CAPE Chemistry – UNIT 2 – Chemical Principles and Applications II

Module 1 – The Chemistry of Carbon Compounds Lecture Notes 19

Accuracy and Precision

The accuracy of a measurement refers to how close a measured value is to the accepted value.
Precision refers to the agreement between two or more measurements that have been carried out exactly
the same way.
Generally, precision deals with replicability of results taken whereas accuracy deals with the taking true
readings. The following images compares accuracy and precision.

However, no matter how precise or accurate a measurement is, there is still some amount of error. This is
because the true value of a quantity cannot be measured with infinite precision as there are always
variations in measurements.

Question:
1. Two students determined the concentration of a hydrogen peroxide solution by the same
volumetric technique. They each carried out the analysis in triplicate and obtained the
following results:

Student A B

0.893 0.884
Hydrogen peroxide
Concentration/moldm -3 0.897 0.882

0.889 0.883

The true concentration of the hydrogen peroxide solution is 0.893 moldm -3 .

(a) Explain which student achieved

(i) the greater precision
(ii) the greater accuracy.
 Error
Error (E) is the difference between a measurement and the true value of the measurement (the quantity
being measured). Error is what causes values to differ when a measurement is repeated and none of the
results can be preferred over the others. Although it is not possible to completely eliminate error in a
measurement, it can be controlled and characterized. The total error is usually a combination of systematic
error and random error.
Random Errors
These are fluctuations in the measured data due to the limitations of the measurement device. Such errors
results due to the experimenter’s inability to take the same measurement repeatedly in exactly the same
way so as to get the exact value. Such errors affect the precision of measurements and may be reduced by
taking a number of reading and using an average of the data set. The following variables are associated
with random errors.
 Visual judgement with respect to reading and recording measurements on laboratory equipment.
 Temperature fluctuations. This may affect the volume of the glassware, the viscosity of a liquid to
be measured or the performance of a balance.
 Wind that cause vibrations in the readings from a balance
NB: Precision depends on the distribution of random errors since it is not based on the true/accepted value.
Systematic Errors
This is a consistent difference between a measurement and its true value and persists throughout an entire
experiment. Such errors affect all the data set in the same way each time a measurement is made and
cannot be reduced or eliminated by taking a number of measurements and using an average of the data
set. Systemic errors affect the accuracy of a measurement and may arise due to:
 Instrument errors, these include:
 Errors caused by an instrument being wrongly calibrated
 Instruments being used under different conditions from which they were calibrated.
 Instrument not reading zero when it should.

 Method errors, these include:

 Incompleteness of reactions
 The occurrence of side reactions cause by impurities

 Personal errors which result from personal judgement such as the end-point or titration reactions
or estimating measurements between scale markings.
Question:

1. In acid/base titrations it is important to use the minimum volume of indicator – usually 2–3 drops
– since acid/base indicators are themselves weak acids or weak bases. In a series of titrations a
student always used 10 drops of indicator per titration. Would this lead to a random or systematic
error in his titre volumes? Explain your answer

2. A student calibrated a pH meter using a buffer solution of pH 7.00 and then went unto measure
the pH values of a number of aqueous solutions. She later discovered that the pH of the buffer
solution she had used to calibrate the pH meter was actually 7.09. Would this cause a random or
systematic error in her pH results?
Error (E) can be calculated as being absolute or relative. Absolute error is the difference between the
measured value and the accepted value and is calculated using the following equation:

E = xmeasured –xaccepted
Relative error is a ratio of the absolute error relative to the true or accepted value and is calculated using
the following equation.

E = xmeasured –xaccepted
xaccepted

Uncertainty
Every measurement has a degree of uncertainty associated with it. Uncertainty is a parameter
characterizing the range of values within which the value of the measurement can be said to lie within a
specified level of confidence. The uncertainty derives from the measuring device and from the skill of the
person doing the measuring. An uncertainty is a natural variation in a measurement that comes about for
a variety of reasons including:
 The premise that no instrument is exactly accurate,
 Different people may be using different types of instruments and,
 The instrument’s adjustment may have changed.
No matter how careful experiments are set up, problems like these always arise. Uncertainty may be
absolute or relative.
The absolute uncertainty (Au) is given by half (1/2) the unit of the smallest graduation on the measuring
instrument. The relative uncertainty (Ru) is given by the following equation.
𝐴𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑈𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦
𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑈𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 = 𝑋 100 %
𝑀𝑒𝑎𝑠𝑢𝑟𝑒𝑚𝑒𝑛𝑡

