CONTENTS CHEM1000 Principles and Processes in Chemistry

Foundations of Stoichiometry

Contents
1 Fundamentals of Stoichiometry 2
1.1 Atomic Mass, Molecular Mass and Moles . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Mass Percentage Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Empirical and Molecular Formulae . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4 Dimensional Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.5 Review Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.6 Advanced Exercises . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

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 CHEM1000 Principles and Processes in Chemistry

1 Fundamentals of Stoichiometry
In this module we are going to review fundamental concepts of stoichiometry, which include the
definition and use of atomic and molecular masses, the concept of mole, as well as the determination
of percentage composition, empirical and molecular formulae of compounds. We are also going to
learn how to perform dimensional analyses of formulae and equations.

Note: in this part of the unit we will not stringently follow the rules of significant figures
and rounding, although you will have to do it in the laboratory and associated submission
of reports. The level of precision you use in your calculation is left to you (for example, you
can use 15.999 or 16.0 g mol−1 as atomic mass of oxygen). However, you are encouraged to
be consistent in your calculations and, as practice, follow as much as possible the rules for
significant figures and rounding.

1.1 Atomic Mass, Molecular Mass and Moles

The atomic mass of an element represents the average mass of the naturally occurring isotopes
(an isotope of an element is an atom with the same number of protons, but different number of
neutrons). Consequently, the molecular mass represents the sum of the atomic masses of all the
elements present in a compound, each multiplied by its stoichiometric index as expressed in the
chemical formula. Atomic and molecular masses, often referred to as molar masses, are expressed in
units of grams per moles (g mol−1 ).

Note: every element has a specific and unique value of atomic mass. In those situations where
an elements must be identified, it is therefore a common strategy to try and determine its
atomic mass.

Example 1
Determine the molecular masses of dioxygen and potassium sulfate, whose chemical formulae
are O2 and K2 SO4 , respectively.

Solution The atomic mass of oxygen is 15.999 g mol−1 . Therefore the molecular mass of O2
is obtained as:

WO2 = 2 · 15.999 g mol−1

= 31.998 g mol−1
The atomic masses of potassium and sulfur are 39.0983 and 32.065 g mol−1 , respectively. There-
fore the molecular mass of K2 SO4 is obtained as:

WK2 SO4 = 2 · 39.0983 g mol−1 + 32.065 g mol−1 + 4 · 15.999 g mol−1

= 174.258 g mol−1

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1.2 Mass Percentage Composition CHEM1000 Principles and Processes in Chemistry

The example before introduce the concept of mole. The units of the molar masses indicate the mass,
in grams, of 1 mole of a substance. For example, 1 mole of atomic oxygen has a mass of 15.999 g,
whereas the mass of a mole of potassium sulfate has a mass of 174.256 g.

Given the mass and molar mass of a compound, its number of moles can be determined using equation
1. Moles are defined by the units mol. A mole of any substance represents a very specific amount of
particles (e.g. atoms or molecules), equal to 6.022 × 1023 . Therefore, the constant Avogadro’s number
is defined as 6.022 × 1023 mol−1 .

m
n= (1)
W
where n is the number of moles, m is the mass of the compound and W is its molecular mass.

Example 2
Calculate the number of moles of aluminium present in a sample of mass 700.0 mg.

Solution The atomic mass of Al is 27.0 g mol−1 . Therefore the number of moles can be
obtained as:

700.0 × 10−3 g
n=
27.0 g mol−1
= 2.60 × 10−2 mol

Example 3

Calculate the mass of 7.00 × 1020 molecules of dichlorine, whose formula is Cl2 .

Solution The molar mass of Cl2 is 70.906 g mol−1 . We can begin by calculating the number
of moles of Cl2 corresponding to 7.00 × 1020 molecules, knowing that 6.023 × 1023 molecules
correspond to 1 mole.

