1 S T O I C H I O M E T R I C R E L AT I O N S H I P S

Introduction
There is a broad community o people working reactions by equations, this chapter discusses the
within a wide variety o scientif c disciplines comprehensive language o chemistry.
and approaching their inquiry with common
For chemists, the mole concept is o
methodology, terminology and reasoning
undamental importance. Its def nitions in
processes. C hemistry can be regarded as the
relation to the number o particles, mass and the
central science, and mathematics the language
volume o a gas elicit universal understanding
o science. In this chapter we begin to lay
and stoichiometry, the quantitative method o
down many o the oundations on which an
examining the relative amounts o reactants
understanding o chemistry is based. From the
and products in a particular chemical reaction
classif cation o matter to the IUPAC organization
is developed. Treatment o the gas laws and the
o the nomenclature o organic and inorganic
application o volumetric analysis complete this
compounds and the representations o chemical
introductory chapter.
HEAD A_UND

1.1 Introduction to the particulate nature O B J TE XT_UND

of matter and chemical change

Understandings Applications and skills
 Atoms o diferent elements combine in  xed  Deduction o chemical equations when
ratios to orm compounds, which have diferent reactants and products are speci ed.
properties rom their component elements.
 Application o the state symbols (s) , (l) , (g) ,
 Mixtures contain more than one element and/ and (aq) in equations.
or compound that are not chemically bonded
 Explanation o observable changes in
together and so retain their individual properties.
physical properties and temperature during
 Mixtures are either homogeneous or changes o state.
heterogeneous.

Nature of science
 Making quantitative measurements with replicates to ensure reliability  de nite and multiple
proportions.

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1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

The atomic theory

A universally accepted axiom o science commonly used today was not available to
today is that all matter is composed o atoms. scientists in the past, who oten made ground-
However, this has not always been so. D uring breaking discoveries in relatively primitive
the seventeenth century the phlogiston theory conditions to eed their appetite or knowledge.
was a widely held belie. To explain the process O ver time, theories and hypotheses have been
o combustion it was proposed that a fre- like tested with renewed precision and understanding.
element called p hlogiston, said to be ound S ome theories do not stand the test o time.
within substances, was released during burning. The best theories are those that are simple and
Quantitative investigations o burning metals account or all the acts.
revealed that magnesium in act gains rather than
The atomic theory states that all matter is
loses mass when it burns in oxygen, contradicting
composed o atoms. These atoms cannot be
the phlogiston theory.
created or destroyed, and are rearranged during
S cientists use a wide range o methodologies, chemical reactions. Physical and chemical
instruments, and advanced computing power properties o matter depend on the bonding and
to obtain evidence through observation and arrangement o these atoms.
experimentation. Much o the technology

TOK
Antoine Lavoisier (17431794) is States of matter
oten reerred to as the ather o Matter is everywhere. We are made up o matter, we consume it, it
modern chemistry. His contribution surrounds us, and we can see and touch many orms o matter. Air is a
to science is well documented. In orm o matter which we know is there, though we cannot see it. O ur
1772 Lavoisier discovered through planet and the entire universe are made up o matter and chemistry
experimentation that when sulur seeks to expand our understanding o matter and its properties.
and phosphorus were combusted
they gained mass. These results made up of
contradicted the belie that mass particles 
atoms,
would be lost during combustion
molecules,
as phlogiston was released. or ions
Could phlogiston have a negative
mass? Empirical data derived
rom Lavoisiers experiments was
eventually accepted by the scientiic
community. His work contained
some o the irst examples o particles are occupies a
quantitative chemistry and the in constant MATTER volume in
law o conservation o mass. His motion space
experiments may appear simple by
present-day standards but they were
ground-breaking in their day.
The discovery o oxygen by Joseph
Priestly and Carl Scheele invalidated
the phlogiston theory. This is an
example o a paradigm shit. The has a mass
dominant paradigm or belie is
replaced by a new paradigm. Is this
how scientifc knowledge progresses?
Figure 1 The characteristics of matter

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The properties o the three states of matter are summarized below.

Soi liqi gas

 f xed volume  f xed volume  no f xed volume

 f xed shape  no f xed shape  takes the shape  no f xed shape  expands to
o the container it occupies occupy the space available
 cannot be compressed  cannot be compressed  can be compressed
 attractive orces between  orces between particles are  orces between particles are
particles hold the particles in weaker than in solids taken as zero
a close-packed arrangement
 particles vibrate in f xed  particles vibrate, rotate, and  particles vibrate, rotate, and
positions translate ( move around) translate aster than in a liquid

The way the particles o matter move depends on the temperature. As SI (Systme International) units are a
the temperature increases the average kinetic energy o the particles set of standard units that are used in
increases  the particles in a solid vibrate more. The particles in liquids science throughout the world. This will be
and gases also vibrate, rotate, and translate more. discussed in great detail in sub-topic 1.2.

Temperature When describing room temperature, we

There are a number o dierent temperature scales. The most commonly might say 25 degrees Celsius (25 C) or
used are the Fahrenheit, C elsius, and Kelvin scales. All three are named 298 kelvin (298 K) (to the nearest kelvin).
in honour o the scientist who developed them. Note that we use just the word kelvin, not
The S I unit or temperature is the kelvin ( K) . The Kelvin scale is used in degrees kelvin. The boiling point of water
energetics calculations ( see topic 5 ) . is 100 C or 373 K, and the melting point of
water is 0 C or 273 K.
Absolute zero is zero on the Kelvin scale, 0 K ( on the C elsius scale
this is 2 73 C ) . It is the temperature at which all movement o particles
stops. At temperatures greater than absolute zero, all particles vibrate,
even in solid matter.
You can convert temperatures rom the C elsius scale to the the Kelvin
evaporation steam
scale using the algorithm:
100
temperature/8C

temperature ( K) = temperature ( C ) + 2 73 .1 5 condensation

water
Changes of state melting
I you heat a block o ice in a beaker it will melt to orm liquid water. I 0
you continue heating the water, it will boil to orm water vapour. Figure 2 freezing
shows a heating curve or water  it shows how its temperature changes ice
during these changes of state. We shall look at the relationship between energy input
temperature and the kinetic energy o particles during these changes o state. Figure 2 The heating curve for water

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1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

Activity What happens to the particles during

1 Explain why the
temperature o a boiling changes of state?
liquid does not increase  As a sample o ice at 1 0 C (2 63 K) is heated, the water molecules
despite energy being in the solid lattice begin to vibrate more. The temperature increases
constantly applied. until it reaches the melting point o water at 0 C (2 73 K) .
2 Deduce which would be  The ice begins to melt and a solidliquid equilibrium is set up.
more painul, scalding your Figure 2 shows that there is no change in temperature while
skin with water vapour or melting is occurring. All o the energy is being used to disrupt the
boiling water. lattice, breaking the attractive orces between the molecules and
allowing the molecules to move more reely. The level o disorder
3 Explain why you might eel
increases. ( The nature o the orces between molecules is discussed
cold and shiver when you get
in sub- topic 4.4.)
out o the water at the beach
on a very hot, windy day.  O nce all the ice has melted, urther heating makes the water
molecules vibrate more and move aster. The temperature rises
until it reaches the boiling point o water at 1 00 C ( 3 73 K) , and
the water starts to boil.
Freeze-drying is a ood
preservation technique
 At 1 00 C a liquidgas equilibrium is established as the water boils.
that uses the process o Again the temperature does not change as energy is required to
sublimation. Foods that require overcome the attractive orces between the molecules in the liquid
dehydration are rst rozen and water in order to ree water molecules rom the liquid to orm a
then subjected to a reduced gas. ( Equilibrium is covered in sub- topic 7.1 .)
pressure. The rozen water  The curve in fgure 2 shows that while the water is boiling its
then sublimes directly to water temperature remains at 1 00 C . O nce all the liquid water has been
vapour, efectively dehydrating converted to steam, the temperature will increase above 1 00 C .
the ood. The process has
 Melting and boiling are endothermic processes. Energy must
widespread applications in
be transerred to the water rom the surroundings to bring about
areas outside the ood industry
these changes o state. The potential energy ( stored energy) o the
such as pharmaceuticals
molecules increases  they vibrate more and move aster.
(vaccines) , document recovery
or water-damaged books, and  C ooling brings about the reverse processes to heating  the
scientic research laboratories. condensation o water vapour to orm liquid water, and the
freezing o liquid water to orm a solid.
 C ondensation and reezing are exothermic processes. Energy
solid is transerred to the surroundings rom the water during these
changes o state. The potential energy o the molecules decreases 
they vibrate less and move slower.
 Vaporization is the change o state rom liquid to gas which may
happen during boiling, or by evaporation at temperatures below
the boiling point. In sublimation matter changes state directly rom
su b
zi n g

lim

the solid to gas phase without becoming a liquid. Deposition is the

g
fre e

dep
ltin

a ti o

reverse process o sublimation  changing directly rom a gas to a solid.

me

osi t

n
ion

vaporization
Elements and compounds
condensation An element contains atoms o only one type. Atoms o elements combine
in a fxed ratio to orm compounds composed o molecules or ions. These
liquid gas rearrangements o the particles o matter are the undamental cornerstone
o chemistry, represented in ormulae and balanced chemical equations.
Figure 3 Changes of state for water
(Atoms are covered in detail in sub-topic 2 .1 .)
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C hemists study how elements and compounds react with one another,
the many dierent chemical and physical properties o the substances
created in these reactions, and how they can be used in many
important applications.
The compound sodium chloride, NaC l, is made up o the elements
sodium and chlorine.
The group 1 alkali metal sodium is a sot metal that undergoes rapid
oxidation in air and violently reacts with water, creating alkaline solutions.
Sodium is stored under oil to prevent these reactions. It is the sixth most
abundant element on the planet, (2 .26% by mass) .

