 3):
18.4, 18.45, 18.54 and 18.7 = _____18.5g/cm3____

## 4. Convert the following values to scientific notation (sci-n) if in standard form(stn). If in

standard form, convert to standard notation.
a) 47,000 kg __________47 x 10^3 kg_______ (sci-n)
b) 0.0008 M HCl _________8 x 10^-4 M HCl________ (sci-n)
c) 675,000,000 m _________675 x 10^6m________ (sci-n)
d) 157,000,000,000,000,000,000,000 pg ________157 x 10^2 1pg_________(sci-n)
e) 0.0000003407 pL _______3.407 x 10^7 pL__________(sci-n)
f) 7.66 x 10–2 mg _________0.0766 mg________ (stn)
e) 7.8 x 105 km_______780,000 km_______(stn)
h) 4.75 x 10–4 cm3 ________0.000475 cm3_______(stn)
f) 6 x 10–3 g _______0.006 g________(stn)
g) 9x 108 km __________900,000,000 km_____________________(stn)
j) 6.022 x 1023 mol _______602,200,000,000,000,000,000,000 mol_____(stn)

## Absolute and Percent Uncertainties

There are two ways to report uncertainty: absolute or percent. The absolute uncertainty has
the same units as the measurement. For example, if I massed an amount of an NaOH on the
electronic balance that reads to the 1/100th place, I would report that value as 21.75 g ± 0.01 g.

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Notice that both the measurement and its corresponding uncertainty (the uncertainty shown
on the back of the electronic balance) are in grams. The absolute uncertainty would be 0.01 g.

The percent uncertainty is exactly what it says: a percent of the actual mass you measure. For
our above mass, we would take the absolute uncertainty (0.01 g) and divide by our mass (21.75
g) and then multiplying by 100.

## % uncertainty = 0.01 g x 100 = 0.05%

21.75 g
We can see that our % uncertainty is very small and that is what we want. We do not want our
error to be such a large percentage of our measurements that we are unable to carry out a
particular experiment with some relative degree of confidence. If our percent uncertainty were
15%, we would definitely need to rethink the experiment and/or our choice of measuring tools
and perhaps the procedure too.

## Calculating absolute uncertainty from percent uncertainty

Suppose you would like to determine the absolute uncertainty and are only given the percent
uncertainty. This is possible by undoing the percent uncertainty to get to the absolute
uncertainty.

Example: Find the absolute uncertainty for the following measurement: 5.2 g ± 2%

Return the percent to a decimal and multiple by the quantity measured—in this case 5.18 g.

Mathematically we have,

## 2 • 5.18 g = 0.02 • 5.2 g = 0.1 g.

100

Therefore, our measurement with absolute uncertainty would be recorded as 5.2 ± 0.1 g.
Notice that both the measurement value and the absolute uncertainty match in that they are
both carried to the 1/10th place.

## a. 2.70 ± 0.05 cm b. 12.02 ± 0.08 cm

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c. 13.21 ± 0.01 m d. 0.002 ± 0.001 g

## e. 1.2 ± 0.1 sec f. 12 ± 1 volts

2. Convert the following to absolute uncertainties. Rewrite the measurement with that
uncertainty to the correct number of significant figures.

a. 3.5 cm ± 10 % b. 16 s ± 8 %

## What happens to the uncertainty when I perform

calculations?
When performing mathematical calculations with measurements that have uncertainty, you
must deal with that uncertainty while you are doing the mathematical operation. There is one
rule for adding and subtrating and another for multiplying and dividding.

The mathematical operation is carried out and the uncertainties of the measurements are
added together. This is true for both adding and subracting. The following example is shown
below with a table of temperature data and the uncertainty for each temperature.

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To get the change in temperature, ∆T, we subtract,

## 57.58 – 23.42 = 34.16oC

We deal with the uncertainty for each measurement by adding them together. Thus,

## • MULTIPLYING AND DIVIDING TWO MEASUREMENTS

When multiplying and dividing, percent uncertainties should be used (not absolute
uncertainties). This is more involved (and more tedious) than for adding or subtracting, but not
necessarily more difficult. Let’s see how this works with the following example.

EXAMPLE: Calculate the moles of 3.45 ± 0.05 L of a 2.55 ± 0.01 M NaOH and write your final
a. uncertainty (percent is assumed)
b. absolute uncertainty.
c. Correct number of significant figures.

2.55 3.45

## Now sum the percent uncertainties: 0.39% + 0.2% = 0.59%

a. Our moles can be written as (3.45 L • 2.55 mol/L) = 8.80 mol ± 0.59%

b. To calculate the absolute uncertainty, we take our percent uncertainty, divide it by 100
and then multiply by our moles. Recall, that we avoid rounding errors by rounding at the
final calculation. Thus we will multiply M • V = 3.45 L • 2.55 mol/L = 8.7975 moles and
keep all of the digits until the end.

## 0.59 x 8.7975 moles = 0.05

100

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We keep to the 1/100th place because our moles are to the 1/100th place.

## • MULTIPLYING OR DIVIDING A MEASUREMENT BY A NON MEASUREMENT

Suppose we want to multiply the volume, 12.12 ± 0.05 mL by 3. We would represent that value
as
The uncertainty of one
12.12 mL •3 = 36.36 mL
measurement is very large
0.05 mL • 3 = 0.15 mL When the uncertainty of one measurement is
with the final value reported as 36.36 ± 0.15 mL so large relative to the uncertainties of the
other measurements, the uncertainty of the
If we need to divide a number (as in an average), we final calculation can be considered as arising
from this measurement with the large
divide the uncertainty as well.
uncertainty.

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## Do problems 6-9 all

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Self Test 11.2
1. a. 3 2. a. 3.74 mg
b. 2 b. 0.0041 g
c. 1 c. 82 mL
d. 2 d. 200,000 km
e. 4 e. 2.001 x 10-12 pL
f. 5 f. 0.012 dg
g. 2 g. 89.7 mL
h. 6
i. 4
j. 3
3. a. 14.882 g 4. a. 4.7 x 104 kg
b. 5.8137 g/mL b. 8 x 10 -4 M HCl
c. 25.6 g c. 6.75 x 108 m
d. 3.32 g d. 1.57 x 1023 pg
e. 3.407 x10-7 pL
e. 37 mm3 f. 0.0766 mg
f. 40 m2 g. 780,000 km
g. 18.5 g/cm3 h. 0.000475 cm3
i. 0.0006 g
j. 900,000,000 km
k. 602,200,000,000,000,000,000,000 mol Self Test
11.3b
1 a. 1.85%
b. 0.67%
c. 0.08%
d. 50%
e. 8.3%
f. 8%

2 a. 3.5 ± 0.4 cm
b. 16 ± 1 sec
c. 8.9 ± 0.1 g
d. 12.12 ± 0.01 cm

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