7.00 × 1020
n=
6.023 × 1023 mol−1
= 1.16 × 10−3 mol
m = 1.16 × 10−3 mol · 70.906 g mol−1
= 8.23 × 10−2 g

1.2 Mass Percentage Composition

The mass percentage composition (or often referred more simply to as % composition) can be cal-
culated by taking the ratio of the mass of a specific element in a compound and the total mass

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1.2 Mass Percentage Composition CHEM1000 Principles and Processes in Chemistry

of the compound, according to equation 2. The value of % composition of atoms in a compound is

independent from the mass of the compound, so you can decide to make the calculation starting from
an arbitrary mass of your choice, that is convenient according to the data you have. For example,
if you have the chemical formula and molecular mass of a substance, you can make your calculation
relative to 1 mole of substance.

mX
%X = · 100 (2)
mtot
where %X is the percentage composition of the element X, mX is the mass of element X and
mtot is the total mass.

It goes without saying that the sum of the % compositions of all the elements of a substance must
be 100%. This is usually a good check to perform to ensure that all the calculations have been
completed correctly.

Example 4

Calculate the % composition of all the elements in aluminium phosphate.

Solution The chemical formula of aluminium phosphate is AlPO4 , and its molar mass is 122.0
g mol−1 . We can arbitrarily consider 1 mol of AlPO4 , whose mass is 122.0 g and contains 1 mol
of Al (27.0 g), 1 mol of P (31.0 g) and 4 mol of O (64.0 g). With these data, we can determine
the % composition of all the elements.

27.0 g
%Al = · 100
122.0 g
= 22.1%
31.0 g
%P = · 100
122.0 g
= 25.4%
64.0 g
%O = · 100
122.0 g
= 52.5%

We can verify that the sum of all the % composition values is 100%.

Mass % compositions can also be used in mixture of compounds, where it refers to % of each
pure compound in the mixture. Equation 2 is used in this case, where X indicates one of the
component of the mixture. When determining the % composition in a mixture it is often necessary
to use simultaneous equations, with the number of required equations depending on the number of
unknown compounds to determine in the mixture. Let’s illustrate the procedure with the following
example.

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1.2 Mass Percentage Composition CHEM1000 Principles and Processes in Chemistry

Example 5
A mixture of Cu2 O and CuO of total mass 3.00 g is reacted with an excess of hydrogen to
form 2.55 g of metallic Cu. Determine the % composition of the mixture.

Solution We need to find two independent equations containing two variables, linked to Cu2 O
and CuO. Given we have the initial mass of the mixture and the total mass of Cu formed, we
can design the equations around these data. If nCu2 O and nCuO are the number of moles of
Cu2 O and CuO, respectively, after calculating their respective molar masses (143.09 g mol−1
for Cu2 O and 79.55 g mol−1 for CuO) we can establish that:

nCu2 O · 143.09 + nCuO · 79.55 = 3.00

The previous equation validates that the mass of Cu2 O and the mass of CuO represent the
total mass of the mixture, which is 3.00 g. We know that two moles of metallic Cu are formed
for every more of Cu2 O, and one mole of metallic Cu is formed for every mole of CuO. Since
the atomic mass of Cu is 63.55 g mol−1 , we can establish the second independent equation
relative to the total mass of Cu formed:

(2 nCu2 O + nCuO ) · 63.55 = 2.55

As we have two independent equations and two variables, we can solve them simultaneously:


(2 n
Cu2 O + nCuO ) · 63.55 = 2.55
nCu O
2 · 143.09 + nCuO · 79.55 = 3.00


127.10 n + 63.55 nCuO = 2.55
Cu2 O
143.09 nCu O + 79.55 nCuO = 3.00
2

We can solve the first equation for nCu2 O , and then substitute in the second equation (solving
by elimination would also be possible):

2.55 − 63.55 nCuO

nCu2 O =
127.10
2.55 − 63.55 nCuO
143.09 + 79.55 nCuO = 3.00
127.10
2.87 − 71.55 nCuO + 79.55 nCuO = 3.00
8.00 nCuO = 0.13
nCuO = 0.016

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1.3 Empirical and Molecular Formulae CHEM1000 Principles and Processes in Chemistry

Now that have calculated the number of moles of CuO in the mixture, we can determine its
mass and % composition, which would be the mass of CuO divided by the total mass and
multiplied by 100.

mCuO = 0.016 mol · 79.55 g mol−1

= 1.27 g
1.27
%CuO = · 100
3.00
= 42.3%
%Cu2 O = 100.0% − 42.3%
= 57.7%

Therefore, the mixture is 57.7% Cu2 O and 42.3% CuO.