Figure 5 The structure of sodium chloride. It consists of a crystalline

Figure 4 Elemental sodium is a reactive alkali metal lattice of sodium ions (purple) and chloride ions (green)

The halogen chlorine is a gas at room temperature. C hlorine, C l 2 , is

highly irritating to the eyes, skin, and the upper respiratory tract.

The highly reactive elements sodium and chlorine combine to orm

the ionic crystalline compound sodium chloride, commonly called
table salt and consumed daily in the ood we eat. The properties
and uses o sodium chloride are very dierent rom those o its
constituent elements.

Mixtures
A p ure substance is matter that has a constant composition. Its
chemical and physical properties are distinct and consistent. Examples
include the elements nitrogen, N 2 and argon, Ar and compounds such as
water, H 2 O , table salt, NaC l, and glucose, C 6 H 1 2 O 6 .
Pure substances can physically combine to orm a mixture. For
example, sea water contains mainly sodium chloride and water. Pure
substances can be separated rom the mixture by physical techniques
such as fltration, ractional distillation, or chromatography. The

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1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

elements or compounds that make up a mixture are not chemically

posts law of constant comosition bound together.
(1806) stated that compounds have
distinct properties and the same Homogeneous mixtures have both uniorm composition and uniorm
elemental composition by mass. properties throughout the mixture. Examples include salt water or a
metal alloy such as brass. Heterogeneous mixtures have a non- uniorm
composition and hence their properties vary throughout the mixture.
Examples include oods such as tom yum goong ( Thai hot and sour
prawn soup) or Irish stew ( a mixture o cubed meat and vegetables) .
Figure 9 summarizes the classifcation o matter into elements,
compounds, and mixtures.
matter  any substance that occupies
space and has mass

mixture  a combination pure substance  has a

of two or more pure denite and constant
substances that retain their composition
individual properties

homogeneous mixture  heterogeneous mixture  element  made up of compound  made up

has both uniform has non-uniform atoms that each have of a combination of
composition composition and the same atomic atoms or ions in a xed
and properties varying properties, number, eg lead, Pb, ratio and having dierent
throughout, eg salad dressing, mercury, Hg, properties from the
eg salt water, paint, garden soil bromine, Br constituent elements, eg
Figure 6 Chlorine reacts vigorously
metal alloys water, H 2 O, carbon dioxide,
with sodium metal CO 2 , sodium chloride, NaCl

Figure 9 Elements, compounds, and mixtures

The language of chemistry

C hemistry has a universal language that transcends borders and
enables scientists, teachers, and lecturers, students, and citizens o
the wider community to communicate with each other. C hemical
symbols and equations are a language that requires no translation.
Knowledge o the symbols or elements and compounds and their
Figure 7 Table salt is the compound sodium relationship to one another as displayed in a balanced equation
chloride, NaCl(s) . It has very diferent properties unlocks a wealth o inormation, allowing understanding o the
rom those o its constituent elements chemical process being examined.
C hemical symbols are a way o expressing which elements are present
and in which proportions, in both organic and inorganic compounds.
The International Union o Pure and Applied C hemistry (IUPAC) is
an organization that develops and monitors a system o standardized
nomenclature or both organic and inorganic compounds. IUPAC s role
is to provide consistency in the naming o compounds, resulting in a
language o symbols and words that require no translation rom one
country or cultures language to another.

usefl resoce
Figure 8 Paper chromatography is used to
investigate industrial dyes by separating them The IUPAC Gold Book (http://goldbook.iupac.org/index.html) is IUPACs
into their pure constituent components compendium of chemical terminology.

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TOK na o oa na o oa

oyatoi io oyatoi io
Language is a crucial component in the communication o ammonium ion NH 4+ phosphate(V) ion PO 43 
knowledge and meaning. Does the language o chemistry with
its equations, symbols, and units promote or restrict universal carbonate ion CO 3 2  phosphonate ion PO 3 3 
understanding? What role does linguistic determinism play? hydrogencarbonate HCO 3  sulate(VI) ion SO 4 2
ion
For example, the concept o equilibrium is oten initially
misinterpreted. Preconceived ideas ocus on a 50:50 balance hydroxide ion OH  sulate(IV) ion SO 3 2
between reactants and products. It requires an understanding nitrate(V) ion NO 3  ethanedioate ion C2 O 42 
that equilibrium means that both the orward and reverse nitrate(III) ion NO 2  peroxide ion O 2 2
reactions are occurring at the same rate beore we can see that
an equilibrium reaction might avour the ormation o products Table 1 Common polyatomic ions
or reactions, or that such a reaction could be non-spontaneous.
na o ai oa
hydrochloric acid HCl
Common combinations of elements: Background
nitric(V) acid HNO 3
to writing equations phosphoric(V) acid H 3 PO 4
An ion is a charged species. Anions are negatively charged and cations are
positively charged. suluric(VI) acid H 2 SO 4
There are a number of common polyatomic ions that exist in many of ethanoic acid CH 3 COOH
the substances you will study and work with. You need to be familiar
Table 2 Common acids
with the names and formulae of these ions, shown in tables 1 to 3 .
na o aio oa nai sfx

Writing and balancing equations sulfde ion S2 -ide

An ability to write equations is essential to chemistry and requires sulate(VI) ion SO 4 2 -ate
a full understanding of the language of equations. At the most
sulate(IV) ion SO 3 2 -ate
fundamental level, formulae for the reactants are put on the left-
hand side along with their state symbols ( s) , ( l) , ( g) , ( aq) , and those Table 3 Naming anions. The prex identies the
for the products on the right- hand side. The arrow represents a element present and the sufx the type o ion
boundary between reactants and products. S tate symbols can be (eg element or polyatomic ion)
deduced by referring to the solubilities of ionic salts and the state of
matter of the element or compound at a given temperature.
A reaction may be described in terms of starting materials and products. Worked example
The process of transforming these words into a balanced chemical Magnesium burns in oxygen to
equation starts with the construction of chemical formulae. Writing form a white powder known as
ionic and covalent formulae will be discussed in depth in topic 4. magnesium oxide. Write a chemical
equation to represent this change,
including state symbols.

Qik qstios Solution

Write equations or the ollowing chemical reactions, including state symbols. Reer The reactants are the metal
to the working method on the next page on balancing equations i you need to. magnesium, a solid at room
temperature, and the diatomic
1 Zinc metal reacts with hydrochloric acid to orm the salt zinc chloride. H ydrogen
molecule, oxygen, which is a
gas is evolved.
gas. The product is the oxide of
2 H ydrogen gas and oxygen gas react together to orm water. magnesium, magnesium oxide
3 At a high temperature, calcium carbonate decomposes into calcium oxide and which is a solid substance.
carbon dioxide. 2Mg(s) + O 2 (g)  2MgO(s)

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1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

Working method: how to balance

S tep 1 : B alance the metal C a frst.
chemical equations It is balanced.
The examples below involve reactions o metals.
Figure 1 0 reminds you that metals are below and
C a( s) + H 2 O ( l)  C a( O H) 2 ( aq) + H 2 ( g)
to the let o the metalloids in the periodic table.
Remember that to balance an equation you
S tep 2 : B alance O next,
change the coefcient o a ormula ( add a number
as it occurs in only one ormula on
in ront o the ormula) . You do not change the each side. ( H occurs in both products.)
ormula itsel. Multiply H 2 O by 2 to balance O .
S tep 1 : First balance the metallic element on
each side o the equation  add a number
in ront o the symbol on one side i Ca(s) + 2H2 O(l)  Ca(OH) 2 (aq) + H2 (g)
necessary so that there is the same number
o atoms o this element on each side. Step 3 :
S tep 2 : B alance any elements that occur in You can now see that hydrogen
only one ormula on the reactant and has been balanced by step 2, which oten
products side. S ometimes polyatomic happens. Always check to make sure.
ions remain unchanged in reactions and
they can be balanced easily at this stage.
S tep 3 : Balance the remaining elements i necessary. The equation is now balanced overall.

5 6 7 8 9 1 Example 2
B C N O F N Potassium hydroxide is a soluble base that can
Boron Carbon Nitrogen Oxygen Fluorine Ne neutralize the diprotic acid suluric acid. D iprotic
13 14 15 16 17 1
acids produce two hydrogen ions when they
Al Si P S Cl dissociate. B alance the ollowing equation.
Aluminium Silicon Phosphorus Sulfur Chlorine Ar
9 30 31 32 33 34 35 3
u Zn Ga Ge As Se Br S tep 1 : B alance K by doubling KO H on
per Zinc Gallium Germanium Arsenic Selenium Bromine Kry the reactant side.
7 48 49 50 51 52 53 5
g Cd In Sn Sb Te I X
H 2 S O 4( aq) + KO H( aq)  K 2 S O 4( aq) + H 2 O ( l)
er Cadmium Indium Tin Antimony Tellurium Iodine Xe
9 80 81 82 83 84 85 8
u Hg Tl Pb Bi Po At R
S tep 2 : B oth O and H
ld Mercury Thallium Lead Bismuth Polonium Astatine Ra
1 112 113 114 115 116 117 1
occur in two compounds on both
sides o the equation. The sulate ion is
metals semi-metals non-metals
unchanged in the reaction and is balanced, so
the coefcient or H 2 S O 4 will stay the same.
Figure 10 Metals are below and to the left of the metalloids in
There are 4 H atoms on the reactant
the periodic table
side, so multiply H 2 O by 2 .