For example, if a student is using a burette whose smallest graduation is 0.1 mL, then the absolute
uncertainty of the burette will be ± 0.05. This is the value of ½ the unit of the smallest graduation (which
is 0.1 mL). Therefore, if the student recorded a measurement from the burette to be 25.5 mL then the true
value of the measurement lies between 25.45 and 25.55 mL.
The relative uncertainty is calculated as follows:
𝐴𝑏𝑠𝑜𝑙𝑢𝑡𝑒 𝑈𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦
𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑈𝑛𝑐𝑒𝑟𝑡𝑎𝑖𝑛𝑡𝑦 = 𝑋 100 %
𝑀𝑒𝑎𝑠𝑢𝑟𝑒𝑚𝑒𝑛𝑡
0.05 𝑚𝐿
= 25.5 𝑚𝐿 𝑋 100%

Relative Uncertainty = 0.196 %

Questions:
1. Calculate the Relative uncertainties of the following measurements.
(a) A measurement recorded on a graduated pipette as 10.1 mL ± 0.05 mL.
 (b) The mass of a crucible recoded on an analytical balance as 30.64g ± 0.005g.
(c) The temperature of a solution taken to be 57.9 oC ± 0.05 oC.

2. Convert the following relative uncertainties into absolute uncertainties.

(a) 22 lbs with a 5% relative uncertainty.
(b) 112.1 mg with a relative uncertainty of 2%.
(c) 1000 tonnes of rice with a relative uncertainty of ± 10%.

3. The relative formula mass of sodium chloride is 58.4425g and has a percentage uncertainty of 3.4
x 10-4 %. Calculate the absolute uncertainty in the relative formula mass of sodium chloride.

4. You have been asked to weigh out 17g of calcium carbonate to within relative uncertainty of
0.2%.Calculate the absolute uncertainty in this mass.

Generally:
 When adding or subtracting values, we add the individual Absolute uncertainty.
 When multiplying or dividing values, we add the individual Relative uncertainties.
Questions:
1. Use the following data to calculate the absolute uncertainty in the mass of sodium chloride
transferred to the weighing bottle.

Mass of weighing bottle + sodium chloride = 18.54g

Mass of weighing bottle = 12.32g

2. In an attempt to identify an unknown mineral its density was determined. A sample of

the mineral was found to have a mass of 4.63 ±0.01 g and a volume of 1.13 ±0.02 cm 3 .

(a) Calculate the relative uncertainty in the mass and the volume of the sample.
(b) Calculate the density of the mineral and its relative and absolute uncertainties.

Significant Figures
The number of significant figures in a result is simply the number of figures that are known with some
degree of reliability.
Rules for determining significant figures
1. All nonzero digits are significant:
 3.256 g has 4 significant figures.
 1.5 g has 2 significant figures.

2. Zeroes between nonzero digits are significant:

 2005 kg has 4 significant figures,
 10.007 mL has 5 significant figures
 3. Leading zeros to the left of the first nonzero digits are not significant; such zeroes merely indicate
the position of the decimal point:
 0.1oC has only 1 significant figure,
 0.0378 g has 3 significant figures.

4. Trailing zeroes that are also to the right of a decimal point in a number are significant:
 0.0370 mL has 3 significant figures,
 0.50 g has 2 significant figures.

5. When a number ends in zeroes that are not to the right of a decimal point, the zeroes are not
necessarily significant:
 190 miles may be 2 or 3 significant figures,
 50,600 moldm-3 may be 3, 4, or 5 significant figures.

The potential ambiguity in the last rule can be avoided by the use of standard exponential, or "scientific,"
notation. For example, depending on whether the number of significant figures is 3, 4, or 5, we would
write 50,600 calories as:
 5.06 × 104 moldm-3 (3 significant figures)
 5.060 × 104 moldm-3 (4 significant figures), or
 5.0600 × 104 moldm-3 (5 significant figures).

Questions:
1. The concentration of magnesium in seawater is 0.00133 moldm-3. What mass of
magnesium written to 3 significant figures would be present in 6.0 litres of seawater?

2. Given that one mole of potassium chloride has a mass of 74.6 g, calculate the number
of moles given to 5 significant figures of potassium chloride in a 2.0 g sample.

3. Calculate the number of molecules in 8.3 mol of carbon dioxide to 3 significant figures.
The Avogadro constant is 6.02 x 1023 molecules mol-1.

4. What volume of 0.150 moldm-3 sodium hydroxide solution, to 2 significant figures,

will contain 0.300 mol of solute?

5. A weighing bottle containing a liquid sample had a total mass of 15.653 g. After
transferring the liquid into a reaction flask, the weighing bottle was reweighed and had
a mass of 12.793 g. Calculate the mass of liquid transferred to the flask to 3 significant
figures.

6. 1.65 x 106 tonnes of a chemical were produced and 9.22 x 105 tonnes were sold.
Calculate the mass of the chemical, to 3 significant figures, that remained unsold.