1.3 Empirical and Molecular Formulae

By combining the molar masses and the % composition of all the elements in a compound, it is possible
to determine its empirical formula. The empirical formula lists all the elements that constitutes the
compound, followed by their respective stoichiometric ratios, whose values are set as the lowest
integer numbers. For example, in any pure sample of sodium sulfate, the number of moles of Na
is always twice the number of moles of S, whereas the number of moles of O is always four times
the number of moles of S. Therefore, the empirical formula is Na2 SO4 , as 2, 1, and 4 are the lowest
integer numbers representing the molar ratios of the elements. Let’s see in the example below how
to determine an empirical formula.

Example 6

The analysis of an unknown compound has determined that it contains 32.81% of chromium,
and that the only other element present is chlorine. Determine the empirical formula of the
compound.

Solution We can easily determine the % composition of chlorine.

%Cl = 100.00% − 32.81%

= 67.19%

We can start from an arbitrary mass of compound, given that the % composition are valid for
any amount. It is convenient to consider 100 g of compound, so that the mass of Cr will be
32.81 g, and that of Cl will be 67.19 g.

From here, we can determine the number of moles of Cr (atomic mass 52.0 g mol−1 ) and Cl
(atomic mass 35.5 g mol−1 ) in 100 g of compound.

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1.3 Empirical and Molecular Formulae CHEM1000 Principles and Processes in Chemistry

32.81 g
nCr =
52.0 g mol−1
= 0.631 mol
67.19 g
nCl =
35.5 g mol−1
= 1.893 mol

Next, to determine the formula Crx Cly , we will take the ratio of moles by dividing every value
for the lowest amount. In this case, the lowest amount is the number of moles of Cr. Therefore,
the molar amount of Cl with respect to Cr is given by:

1.893 mol
y=
0.631 mol
=3

The value of x is 1, given that it is the number of moles of Cr divided by itself, therefore the
formula is CrCl3 .

The previous example can be used as a generic method to determine the empirical formula of a
compound from its % composition and atomic masses. Note that the formula must always be given
with the stoichiometric ratios as integer numbers. So in the event that fractional values are obtained
at the end of the process, all the values are appropriately multiplied so that they become integer.
For example, if a formula XY1.5 Z2 is obtained, you can multiply the stoichiometric ratios by 2 to
obtain the empirical formula as X2 Y3 Z4 .

If a compound is constituted by discrete molecules, whereby all the atoms within an individual
molecule are connected by covalent bonds, then it is more common to provide a molecular formula,
rather than an empirical formula. Let’s consider for example the sugar glucose. In any amount of
glucose, the molar amount of carbon and oxygen is identical, and the molar amount of hydrogen is
twice that of carbon. Therefore, its empirical formula would be CH2 O. Since within an individual
molecule there are 6 atoms of C, 12 atoms of H and 6 atoms of O (which are as expected from the
empirical formula in a ratio of 1:2:1), the molecular formula of glucose is C6 H12 O6 .

To determine the molecular formula, it is necessary to know the empirical formula and the molec-
ular mass of the compound. Let’s illustrate the process in the example below, which features the
analysis of a compound via analysis of produced quantities after targeted reaction (e.g. combustion).

Example 7

The molecular mass of fructose is 180 g mol−1 . The combustion of 150.0 mg of fructose in
excess of oxygen leads to the formation of 220.0 mg of CO2 and 90.0 mg of H2 O. Determine
the molecular formula of fructose.