Example 1
The alkaline earth metal calcium reacts with H 2 S O 4 ( aq) + 2 KO H ( aq)  K 2 S O 4( aq) + H 2 O ( l)
water to produce an alkaline solution. B alance the
H 2 S O 4( aq) + 2 KO H( aq)  K 2 S O 4( aq) + 2 H 2 O ( l)
ollowing equation.
The equation is now balanced.

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So tys o atio The names and symbols o

cobiatio or sytsis reactions involve the combination o two or more the elements can be ound in
substances to produce a single product: section 5 o the Data booklet.
C(s) + O 2 (g)  CO 2 (g)
doositio reactions involve a single reactant being broken down into two or
more products:
CaCO 3 (s)  CaO(s) + CO 2 (g)
Si at reactions occur when one element replaces another in a
compound. An example o this type o reaction is a redox reaction (topic 9) :
Mg(s) + 2HCl(aq)  MgCl 2 (aq) + H 2 (g)
dob at reactions occur between ions in solution to orm insoluble
substances and weak or non-electrolytes, also termed tatsis reactions:
HCl(aq) + NaOH(aq)  NaCl(aq) + H 2 O(l)
This example is an acid-base reaction discussed urther in topic 8.

Some applications and reactions of butane

Fuels and rerigerants
B utane, C 4H 1 0 is mixed with other hydrocarbons such as propane to
create the uel liquefed petroleum gas ( LPG) . This is used in a wide
variety o applications.
Methylpropane (also called isobutane) is an isomer o butane. Isomers
have the same chemical ormula but their atoms are arranged structurally
in a dierent way. Methylpropane is used as a rerigerant, replacing the
CFCs that were previously used or this purpose. cfcs a t iat o
O zone occurs naturally in the stratosphere, in the upper atmopshere. si a tooy
O zone flters out most o the harmul ultraviolet rays rom the sun. The process o rerigeration
Without this protection the ultraviolet radiation would be harmul to involves the energy changes o
many orms o lie, causing skin cancer in humans and other problems. a condensationevaporation
cycle using volatile liquids.
H H H Chlorofuorocarbons (CFCs)
were traditionally used
O in rerigerators and air-
H
C C conditioning units. They cause
O O depletion o the ozone layer
H
C H in the atmosphere, which
H C H protects us rom the harmul
eects o ultraviolet radiation
H in sunlight.
H
CFCs are now banned in many
Figure 11 Ozone, O 3 Figure 12 Methylpropane is used as a refrigerant countries, and non-halogenated
C FC s undergo reactions with the ozone in the stratosphere, causing it hydrocarbons such as propane
to break down. The ozone hole is a thinning o the ozone layer that are more commonly used
appears over the polar regions o the E arth each spring. The use o instead. There is more about this
C FC s has caused this depletion o the ozone layer, so they have now in sub-topic 5.3.
been replaced by methylpropane.

9
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

The combustion o
hydrocarbons, CxH y produces
carbon dioxide and water.

Since 1997, taxis in Hong Kong

have been powered by liquefed
petroleum gas (LPG) . Today
there are over 18 000 LPG
taxis and 500 LPG light buses
operating there. LPG, consisting
o butane and/or propane,
undergoes combustion to
release energy to power the
vehicle. The reaction produces
carbon dioxide and water
(sub-topic 10.2) . LPG burns
much more cleanly than petrol
or diesel.
Figure 13 The ozone hole was frst noticed in the 1970s and is monitored by scientists
worldwide

Balancing the equation or the combustion o butane

The combustion o butane is an exothermic reaction.
C 4H 1 0 ( g) + O 2 ( g)  C O 2 ( g) + H 2 O ( l)
S tep 1 : There are no metal atoms to balance, so balance the carbon
atoms frst by multiplying C O 2 by 4.
C 4H 1 0 ( g) + O 2 ( g)  4C O 2 ( g) + H 2 O ( l)
S tep 2 : O xygen is ound in two compounds on the product side so
leave this until last. Hydrogen has 1 0 atoms on the let and 2 atoms on
the right, so multiply H 2 O by 5 .
C 4H 1 0 ( g) + O 2 ( g)  4C O 2 ( g) + 5 H 2 O ( l)
S tep 3 : The products now contain 1 3 oxygen atoms, an odd number.
To balance the equation 6.5 molecules o oxygen are required.
C 4H 1 0 ( g) + 6.5 O 2 ( g)  4C O 2 ( g) + 5 H 2 O ( l)
Fractions are not used in balanced equations, except when calculating
lattice enthalpy ( see topic 1 5 ) . We thereore multiply the whole
equation by 2 .
2 C 4H 1 0 ( g) + 1 3 O 2 ( g)  8C O 2 ( g) + 1 0H 2 O ( l)
The complex coefcients in this example show why the method o
balancing equations on page 8 is more efcient than just trial and error.
Figure 14 Rush hour in Hong Kong

10
 1 . 1 I n T r O d u c T I O n T O T h e p A r T I c u l AT e n AT u r e O f m AT T e r A n d c h e m I c A l c h A n g e

The atom economy

The global demand or goods and services along with an increasing world
population, rapidly developing economies, increasing levels o pollution,
and dwindling fnite resources have led to a heightened awareness o the
need to conserve resources. Synthetic reactions and industrial processes
must be increasingly efcient to preserve raw materials and produce
ewer and less toxic emissions. S ustainable development is the way o
the uture.
To this end the atom economy was developed by Proessor B arry
Trost o S tanord University S tanord, C A, US A. This looks at the level
o efciency o chemical reactions by comparing the molecular mass o
atoms in the reactants with the molecular mass o useul compounds.

percentage Molecular mass o atoms o useul products

= ____  1 00%
atom economy Molecular mass o atoms in reactants

The atom economy is important in the discussion o Green C hemistry,

which we will discuss later in this book. In an ideal chemical process
the amount o reactants = amounts o products produced. S o an atom
economy o 1 00% would suggest that no atoms are wasted.

Ativity
a) Suggest why even i a chemical reaction has a yield close to 100%, the atom
economy may be poor. Carry out some research into this aspect.
b) Discuss some other ways a chemical process may be evaluated other than
the atom economy, eg energy consumption etc.
) Deduce the percentage atom economy or the nucleophilic substitution
reaction:
CH 3 (CH 2 ) 3 OH + NaBr + H 2 SO 4  CH 3 (CH 2 ) 3 Br + H 2 O + NaHSO 4

Qik qstios
Identiy the type o reaction and then copy and balance 4 Al(s) + O 2 (g)  Al 2 O 3 (s)
the equation, using the smallest possible whole number
5 KClO 3 (s)  KCl(s) + O 2 (g)
coefcients.
6 C3 H 8 (g) + O 2 (g)  CO 2 (g) + H 2 O(g)
1 SO 3 (g) + H 2 O(l)  H 2 SO 4(aq)
7 Ni(OH) 2 (s) + HCl(aq)  NiCl 2 (aq) + H 2 O(l)
2 NCl 3 (g)  N 2 (g) + Cl 2 (g)
8 AgNO 3 (aq) + Cu(s)  Cu(NO 3 ) 2 (aq) + Ag(s)
3 CH 4 (g) + O 2 (g)  CO 2 (g) + H 2 O(g)
9 Ca(OH) 2 (s)  CaO(s) + H 2 O(l)

11
1 S TO I c h I O m e T r I c r e l AT I O n S h I p S

1.2 T o ot

Understandings Applications and skills
 The mole is a f xed number o particles and
 Calculation o the molar masses o atoms, ions,
reers to the amount, n, o substance. molecules and ormula units.
 Masses o atoms are compared on a scale
 Solution o problems involving the
relative to 1 2 C and are expressed as relative relationships between the number o particles,
atomic mass (A r) and relative ormula/ the amount o substance in moles and the
molecular mass (Mr) . mass in grams.
 Molar mass (M) has the units g mol  1 .
 Interconversion o the percentage composition
 The empirical ormula and molecular ormula by mass and the empirical ormula.
o a compound give the simplest ratio and the  Determination o the molecular ormula o
actual number o atoms present in a molecule a compound rom its empirical ormula and
respectively. molar mass.
 Obtaining and using experimental data or
deriving empirical ormulas rom reactions
involving mass changes.

Nature of science
 Concepts  the concept o the mole developed rom the related concept o equivalent mass in the early
19th century.

SI: the international system of measurement

Throughout history societies have developed dierent orms o
measurement. These may vary rom one country and culture to another,
so an internationally agreed set o units allows us to understand
measurements regardless o the language o our culture.
Units o measurement are essential in all walks o lie. The
f nancial world speaks in US dollars, the resources industries use
million tonnes ( MT) , precious metals are measured in ounces,
agricultural manuacturing uses a range o measures including yield
per hectare, and environmental protection agencies, amongst others,
talk about parts per million ( ppm) o particulate matter. Which units
do chemists use?
The de sire o r a standard inte rnatio nal se t o  u nits le d to the
de ve lo p me nt o  a syste m that transce nds all langu age s and
cultu re s  the S ys tm e Internatio nal d Units ( S I) . Tab le 1 sho ws
the se ve n b ase u nits o  the S I syste m. All o the r u nits are de rive d
ro m the se se ve n b ase u nits.

