CHM116 – Fundamentals in Chemistry I

Measurement, Accuracy and Precision

Measurements represent an action by someone with some measuring instruments. Measurements have built-
in uncertainty; no measurement is exact. The uncertainty in a measurement needs to be communicated. The
error in a measurement is the difference between an individual measurement and the true (accepted) value
of the quantity being measured.

Accuracy refers to the closeness of a measured value to a standard or known value. For example, if in lab
you obtain a weight measurement of 3.2 kg for a given substance, but the actual or known weight is 10 kg,
then your measurement is not accurate. In this case, your measurement is not close to the known value.

Precision refers to the closeness of two or more measurements to each other. Using the example above, if
you weigh a given substance five times, and get 3.2 kg each time, then your measurement is very precise.
Precision is independent of accuracy. You can be very precise but inaccurate, as described above. You can
also be accurate but imprecise.

For example, if on average, your measurements for a given substance are close to the known value, but the
measurements are far from each other, then you have accuracy without precision.

A good analogy for understanding accuracy and precision is to imagine a basketball player shooting baskets.
If the player shoots with accuracy, his aim will always take the ball close to or into the basket. If the player
shoots with precision, his aim will always take the ball to the same location which may or may not be close
to the basket. A good player will be both accurate and precise by shooting the ball the same way each time
and each time making it in the basket.
 Type of Example
Error

Random Random errors in experimental You measure the mass of a ring three times
Errors measurements are caused by unknown and using the same balance and get slightly
unpredictable changes in the experiment. different values: 17.46 g, 17.42 g, 17.44 g
These changes may occur in the measuring
instruments or in the environmental
conditions. The precision is limited by the
random errors. It may usually be
determined by repeating the
measurements. Random error is often
quantified by using the standard deviation

Systematic Systematic errors in experimental The cloth tape measure that you use to
Errors observations usually come from the measure the length of an object had been
measuring instruments. They may occur stretched out from years of use. (As a
because: result, all of your length measurements
were too small.)
• there is something wrong with
the instrument or its data The electronic scale you use reads 0.05 g
handling system, or too high for all your mass measurements
• because the instrument is (because it is improperly tared throughout
wrongly used by the your experiment).
experimenter.

Systematic errors unlike random errors

• Random error is directly related to the precision of measurements and can only be seen after
repeated measurements are taken. Sometimes called human error, random error is determined
by the experimenter’s skill or ability to perform the experiment and read scientific
measurements. These errors are random since the results yielded may be too high or low.
Often random error determines the precision of the experiment or limits the precision
 • Systematic error is directly related to how accurate the measurement is to the true value.
These values are usually skewed in one direction – all the values from the error are all
higher than the true value or all lower.

An example to highlight the difference:

A series of shots is fired at a target. Random errors are caused by anything that makes the shots
inconsistent and arrive at the target at random different points. For example, the shooter has an
unsteady hand or a change in the environment may distort the shooter’s view. These errors
would result in the scattering of shots shown by the right target in the figures to the left. A
systematic error, on the other hand, would include consistent errors that always arise. For
example, the gun may be misaligned or there may be some other type of technical problem
with the gun. This type of error would yield a pattern similar to the left target with shots
deviating roughly the same amount from the center area. (The diagram below is in your lab
sheet)

How to minimize error

1. Take more data. Random errors can be evaluated through statistical analysis and can be
reduced by averaging over a large number of observations.
2. Systematic errors are difficult to detect and cannot be analyzed statistically, because all
of the data is off in the same direction (either too high or too low). Spotting and correcting
for systematic error takes a lot of care. How would you compensate for the incorrect results
of using the stretched out tape measure? How would you correct the measurements from
improperly tared scale?