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1.3 Empirical and Molecular Formulae CHEM1000 Principles and Processes in Chemistry

Solution All the C and H atoms in the CO2 and H2 O products originally belong to fructose,
so we can determine their molar amount. The number of moles of C in fructose is equal to the
number of moles of CO2 produced, whereas the number of moles of H in fructose is equal to
twice the number of moles of H2 O.

220.0 × 10−3 g
nC =
44.0 g mol−1
= 5.00 × 10−3 mol
90.0 × 10−3 g
nH = 2 ·
18.0 g mol−1
= 1.00 × 10−2 mol

Because oxygen was provided in excess during the combustion, we don’t know whether some of
the oxygen present in the combined amount of produced CO2 and H2 O comes from the added
O2 rather than fructose. Therefore, to determine the amount of O present in fructose we’ll
take the difference between the total mass of the compound, and the combined masses of C
and H, which we can determine with the calculated number of moles. Then, with the mass of
O in fructose, we can determine its number of moles.

mO = 150.0 × 10−3 g − 5.00 × 10−3 mol · 12.0 g mol−1 − 1.00 × 10−2 mol · 1.00 g mol−1
= 80.0 × 10−3 g
80.0 × 10−3 g
nO =
16.0 g mol−1
= 5.00 × 10−3 mol
Given that the number of moles of C and O are identical, and the number of H is twice that
amount, we can establish that the empirical formula of fructose is CH2 O. To determine the
molecular formula, you can proceed as follows:
(i) calculate the molar mass corresponding to the empirical formula;
(ii) calculate the ratio between the molar mass of the compound and the molar mass corre-
sponding to the empirical formula;
(iii) multiply the stoichiometric ratios in the empirical formula by the value obtained.
Let’s apply the process to fructose. The molar mass corresponding to the empirical formula is
30.0 g mol−1 . we can now calculate the ratio x of molar masses:

30.0 g mol−1
x=
180 g mol−1
=6

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1.4 Dimensional Analysis CHEM1000 Principles and Processes in Chemistry

Multiplying by 6 the stoichiometric ratios 1:2:1 in the empirical formula of C, H and O,

respectively, we obtain C6 H12 O6 (glucose and fructose have the same molecular formula, but
different connectivity between atoms).

You can use the example illustrated above as a generic method to determine the molecular formula
of a compound given the empirical formula and the molecular mass.

1.4 Dimensional Analysis

Whenever a value is provided at the end of a calculation, it is essential to accompany it with its
associated units (unless the value in question is dimensionless). This aspect is important, as the
meaning of a value can be quite different depending on its unit; for example, there is a big difference
between 20.0 L and 20.0 mL of water, despite the fact that the value 20.0 is the same.

A dimensional analysis provides confirmation that a calculation has been performed correctly,
and that the final value represents the actual quantity when associated to its unit. To complete a
dimensional analysis, you can algebraically manipulate the units of all the values that you are using
in a calculation. A dimensional analysis will also indicate you what values to use in specific equations;
for example, it will tell you whether you should use the ideal gas constant as 8.314 J mol−1 K−1 or
0.0821 L atm mol−1 K−1 .

When completing a calculation, always make sure that all the units simplify to provide the units
corresponding to the expected quantity. For example, if you are calculating a volume, you are ex-
pecting the final unit to be in m3 or L (or submultiple units such as cm3 or mL), an energy to be in
J or cal, a mass to be in g etc., depending as to whether SI units are used or not. It is a good idea
to always write down the units after every value when making a calculation.

Let’s make an example on how a dimensional analysis can be used to identify what a quantity
corresponds to.

Example 8
Demonstrate that if you multiply the gas constast R by the temperature T , the obtained
quantity is an energy.