12
 1 .2 Th e m Ole cOn cepT

Accuracy and SI units

C ontinual improvements in the precision o instrumentation used
in the measurement o S I units have meant that the values o some
physical constants have changed over time. The International
B ureau of Weights and Measures ( known as B IPM rom its
initials in French) monitors the correct use o SI units, so that in all
applications o science, rom the school laboratory to the US National
Aeronautics and Space Administration ( NASA) , S I units are used and
are equivalent in all cases.

prorty uit Sybo

mass kilogram kg
temperature kelvin K
time second s
Figure 1 A platinumiridium cylinder
amount mole mol at the National Institute o Standards
electric current ampre A and Technology, Gaithersburg, MD, USA,
represents the standard 1 kg mass
luminosity candela cd
length metre m
Stdy tis
Table 1 The seven base units o the SI system
Physical constants and unit
Table 2 shows two quantities that are used throughout the study o conversions are available in
chemistry, along with their units. Table 3 is a list o standard prefxes section 2 of the Data booklet.
used to convert SI units to a suitable size or the application you are The value of Avogadros
measuring. constant (L or NA) will be
provided in Paper 1 questions,
moar vo o a ida gas at 273 K ad and may be referred to in the
Avogadros ostat (NA) Data booklet when completing
100 kpa
both Papers 2 and 3.
6.02  10 23 mol  1 2.27  10  2 m 3 mol  1 (= 22.7 dm 3 mol  1 )
Table 2 Useul physical constants and unit conversions

prfx Abbrviatio Sa

Amount of substance: The mole nano n 10  9
C hemists need to understand all aspects o a chemical reaction in order
micro  10  6
to control and make use o the reaction. From large- scale industrial
processes such as electrolytic smelting o aluminium and industries milli m 10  3
involved in processing o ood and beverages, to pharmaceutical centi c 10  2
companies synthesizing medicines and drugs, the ability to measure deci d 10  1
precise amounts o reacting substances is o crucial importance.
standard  1
All chemical substances are made up o elements that are composed
kilo k 10 3
o their constituent atoms, which vary in the number o protons,
neutrons, and electrons ( topic 2 ) . C hemists use a system to measure
mega M 10 6
equal amounts o dierent elements regardless o how big their atoms giga G 10 9
are, which allows them to calculate reacting quantities. The mole is an Table 3 Useul prefxes, their
S I unit, symbol mol, defned as a fxed amount, n, o a substance. This abbreviations and scales

13
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

defnition can be applied to atoms, molecules, ormula units o ionic

Stoichiomety uses the compounds, and electrons in the process o electrolysis.
quantitative relationships
between amounts o This fxed amount is a number o particles called Avogadros constant
reactants and products in ( symbol L or NA) and it has a value o 6.02  1 0 23 mol  1 . Avogadros
a chemical reaction. These constant enables us to make comparisons between chemical species. A
relationships depend on the mole o any chemical species always contains an identical number o
law o conservation o mass representative units.
and denite proportions. They
allow chemists to calculate Relative atomic mass, relative formula mass,
the proportions o reactants to
mix, and to work out expected and molar mass
yields, rom the ratios o Isotop es are atoms o the same element that have the same number
reactants and products o protons in the nucleus but dierent numbers o neutrons ( see sub-
according to the balanced topic 2 .1 ) . Isotopes o an element have dierent mass numbers. The
chemical equation. relative abundance o each isotope is a measure o the percentage that
occurs in a sample o the element ( table 4) .
The masses o atoms are compared with one another on a scale in which
a single atom o carbon- 1 2 equals 1 2 units. The relative atomic mass
relative Atomic A r o an atom is a weighted average o the atomic masses o its isotopes
Isotope and their relative abundances. The existence o dierent isotopes results
abundance mass
35
in carbon having an A r o 1 2 .01 . The relative molecular mass or
Cl 75% 35.0 relative formula mass Mr or a molecule or ormula unit is determined
37
Cl 25% 37.0 by combining the A r values o the individual atoms or ions. A r and Mr
have no units as they are both ratios.
relative atomic mass A  35.5
The molar mass is defned as the mass o one mole o a substance. It
Table 4 The relative atomic mass of
has the unit o grams per mole, g mol 1 ( fgure 2 ) .
chlorine is the weighted average of
the atomic masses of its isotopes
and their relative abundance
Mg NaCl H 2O

24.31 g 58.44 g 18.02 g

6.02  10 23 6.02  10 23 6.02  10 23

atoms formula units molecules
of Mg of NaCl of H 2 O
Figure 2 The molar mass of a substance contains Avogadros number of representative
particles (the particles may be atoms, molecules, or ions)

TOK
Scientic discoveries are the product o many diferent ways o knowing
(WOK) . To construct knowledge and understanding, scientists can use
intuition, imagination, reasoning, and even emotion, as well as detailed
investigation and analysis o large volumes o data that either support or
disprove observations and hypotheses. Sometimes it can just be a matter
o serendipity. The scale o Avogadros constant (602 000 000 000 000 000
000 000) passes beyond the boundaries o our experience on Earth. The
population o the planet is dwared by this number. How does this experience
limit our ability to be intuitive?

14
 1 .2 Th e m Ole cOn cepT

13
Worked examples: A r and Mr Al
Example 1 26.98
S tate the relative atomic mass A r of aluminium. Figure 3 The element aluminium as
represented in the periodic table
Solution
Figure 3 shows the periodic table entry for aluminium.
A r( Al) = 2 6.98

Example 2
C alculate the molar mass Mr of sulfuric acid, H 2 SO 4.
ngativ idis ad uits
Solution An idx or ow is a mathematical
Table 5 shows the data needed to answer this question. notation that shows that a quantity
or physical unit is repeatedly
multiplied by itsel:
et rativ atoi nub of cobid
ass A  atos ass/g m  m = m2
hydrogen 1.01 2 2.02 A gativ idx shows a reciprocal:
1 = x 1
_
sulur 32.07 1 32.07 x
dm  3 = _ 1
oxygen 16.00 4 64.00 dm 3
Table 5 cotatio (oaity) : units
may be written as mol dm  3 , M, or
Mr( H 2 S O 4) = ( 2  1 .01 ) + ( 1  3 2 .07) + ( 4  1 6.00) mol L 1 (US) .
Mr( H 2 S O 4) = 98.09 g mol 1 . etay of utaizatio: units
are kJ mol  1 .
Example 3 Iitia at of atio: units are
C alculate Mr of copper( II) sulfate pentahydrate, C uSO 4 5 H 2 O . mol dm  3 s  1 .

Solution
Many transition metal complexes ( sub- topic 1 3 .1 ) contain water
molecules bonded to the central metal ion. The formula C uS O 4 5 H 2 O
shows that 5 mol of water combines with 1 mol of copper( II) sulfate.

et rativ atoi nub of cobid

ass A  atos ass/g Study tis
copper 63.55 1 63.55  When adding and subtracting
numbers, always express
sulur 32.07 1 32.07 the fnal answer to the same
oxygen 16.00 4 64.00 number o decimal places as
the least precise value used.
oxygen 16.00 5 1=5 80.00
 When dividing or multiplying,
hydrogen 1.01 5  2 = 10 10.10 always express the answer to
Table 6 Calculating the molar mass of copper(II) sulfate pentahydrate the same number o signifcant
fgures as the least precise
Mr( C uS O 4 5 H 2 O ) = 2 49.72 g mol 1 . value used.

15
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

Quick question primary standards

Calculate the molar mass o the A rimary standard is any substance o very high purity and large molar mass,
ollowing substances and ions. which when dissolved in a known volume o solvent creates a primary standard
a) M g(NO 3 ) 2 solution.
Primary standard solutions are used in acidbase titrations to improve the
b) N a 2 CO 3
accuracy o the fnal calculation. The concentration o a primary standard can be
c) Fe 2 (SO 4) 3 determined accurately.
d) S 8
e) Zn(OH ) 2 Mole calculations
f) Ca(H CO 3 ) 2 All che mists, whether in the scie ntifc community, manuacturing
industries, or research acilities, work every day with re acting
g) I 2
quantities o chemical substances and so need to pe rorm
h) M gSO 4 7H 2 O stoichiometric calculations. The relationship be twee n the amount ( in
i) [Al(H 2 O) 6 ] 3+ mol) , number o particles, and the mass o the sample is summarized
in fgure 4.
j) P2 O 5
number of  Avogadros constant, L  molar mass
moles mass (g)
particles
 Avogadros constant, L  molar mass
Figure 4 The relationship between amount, mass, and number of particles

Worked examples: mole calculations

Example 1  1 .5 0 mol o glucose contains 9 mol o C atoms.
C alculate the amount ( in mol) o carbon dioxide, number o atoms = amount ( in mol) n 
n( C O 2 ) in a sample o 1 .5 0  1 0 23 molecules. Avogadro' s constant, L
= 9 mol  6.02  1 0 23 mol 1
Solution = 5 .42  1 0 24 C atoms
number o particles
amount ( in mol) n = ___
Avogadros constant, L Study ti
Rearranging and substituting values: The answer is recorded to 3 signifcant fgures, as this is
the precision o the data given by the examiner (1.50 mol).
1 .5 0  1 0 23
n( C O 2 ) = __
6.02  1 0 23 mol  1
= 0.2 49 mol Example 3
C alculate the amount ( in mol) o water molecules
Example 2 in 3 .01  1 0 22 ormula units o hydrated
C alculate the number o carbon atoms contained ethanedioic acid, H 2 C 2 O 4 2 H 2 O .
in 1 .5 0 mol o glucose, C 6 H 1 2 O 6 .
Solution
Solution  For every 1 ormula unit there are 2 molecules
 1 molecule o glucose contains 6 atoms o o water.
carbon, 1 2 atoms o hydrogen, and 6 atoms  1 mol o a substance contains Avogadros
o oxygen. number o particles.
 1 mol o glucose contains 6 mol o C atoms.