Methods of Reducing Error

While inaccuracies in measurement may arise from the systematic error of equipment or random
error of the experimenter, there are methods that can be employed to reduce error:
Weighing by difference: Mass is an important measurement in many experiments and it is critical
for labs to reduce error in mass measurements whenever possible. A simple way of reducing the
systematic error of electronic balances commonly found in labs is to weigh masses by difference.
This procedure entails the following:

1. finding the mass of both the desired material and the container holding the material,
2. transferring an approximate amount of the material to another container,
3. re-measuring the mass of the original container, and
4. Calculating the mass of the removed sample by taking the difference between the initial
and final weights of the original container. The following formula illustrates the procedure
used for weighing by difference:

(mass of container + mass of material) - (mass of container + mass of material after removing
material) = mass of removed material

While most electronic balances have a "tare" or "zero" function that allows one to automatically
calculate a mass by difference, equipment can be faulty so it is important to remember the
fundamental logic behind weighing by difference.

• Averaging Results: Since the accuracy of measurements is limited in part to the capacity
of an experimenter to interpret their equipment, it makes sense that the average of several
trials would be taken rather than a single trial. The reasoning behind averaging results is
that an error of a measured value that falls below the actual value may be accounted for by
averaging with an error that is above the actual value. By performing a series of trials (the
more trials the more accurate the averaged result), an experimenter can account for some
of their random error and yield a measurement with higher accuracy.

• Calibrating Equipment: Just as random error can be reduced by averaging several trials;
systematic error of equipment can be reduced by calibrating a measuring device. This
usually entails comparing a standard device of well-known accuracy to the second device
requiring calibration. Additionally, procedures exist for different kinds of equipment that
can reduce the systematic error of the device. For example, a typical burette in a lab may
be used to carry out a titration involving neutralization of an acid and base. If the burette
formerly held acid but must now hold a base, then it would benefit the experimenter to
condition the burette with the base before carrying out the titration so that the burette may
acclimate to the new substance and provide a more accurate reading. Such procedures,
together with calibration, can reduce the systematic error of a device.
 Measuring Accuracy and Precision in the Lab

Measurements represent an action by someone with some measuring instruments. Measurements have built-
in uncertainty; no measurement is exact. The uncertainty in a measurement needs to be communicated.

Accuracy refers to the closeness of a measured value to a standard or known value. Error in accuracy can
therefore be determined by calculating the absolute error.

Absolute error has no sign. Absolute error is the difference between the measured value and the true value.
Sometimes the measured value is taken as an average when several measurements are taken.

Precision refers to the closeness of two or more measurements to each other. Using the example above, if
you weigh a given substance five times, and get 3.2 kg each time, then your measurement is very precise.
Precision is independent of accuracy. You can be very precise but inaccurate, as described above. You can
also be accurate but imprecise. The precision can be quantified by determining the standard deviation of a
set of values. A set of values with a low standard deviation is more precise than if the standard deviation
was high.

Example 1: Jane measured 20g using a balance and obtained the following after measuring four times:
25.4g, 22.3g 19.2g and 18.4g

Steps in determining the standard deviation (Using example 1 above to illustrate)

Formula:

1. Find the average or mean value of the measurements

Mean = (25.4 + 22.3+19.2+18.4) ÷ 4 = 21.3g

2. Subtract the mean from each individual value and then square the answer.

(25.4 – 21.3)² = 4.1² = 16.81 (22.3 – 21.3)² = 1² = 1

(19.2 – 21.3)² = (-2.1)² = 4.41 (18.4 – 21.3)² = (-2.9)² = 8.41

3. Add up

16.81 + 1 + 4.41+ 8.41 = 30.63

4. Count the number of measurements this is n. In this example n = 4 as four measurements were
taken. However according the formula you use n -1 so n-1 = 3. Divide the Sum by n-1 and then
find the square root
 30.63
= 10.21 = 3.2 Thus measurement: 21.3 ±3.2.
3

Interpreting the results of example 1! The mean tells us that the values were inaccurate as they were far
away from the true value of 20. This suggests that there must have been some systematic error introduced
into the experiment. In addition the measurements were not precise as the standard deviation was very large.
This suggests some random error.