Solution The units of R are J mol−1 K−1 , so for consistency of units, we’ll set T in K (rather
than ◦ C, for example). Performing the dimensional analysis on R × T we obtain:

J mol−1 
K−1

× K = J mol−1
The analysis demonstrates that the obtained value is an energy. Note that J or J mol−1 are
both units of energy, with the latter representing the combined energy of one mole (6.023 ×
1023 ) atoms or molecules, for example.

But what if we used R in units of L atm mol−1 K−1 ? The dimensional analysis would have

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1.5 Review Exercises CHEM1000 Principles and Processes in Chemistry

resulted in:

L atm mol−1 
K−1

× K = L atm mol−1

Can we demonstrate that L atm is also an energy? Let’s convert the units in SI, m3 for
a volume and Pa for a pressure. Pa is a derived SI unit, which can also be expressed as
kg m−1 s−2 . Therefore:

−1
 −2
m
3 · kg 
m s = kg m2 s−2

The result is still an energy, as kg m2 s−2 is equal to J. This example illustrates that also the
multiplication of a volume by a pressure results in an energy.

1.5 Review Exercises

Exercise 1
Determine the % composition of H2 O in hydrated calcium sulfate, CaSO4 ·2H2 O. If all the
water contained in 140.0 g of CaSO4 ·2H2 O is removed, what would be the remaining mass of
CaSO4 ?

Answer: 20.9% and 110.7 g.

Exercise 2
A unknown solid compound is inserted within a completely empty vessel, and heated to high
temperatures. The quantitative thermal decomposition produces a mixture of gases: 3.406
g of NH3 , 8.802 g of CO2 and 3.604 g of H2 O. Determine the empirical formula of the compound.

Answer: NH5 CO3

Exercise 3
10.0 g of P4 react with exactly 0.484 mol of Cl2 , forming exclusively one pure compound.
Determine its empirical formula.

Answer: PCl3

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1.6 Advanced Exercises CHEM1000 Principles and Processes in Chemistry

Exercise 4
239.6 mg of an iron oxide are quantitatively decomposed at elevated temperature, yielding
gaseous O2 and metallic Fe. The amount of Fe obtained is 167.7 mg. Determine the empirical
formula of the starting iron oxide.

Answer: Fe2 O3

Exercise 5
The analysis of an organic compound has provided the following result: 14.3% C, 1.2% H,
84.5% Cl. Determine its molecular formula, knowing that its molecular mass is 168.0 g mol−1 .

Answer: C2 H2 Cl4

Exercise 6
The Van der Waals equation to describe the behaviour of real gases, as opposed to the ideal
gas law, is reported below:

a n2
 
p + 2 (V − n b) = n R T
V
where p is the pressure, R is the gas constant, T is the temperature, V is the volume and n
is the number of moles. The parameters a and b depend on the nature of the gas. Determine
the units of a and b using the SI system.

Answer: [Pa m6 mol−2 ] for a and [m3 mol−1 ] for b.

1.6 Advanced Exercises

Exercise 7
A certain element M forms the compound MBr3 by reaction with liquid Br2 . Knowing that
Br represents 82.17% of the total mass of MBr3 , identify the element M.

Answer: Cr

Exercise 8
The elements X and Y form two different compounds: X2 Y3 and XY2 . Knowing that 0.18
mol of XY2 have a mass of 12.15 g, and that 0.18 mol of X2 Y3 have a mass of 21.42 g, identify
the elements X and Y.

Answer: X = Cl; Y = O.

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1.6 Advanced Exercises CHEM1000 Principles and Processes in Chemistry

Exercise 9
In the laboratory, you need to prepare a mixture of potassium sulfate, K2 SO4 , and calcium
sulfide, CuS. The mixture must contain an identical number of moles of both compounds and
must have a total mass of 1.00 kg. Determine the mass of each compound that must be used
to prepare the mixture.

Answer: 644 g of K2 SO4 and 356 g of CuS.

Exercise 10
When 10.00 g of MoO3 are treated with an excess of a reducing agent, all the molydbenum is
transformed into 8.33 g of another oxide. Determine its empirical formula.

Answer: Mo2 O3 .

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