16
 1 .2 Th e m Ole cOn cepT

Thereore, Example 6
number o particles
amount ( in mol) n = ___ C alculate the number o chlorine atoms in a
Avogadros constant, L
6.00 mg sample o the anti-cancer drug cisplatin,
3 .01  1 0 22
n( H 2 C 2 O 4 2 H 2 O ) = __ = 0.05 00 mol cis- diamminedichloroplatinum( II) , Pt( NH 3 ) 2 C l 2 .
6.02  1 0 23
n( H 2 O ) = 2  0.05 00 mol = 0.1 00 mol Solution
 First convert the mass in mg to g.
uits  Next fnd the amount in mol by calculating
Amount of substance n has the units mol the molar mass.
n = ___ m
 Finally remember that there are 2 mol o
molar mass
chlorine atoms in every mol o cisplatin.
Mass m has the units g; molar mass has the units g mol 1 .
6.00 mg = 6.00  1 0 3 g
n[Pt( NH 3 ) 2 C l 2 ]
Example 4 6.00  1 0  3 g
= ____
C alculate the amount ( in mol) in 8.80 g o carbon 1 95 .08 + 2 ( 1 4.01 ) + 6( 1 .01 ) + 2 ( 3 5 .45 )
dioxide, C O 2 .
= 2 .00  1 0  5 mol

Solution n(C l) = 2  2.00  1 0  5 mol = 4.00  1 0 5 mol

m
n( C O 2 ) = __ number o atoms ( C l) = 4.00  1 0  5 mol 
molar mass
6.02  1 0 23 mol  1
8.80 g
= ___ = 2 .41  1 0 1 9
1 2 .01 + 2 ( 1 6.00) g mol  1
= 0.2 00 mol

H H Cl
Example 5
C alculate the mass in g o 0.01 2 0 mol o suluric
N
acid, H 2 SO 4.
H Pt H
Solution
C alculate the molar mass o H 2 S O 4 and substitute N
into the equation: Cl
H H
mass ( g) = n( H 2 S O 4)  Mr( H 2 SO 4)
= 0.01 20 mol  [2(1 .01 ) + 32.07 +
4 (1 6.00) ] g mol1
Figure 5 The anti-cancer drug cisplatin
= 1 .1 8 g

Qik qstios
1 Calculate the amount (in mol) in each of the following masses:
a) 8.09 g of aluminium
b) 9.8 g of sulfuric acid
) 25.0 g of calcium carbonate
d) 279.94 g of iron(III) sulfate.
17
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

2 Calculate the mass (in grams) in each of the following:

a) 0.150 mol of nitrogen, N 2
b) 1.20 mol of sulfur dioxide, SO 2
c) 0.710 mol of calcium phosphate, Ca 3 (PO 4 ) 2
d) 0.600 mol of ethanoic acid, C2 H 4O 2 .
3 Calculate the number of particles present in the following:
a) 2.00 mol of vanadium, V
b) 0.200 mol of sodium chlorate(VII) , NaClO 4
c) 72.99 g of iron(III) chloride, FeCl 3
d) 4.60 g of nitrogen(IV) oxide.

Experimental empirical and molecular formula

determination
The term empirical describes inormation that is derived through
observation and/or investigation, using scientifc methods. Chemical
laboratories involved in medical research and development, manuacturing,
or ood production will oten carry out analyses o the composition o a
compound in processes that may be either qualitative or quantitative in
nature.
Qualitative analysis ocuses on determining which elements are
present in a compound. It could also veriy the purity o the substance.
Quantitative analysis enables chemists to determine the relative masses
o elements which allows them to work out their exact composition.
The empirical formula o a compound is the simplest whole-number ratio
o atoms or amount (in mol) o each element present in a compound. The
molecular formula is the actual number o atoms or amount (in mol) o
elements in one structural unit or one mole o the compound, respectively.
Thereore the molecular ormula is a whole-number ratio o the empirical
ormula. Sometimes the empirical ormula is the same as the molecular
ormula. Table 7 shows some examples.
For ionic compounds the empirical ormula is the same as the ormula
or the compound, since the ormula represents the simplest ratio o ions
within the structure ( fgure 6) .

Substanc molcular forula epirical forula

ethane C2 H 6 CH 3
water H 2O H 2O
hydrogen peroxide H2O2 HO
butanoic acid C4 H 8 O 2 C2 H 4O
Figure 6 Sodium fuoride, NaF has a 1:1 ratio o glucose C6 H 1 2 O 6 CH 2 O
ions in its empirical ormula. It is used in some
countries to enhance the health o teeth Table 7 Some examples o molecular and empirical ormulae

18
 1 .2 Th e m Ole cOn cepT

Worked examples: percentage composition by mass

You can use your understanding o how to calculate S ometimes multiplication is needed to convert the
the molar mass o a compound to calculate the ratio to whole numbers:
percentage by mass o elements in a compound.
example 1 1 :1 .2 5 Multiply each side by 4:
4( 1 ) :4( 1 .2 5 )  4:5
Example 1
example 2 1 :1 .3 3 Multiply each side by 3 :
C alculate the percentage by mass o sulur in
3 ( 1 ) :3 ( 1 .3 3 )  3 :4
suluric acid, H 2 S O 4.

Solution Study ti

A r( S ) Empirical formulae are based on experimental
% sulur = _  1 00% data; those for example 2 would likely have been
M r( H 2 SO 4)
3 2 .07 determined by a combustion reaction. The value
= ___  1 00%
2 ( 1 .01 )  ( 3 2 .07)  4( 1 6.00) of 3.97 rather than 4 for hydrogen comes from
= 32 .69%
experimental error.

I you have a compound o unknown ormula

but you know the percentage composition by Example 3
mass o the elements present, you can calculate Upon analysis, a sample o an acid with a molar
the empirical ormula and, in some cases, the mass o 1 94.1 3 g mol 1 was ound to contain
molecular ormula. 0.2 5 g o hydrogen, 8.0 g o sulur, and 1 6.0 g o
oxygen. D etermine the empirical ormula and the
Example 2 molecular ormula.
D etermine the empirical ormula o an organic 8.0 0.2 5
n( S) = _ = 0.2 5 _ = 1
compound that contains 75 % carbon and 2 5 % 3 2 .07 0.2 5
hydrogen by mass. 1 6.0 1 .0
n( O ) = _ = 1 .0 _ = 4
1 6.00 0.2 5
Solution 0.2 5
n( H) = _ = 0.2 5
0.2 5
_ = 1
The f rst step is to determine the ratio o 1 .01 0.2 5
n( C ) to n( H) : Thereore the empirical ormula is HS O 4.
% composition
relative amount o substance = __ To calculate the molecular ormula, calculate the
molar mass
75
n( C ) = _ = 6.2 4 empirical ormula mass and determine how many
1 2 .01
empirical ormulae make up the molar mass.
25
n( H) = _ = 2 4.75
1 .01 ___ molar mass
empirical ormula mass
Now take the smallest quotient ( 6.2 4) . Use this as
1 94.1 3 1 94.1 3
the divisor to determine the lowest whole- number = ___ = _ = 2
ratio o the elements: 1 .01 + 3 2 .07 + 4( 1 6.00) 97.08
6.2 4
_
carbon = 1 The molecular ormula o the acid is 2 ( HS O 4) or
6.2 4
2 4.75 H 2 S 2 O 8 . This compound is called peroxodisuluric
hydrogen _ = 3 .97
6.2 4 acid ( f gure 7) .

B ecause the percentage composition is O

O
O H
experimentally determined it is acceptable to O
S
round to the nearest whole number i the number S
is close to a whole number. Thereore the simplest H O
O O O
whole- number ratio o carbon to hydrogen is 1 :4
and the empirical ormula is C H 4. Figure 7 Molecular model of peroxodisulfuric acid

19
1 S TO I c h I O m e T r I c r e l AT I O n S h I p S

1.3 ratig asss ad vous

Understandings Applications and skills
 Reactants can be either limiting or excess.
 Solution o problems relating to reacting
 The experimental yield can be diferent rom quantities, limiting and excess reactants,
the theoretical yield. theoretical, experimental, and percentage yields.
 Avogadros law enables the mole ratio o  Calculation o reacting volumes o gases using
reacting gases to be determined rom volumes Avogadros law.
o the gases.  Solution o problems and analysis o
 The molar volume o an ideal gas is a constant graphs involving the relationship between
at speci ed temperature and pressure. temperature, pressure, and volume or a  xed
 The molar concentration o a solution is mass o an ideal gas.
determined by the amount o solute and the  Solution o problems relating to the ideal gas
volume o solution. equation.
 A standard solution is one o known  Explanation o the deviation o real gases rom
concentration. ideal behaviour at low temperature and high
pressure.
 Obtaining and using experimental values to
calculate the molar mass o a gas rom the ideal
gas equation.
 Solution o problems involving molar
concentration, amount o solute, and volume o
solution.
 Use o the experimental method o titration to
calculate the concentration o a solution by
reerence to a standard solution.

Nature of science
 Making careul observations and obtaining evidence or scienti c theories  Avogadros initial
hypothesis.

Stoichiometry
A balanced chemical equation provides inormation about what the
reactants and products are, their chemical symbols, their state o matter,
and also the relative amounts o reactants and products. C hemical
equations may also include specif c quantitative data on the enthalpy
o the reaction ( see topic 5 ) . S toichiometry is the quantitative method
o examining the relative amounts o reactants and products. An
understanding o this is vital in industrial processes where the ef ciency
o chemical reactions, particularly the p ercentage yield, is directly
linked to the success and prof tability o the organization.
20
 1 . 3 re AcTI n g m ASS e S An d vO lu m e S

From a balanced chemical equation the coefcients can be interpreted

TOK
as the ratio o the amount, in mol, o reactants and products. This is the
equation or the reaction used or the manuacture o ammonia in the When comparing the eight
Haber process ( see topic 7) : areas o knowledge (AOK),
N 2 ( g) + 3 H 2 ( g)  2 NH 3 ( g)  H =  92 .2 2 kJ Mathematics involves
knowledge and understanding
It shows that one molecule o nitrogen gas and three molecules o
o the highest certainty. The
hydrogen gas combine in an exothermic reaction to produce two
Nature o Science (NOS)
molecules o ammonia. However, when setting up a reaction the reactants
inorms us that experimental
may not always be mixed in this ratio  their amounts may vary rom the
data is oten quantitative
exact stoichiometric amounts shown in the balanced chemical equation.
and mathematical analysis
is required to enable precise
The limiting reagent descriptions, predictions
E xperimental designers o industrial processes use the concept o a and, eventually, laws to be
limiting reagent as a means o controlling the amount o products developed. Mathematics
obtained. The limiting reagent, oten the more expensive reactant, will is an integral part o
be completely consumed during the reaction. The remaining reactants scientic endeavours. The
are present in amounts that exceed those required to react with the use o numbers and an
limiting reagent. They are said to be in excess. understanding o the mole
concept have helped develop
It is the limiting reagent that determines the amount o products ormed. Chemistry into a physical
Using measured, calculated amounts o the limiting reagent enables science. Why is mathematics
specifc amounts o the products to be obtained. The assumption made so efective in describing the
here is that the experimental or actual yield o products achieved is natural world?
identical to the theoretical or predicted yield o products. This is rarely the
IB Diploma Chemistry Syllabus
case. Much eort is ocused on improving the yield o industrial processes,
as this equates to increased profts and efcient use o raw materials.

Worked example: determining the limiting reagent

In the manuacture o phosphoric acid, m
n( O 2 ) = _
molten elemental phosphorus is oxidized M
and then hydrated according to the ollowing 1 00.0 g
chemical equation: = __ 1
= 3 .1 2 5 mol
2 ( 1 6.00) g mol
P 4( l) + 5 O 2 ( g) + 6H 2 O ( l)  4H 3 PO 4( aq) P4(l) + 5O 2 (g) + 6H 2 O(l)  4H 3 PO 4(aq)
I 2 4.77 g o phosphorus reacts with 1 00.0 g o ______________________________
oxygen and excess water, determine the limiting
reagent, the amount in mol o phosphoric( V) acid M( g mol- 1 ) 1 23.88 32.00
produced ( the theoretical yield) and the mass, ______________________________
in g, o phosphoric acid. m/g 24.77 1 00.0 excess
______________________________
Solution
n i/mol 0.200 3.1 25 excess 0
The amount in mol o phosphorus and oxygen
______________________________
is determined using the working method rom
sub-topic 1 .2 : n /mol ______________________________
m To determine the amount o oxygen that will
n( P 4) = _
M react with the phosphorus we can use a cross-
2 4.77 g
= __ = 0.2 000 mol multiplication technique:
4( 3 0.97) g mol  1

21
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

P4 : O 2 P 4( s) + 5 O 2 ( g) + 6H 2 O ( l)  4H 3 PO 4( aq)
1 :5 _________________________________
M(g mol-1 ) 1 2 3 .88 3 2 .00
0.2 00 : 
_________________________________
1   = 0.2 000  5
m/g 2 4.77 1 00.0 excess
5
 = 0.2 000  _ _________________________________
1
n i/mol 0.2 000 3 .1 2 5 excess 0
 = 1 .000 mol
_________________________________
Therefore 0.2 000 mol of phosphorus requires
n f/mol 0.0 2 .1 2 5 excess 0.8000
1 .000 mol of oxygen to completely react. There is
_________________________________
3 .1 2 5 mol of oxygen available so this is in excess
and phosphorus is the limiting reagent. All the The mass of phosphoric acid, H 3 PO 4 produced can
phosphorus will be consumed in the reaction and be determined by multiplying n f by Mr:
3 .1 2 5  1 .000 = 2 .1 2 5 mol of oxygen will remain
after the reaction comes to completion. m= M n

The limiting reagent dictates the amount of = [3 ( 1 .01 ) + 3 0.97 + 4( 1 6.00) ] g mol - 1
phosphoric acid produced. The mole ratio is used  0.8000 mol = 78.40 g
to determine the amount of product, in mol. Four This value represents the theoretical yield of
times the amount in mol of phosphoric acid will be phosphoric acid. Theoretical yields are rarely
produced compared with the amount of phosphorus: achieved in practice.

Quick questions
1 Butane lighters work by the release and combustion c) Calculate the mass, in g, of K2 CO 3 produced.
of pressurized butane: d) Calculate the mass, in g, of O 2 produced.
2C4 H 1 0 (g) + 13O 2 (g)  8CO 2 (g) + 10H 2 O(l) 4 A solution of 155 g of potassium iodide, KI is added to
Determine the limiting reagent in the following a solution of 175 g of nitric acid, HNO 3 . The acid acts
reactions: as an oxidizing agent.
a) 20 molecules of C4 H 1 0 and 100 molecules of O 2 6KI(aq) + 8HNO 3 (aq)  6KNO 3 (aq) + 2NO(g)
+ 3I 2 (s) + 4H 2 O(I)
b) 10 molecules of C4H 10 and 91 molecules of O 2
c) 0.20 mol of C4H 1 0 and 2.6 mol of O 2 a) Deduce which reagent is in excess.
d) 8.72 g of C4H 1 0 and 28.8 g of O 2 b) Determine how many grams of this reactant will
remain unreacted.
2 Two aqueous solutions, one containing 5.3 g of sodium
carbonate and the other 7.0 g of calcium chloride, are c) Determine how many grams of nitrogen
mixed together. A precipitation reaction occurs: monoxide, NO will be produced.
5 Chlorine gas is produced by the reaction of
Na 2 CO 3 (aq) + CaCl 2 (aq)  2NaCl(aq) + CaCO 3 (s)
hydrochloric acid, and the oxidizing agent
Determine the limiting reagent and the mass, in g, of manganese(IV) oxide, MnO 2 :
precipitate formed (the theoretical yield) .
MnO 2 (s) + 4HCl(aq)  MnCl 2 (aq) + Cl 2 (g) + 2H 2 O(l)
3 The oxygen required in a submarine can be produced
by a chemical reaction. Potassium superoxide, KO 2 At 273.15 K and 100 kPa, 58.34 g of HCl reacts with
reacts with carbon dioxide, CO 2 to produce oxygen and 0.35 mol of MnO 2 to produce 7.056 dm 3 of chlorine gas.
potassium carbonate, K2 CO 3 . a) Deduce the limiting reagent.
a) Write the balanced chemical equation for this reaction. b) Calculate the theoretical yield of chlorine.
b) 28.44 g of KO 2 reacts with 22.00 g CO 2 . Deduce
the limiting reagent.

22
 1 . 3 re AcTI n g m ASS e S An d vO lu m e S

Theoretical and experimental yields

The balanced chemical equation represents  changes in reaction conditions, such as
what is theoretically possible when a reaction is temperature and pressure
carried out under ideal conditions. It allows the  reverse reactions consuming products in
expected amount o products to be calculated  the equilibrium systems
theoretical yield.
 the existence o side-reactions due to the
S cientists in industry work to maximize the yield presence o impurities.
o reactions and maximize profts. However, under
To calculate the p ercentage yield a comparison
experimental conditions and especially in large-
is made between the theoretical yield and the
scale processes, many actors result in a reduced
actual amount produced in the process  the
yield o products. These actors could include:
experimental yield:
 loss o products rom reaction vessels
experimental yield
 impurity o reactants % yield = __  1 00%
theoretical yield

Worked example: determining theoretical yield

Respirators are being used increasingly with S tep 2 : Using mole ratios, determine the limiting
concern or workplace saety and rising levels o reagent.
environmental pollution. Iodine( V) oxide, I 2 O 5
I2 O 5 : C O
reacts with carbon monoxide, C O and can be used
to remove this poisonous gas rom air: 1 :5

I2 O 5 ( s) + 5 C O ( g)  I 2 ( g) + 5 C O 2 ( g) 0.3 000 : 
1 00.0 g o I2 O 5 1   = 0.3 000  5
reacts with 3 3 .6 g 5
 = 0.3 000  _
o C O . C alculate 1
the theoretical  = 1 .5 00 mol
yield o carbon The reaction o 0.3000 mol o I2 O 5 requires 1 .50 mol
dioxide and given o CO or completion. However, only 1 .20 mol o CO
an experimental is available; thereore this is the limiting reagent.
yield, in mol, o
0.900 mol C O 2 , The ratio o limiting reagent C O to product C O 2
calculate the Figure 1 A chemist wearing a is 5 :5 or 1 :1 . The number o mol o C O 2 that is
percentage yield. respirator for safety theoretically possible is thereore 1 .2 mol.
It was ound that 0.90 mol or 3 9.61 g o C O 2 was
Solution produced. This is the exp erimental yield.
S tep 1 : C alculate the initial amount in mol o
To determine the percentage yield o C O 2 we frst
reactants and determine the limiting reagent:
need to calculate the theoretical yield o C O 2 :
m
n( I 2 O 5 ) = _ m= M n
M
1 00.0 g = [1 2 .01 + 2 ( 1 6.00) ] g mol  1  1 .2 0 mol
= ___
2(1 26.90) + 5(1 6.00) g mol 1 = 5 2 .8 g
= 0.2996 mol Then:
m
n( C O ) = _ experimental yield
% yield = __  1 00%
M
33.6 g theoretical yield
= ___
1 2.01 + 1 6.00 g mol 1 39.61 g
= _  1 00% = 75 .0%
= 1 .2 0 mol 5 2 .8 g

23
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

Quick questions
1 Acetylsalicylic acid, also known as aspirin, C9 H 8 O 4 is 2NaHCO 3 (s)  Na 2 CO 3 (s) + H 2 O(l) + CO 2 (g)
synthesized by reacting salicylic acid, C7 H 6 O 3 with
I a 1.68 g sample o sodium hydrogen carbonate is
acetic anhydride, C4H 6 O 3 :
heated, calculate the mass, in g, o sodium carbonate
C7 H 6 O 3 (s) + C4 H 6 O 3 (l)  C9 H 8 O 4(s) + C2 H 4O 2 (l) produced.

O O 3 Sulur trioxide, SO 3 can be produced in the ollowing

O
O
H CH 3 O H O two-step reaction:
+O + H3C
OH CH 3 O OH 4FeS 2 (s) + 11O 2 (g)  2Fe 2 O 3 (s) + 8SO 2 (g)
O
O CH3 2SO 2 (g) + O 2 (g)  2SO 3 (g)
30.0 g o iron disulfde (pyrite) , FeS 2 reacts in the
a) Calculate the theoretical yield, in g, o aspirin presence o excess oxygen to completion.
when 3.0 g o salicylic acid is reacted with 4.0 g o a) Calculate the theoretical yield, in g, o sulur
acetic anhydride. trioxide.
b) I the experimental yield o aspirin is 3.7 g, b) I an experimental yield o 28.0 g o sulur
calculate the percentage yield. trioxide is achieved, deduce the percentage
2 The thermal decomposition o sodium hydrogen yield.
carbonate, NaHCO 3 results in a 73.8% yield o sodium
carbonate, Na2 CO 3 :

Avogadros law and the molar volume of a gas

The kinetic theory of gases is a model used to explain and predict the
behaviour o gases at a microscopic level. The theory is based upon a
number o p ostulates or assumptions that must be true or the theory
to hold. These postulates are:
1 Gases are made up o very small particles, separated by large
distances. Most o the volume occupied by a gas is empty space.
2 Gaseous particles are constantly moving in straight lines, but random
directions.
3 Gaseous particles undergo elastic collisions with each other and the
walls o the container. No loss o kinetic energy occurs.
4 Gaseous particles exert no orce o attraction on other gases.
Under conditions o standard temperature and pressure, an ideal gas
The SI unit o pressure is obeys these postulates and the equations that ollow rom the kinetic
the pascal (Pa) , N m  2 . Many theory. At high temperature and low pressure, the signifcance o any
other units o pressure orces o attraction between the gas molecules is minimized  there is a
are commonly used in high degree o separation and they act in a way that adheres to the ideal
dierent countries, including gas model.
the atmosphere (atm) ,
However, at high pressure and low temperature the particles o a gas
millimetres o mercury
move more slowly and the distances between the particles decrease.
(mm Hg) , torr, bar, and
Intermolecular attractions ( sub- topic 4. 4) become signifcant and
pounds per square inch
eventually the gas can liquey. These responses to changing conditions
(psi) . The bar (10 5 Pa) is now
mean that gases can depart rom ideal gas behaviour and exhibit the
widely used as a convenient
behaviour o real gases.
unit, as it is very close to
atmospheric pressure, 1 atm. The early postulates o the kinetic theory were explained in quantitative
terms by scientists such as Robert B oyle, Edme Mariotte, Jacques C harles,
and Joseph Louis Gay-Lussac.
24
 1 . 3 re AcTI n g m ASS e S An d vO lu m e S

In 1 8 0 6 , Gay- Lussac proposed that the relationship between the

volumes o reacting gases and the products could be expressed as a Sty tips
ratio o whole numbers. Physical constants and unit
There are many important gas- phase reactions and the gas laws conversions can be found in
and Avogadros law enable us to understand their behaviour and the Data booklet. The molar
examine gaseous systems quantitatively. The models used to explain volume of an ideal gas is
the behaviour o gases are simple to apply. An important physical found in section 2.
property o a gas is its p ressure, the orce exerted by a gas as its
particles collide with a surace.
Imagine taking a mass numerically equal to the molar mass o dierent
gases and using each to infate a balloon. Under the same conditions o
temperature ( 0 C /2 73 K) and pressure ( 1 00kPa) the balloons will have
the same volume ( gure 2 ) . These particular temperature and pressure
conditions are known as standard temp erature and p ressure, S TP.

H2 He CH 4 N2 O2 Cl 2

2.02 g mol -1 4.00 g mol -1 16.05 g mol -1 28.02 g mol -1 32.00 g mol -1 70.90 g mol -1
Figure 2 The molar volume of any gas is identical at a given temperature and pressure
Figure 3 Amedeo Avogadro
3 1 (17761856) proposed in 1811
At S TP the balloons will have identical volumes o 2 2 . 7 dm mol .
that equal volumes of any gas
This is the m olar volum e o f an ideal gas and it is constant at a at the same temperature and
given temperature and pressure. E ach balloon contains 1 mol o the pressure contain the same number
gas so it contains 6 . 0 2  1 0 2 3 atoms or molecules o the gas. This of molecules
relationship is known as Avogadros law: equal volumes o any gas
measured at the same temperature and pressure contain the same
number o molecules.
Avogadros law simplies stoichiometric calculations involving reacting
gases. The coecients o a balanced chemical equation involving gases
correspond to the ratio o volumes o the gases ( gure 4) .

C 3 H 8 (g) + 5O 2 (g) 3CO 2 (g) + 4H 2 O(l)

Figure 4 Volumes of gases obey Avogadros law

25
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

Quick question Worked examples: Avogadros law

Ammonium carbonate
decomposes readily when
Example 1
heated: C alculate n( O 2 ) ound in a 6.73 dm 3 sample o oxygen gas at S TP.
(NH 4) 2 CO 3 (s)  2NH 3 (g) 1 mol O 2 occupies 2 2 .7 dm 3 at S TP
+ CO 2 (g) + H 2 O(l)
Determine the volume, in
Solution
dm 3 , of the individual gases 6.73 dm 3
n( O 2 ) = _3 = 0.2 96 mol
produced on decomposition 2 2 .7 dm
of 2.50 mol of ammonium
carbonate. Example 2
The hydrogenation o ethyne, C 2 H 2 involves reaction with hydrogen
gas, H 2 in the presence o a fnely divided nickel catalyst at 1 5 0 C .
The product is ethane, C 2 H 6 :
C 2 H 2 ( g) + 2 H 2 ( g)  C 2 H 6 ( g)
When 1 00 cm 3 o C 2 H 2 reacts with 2 5 0 cm 3 o H 2 , determine the
volume and composition o gases in the reaction vessel.

Solution
According to Avogadros law, or every 1  molecule o ethyne and
2  molecules o hydrogen, 1  molecule o ethane will be ormed.
Looking at the volumes reveals that only 2 00 cm 3 o the hydrogen is
required, and that 1 00 cm 3 o ethane will be ormed. The fnal mixture
o gases contains both ethane and unreacted hydrogen:
C 2 H 2 (g) + 2H 2 (g)  C 2 H 6(g)
initial volume, Vi/cm 3 1 00 250 0
fnal volume, V/cm 3 0 50 1 00

Ater reaction there will be 1 50 cm 3 o gases in the vessel comprising

50 cm3 o H 2 and 1 00 cm 3 o C 2 H 6 .

The gas laws

The gas laws are a series o relationships that predict the behaviour o a fxed
mass o gas in changing conditions o temperature, pressure, and volume.
You have seen that Avogadros law states that the molar volume (2 2.7 dm 3
at STP) is independent o the composition o the gas.

Boyles law
Robert B oyle (1 62 71 691 ) discovered that when the temperature remains
constant, an inverse relationship exists between pressure and volume.
Gases contained in smaller volumes will have an increased number o
collisions with the surace o the container, so exert a higher pressure.
The relationship between pressure p and volume V can be expressed as:
1
p_ or V1 p 1 = V2 p 2
V

26
 1 . 3 re AcTI n g m ASS e S An d vO lu m e S

where V1 and p 1 represent the initial volume and pressure and V2 and p 2
the fnal volume and pressure, respectively.
pressure, P/Pa

pressure, P/Pa
volume, V/dm 3 1/V / dm 3
Figure 5 Boyles law: the pressure of a gas is inversely proportional to the volume at constant temperature

Worked example: Boyles law

A helium-flled weather balloon is designed to rise to altitudes as high
as 37 000 m. A balloon with a volume o 5 .5 0 dm 3 and a pressure
o 1 01 kPa is released and rises to an altitude o 35 00 m where the
atmospheric pressure is 68 kPa. C alculate the new volume,
in dm 3 . It is assumed that the temperature and amount, in mol,
remain constant.

Solution
First make a summary o the data:
p 1 = 1 01 kPa
V1 = 5 .5 0 dm 3
p 2 = 68 kPa
V2 =  dm 3
Making V2 the subj ect o the expression:
p1
V2 = V1  _
p2
1 01 kPa
= 5 .5 0 dm 3  _
68 kPa
= 8.1 7 dm 3

Charless law
Jacques C harles ( 1 7461 82 3 ) investigated the relationship between
the temperature and volume o a gas. He discovered that or a fxed
mass o gas at a constant pressure, the volume V o the gas is directly

27
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

proportional to the absolute temperature T in kelvin. This relationship

Absolute zero can be expressed as:
We saw in sub-topic 1.1 V1 V2
that absolute zero is zero V  T or _ = _
T1 T2
on the kelvin scale, 0 K
(-273.15 C) . The idea o When an infated balloon is placed into a container o liquid nitrogen
negative temperatures and (boiling point 1 96 C) , the average kinetic energy o the particles decreases.
the existence o a minimum The gaseous particles collide with the internal wall o the balloon with less
possible temperature had requency and energy and it begins to defate  the volume reduces. I the
been widely investigated balloon is then removed rom the liquid nitrogen and allowed to return to
by the scientifc community room temperature the balloon will reinfate.
beore Lord Kelvins time
(18241907) . Kelvin stated
that absolute zero is the
temperature at which molecular
motion ceases. According to
Charless law, i the temperature
o a system was to double rom
10 K to 20 K, the average kinetic
energy o the particles would
double and the volume would
correspondingly double.

Figure 6 Reducing the temperature reduces the average kinetic energy of the
particles of a gas, and the volume reduces
volume, V

Worked example: Charless law

A glass gas syringe contains 76.4 cm 3 o a gas at 2 7.0 C . Ater running
ice- cold water over the outside o the gas syringe, the temperature
temperature, T (K) o the gas reduces to 1 8.0 C . C alculate the new volume, in cm 3 ,
occupied by the gas.
Figure 7 Charless law: the volume of a
gas is directly proportional to absolute
temperature at constant pressure
Solution
V1 = 76.4 cm 3
T1 = 2 7.0 + 2 73 .1 5 = 3 00.1 5 K
V2 =  cm 3
T2 = 1 8.0 + 2 73 .1 5 = 2 91 .1 5 K
V1
_ V2
= _
T1 T2
V1  T2
V2 = _
T1

= 74.1 cm 3

28
 1 . 3 re AcTI n g m ASS e S An d vO lu m e S

Gay-Lussacs law
Having established gas laws stating that pressure is inversely Collaboration
proportional to volume at constant temperature and that volume The scientifc community
is directly proportional to temperature at constant pressure, the is highly collaborative.
remaining relationship involves pressure and temperature, at Evidence that is undamental
constant volume. to understanding is oten
challenged, tested, and
Gay- Lussacs ( 1 7781 85 0) work with ideal gases led him to the
utilized by other scientists to
understanding that when the volume o a gas is constant, the pressure
develop new understanding
o the gas is directly proportional to its absolute temperature. The
and investigate the
relationship can be expressed as:
possibility o developing
p1 p2 new general laws.
p  T or _ = _
T1 T2

Figure 8 demonstrates that when the temperature reaches absolute zero

( 0 K) , the kinetic energy o the ideal gas particles is zero and it exerts
no pressure. As the temperature increases, the particles collide with
the walls o the container with increased orce and requency, causing

pressure P
increased pressure.

The combined gas law

absolute
The three gas laws, C harless law, B oyles law, and Gay-Lussacs law, are zero, 0 K
combined in one law called the combined gas law. For a fxed amount
o gas, the relationship between temperature, pressure, and volume is:
temperature T
p 1 V1 p 2 V2
_ = _ Figure 8 Gay-Lussacs law: the pressure of
T1 T2 a gas is directly proportional to absolute
temperature at constant volume
The ideal gas equation
The ideal gas equation describes a relationship between pressure,
volume, temperature, and the amount, in mol, o gas particles. Having
established that pressure and volume are inversely proportional and that
both pressure and volume have a direct relationship with the temperature
o a gas and the amount o gas particles, the ideal gas equation combines
these interrelationships:
pV = nRT

Th as ostat a th its of th ia as qatio
R is called the as ostat and it has a value of 8.31 J K1 mol 1 . This value is
provided in section 2 of the Data booklet.
The inclusion of R in the ideal gas equation requires the following units: p (Pa) ,
V (m 3 ) , and T (K) . Note that 1 Pa = 1 J m 3 ; this allows you to see how the units in
the ideal gas equation are balanced:
p(J m 3 )  V(m 3 ) = n(mol)  R(J K1 mol 1 )  T (K)
1 dm 3 = 1  10 3 m 3 .

29
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

TOK
Worked example: using the ideal gas
The ideal gas equation is a
model which is the product
equation to calculate volume
o a number o assumptions C alculate the volume, in m 3 , o a balloon flled with 0.400 mol o
about the ideal behaviour hydrogen gas at a temperature o 2 2 .90 C and a pressure o 1 .2 0 Pa.
o gases. These have been
discussed earlier in the
Solution
topic. Scientifc models C onvert all data to SI units to enable the use o R as 8.3 1 J K 1 mol 1 .
are developed to explain p = 1 .2 0 Pa
observed behaviour. In the
development o models what V =  m3
role do imagination, sensory n = 0.400 mol
perception, intuition, or the
R = 8.3 1 J K  1 mol  1
acquisition o knowledge in
the absence o reason play? T = 2 2 .90 + 2 73 .1 5 = 2 96.05 K

nRT
V= _p
real gases deviate rom
0.400 mol  8.3 1 J K  1 mol  1  2 96.05 K
ideal behaviour at very low = ____
temperature and high pressure. 1 .2 0 Pa
Under these conditions = 82 0 m 3
the orces between the gas
particles become signifcant,
and the gas gets closer to the
point where it will condense Worked examples: determining the molar
rom gas to liquid.
mass of a substance
An organic compound A containing only the elements carbon,
hydrogen, and oxygen was analysed.

Example 1: Empirical ormula

A was ound to contain 5 4.5 % C and 9.1 % H by mass, the remainder
being oxygen. D etermine the empirical ormula o the compound. [3]

Solution
5 4.5 4.5 4
n( C ) = _ = 4.5 4 _  2
1 2 .01 2 .2 8
9.1 9.0
n( H) = _ = 9.0 _  4
1 .01 2 .2 8
3 6.4 2 .2 8
_
n( O ) = _ = 2 .2 8 = 1
1 6.00 2 .2 8

The empirical ormula is C 2 H 4O .

Example 2: Relative molecular mass

A 0.2 30 g sample o A when vaporized had a volume o 0.0785 dm 3
at 95 C and 1 02 kPa. D etermine the relative molecular mass o A. [3]

30
 1 . 3 re AcTI n g m ASS e S An d vO lu m e S

Solution
pV = nRT

n = m/M

mRT
pV = _
M
mRT 0.2 3 0 g  8.3 1 J K  1 mol  1  3 68 K
M = _ = ____ = 87.9 g mol  1
pV 1 02  1 0 3 Pa  0.0785  1 0  3 m 3

Example 3: Molecular ormula Figure 9 A homogeneous mixture

is characterized by a constant
D etermine the molecular ormula o A using your answers
composition throughout
rom parts ( a) and ( b) . [1 ]

Solution
___ molar mass 87.8
= ___
empirical ormula mass 2 ( 1 2 .01 ) + 4( 1 .01 ) + ( 1 6.00)
87.8
= _2
44.06
molecular ormula = C 4H 8 O 2
IB , Nov 2 005

Concentration
In a typical laboratory the maj ority o reactions carried out are in
solution rather than in the gaseous phase. C hemists need to make up
solutions o known concentrations.
A solution is a homogenous mixture o a solute that has been dissolved in
a solvent. The solute is usually a solid, but could be a liquid or gas. When To make up solutions o known
the solvent is water the solution is described as an aqueous solution. concentration, volumes must
The molar concentration o a solution is defned as the amount (in mol)
be measured accurately.
o a substance dissolved in 1 dm 3 o solvent. 1 dm 3 = 1  litre (1 L) .
Apparatus used to do this
include burettes, pipettes and
amount o substance n/mol volumetric fasks.
concentration c/mol dm  3 = ___
volume o solution V/ dm 3

uits of otatio Parts per million (ppm) is not an SI unit but is oten used
Units o concentration include: or very dilute concentrations such as when measuring
pollutants (see sub-topic 9.1) .
 mass per unit volume, g dm 3
Concentration in mol dm 3 may also be reerred to as oaity,
 mol per unit volume, mol dm 3 and square brackets are sometimes used to denote molar
 parts per million (ppm) : one part in 1  10 6 parts. concentration, or example [MgCl 2 ] = 4.87  10 2 mol dm 3 .
1 ppm = 1 mg dm - 3

31
1 S TO I C H I O M E T R I C R E L AT I O N S H I P S

Worked examples: concentration calculations

Example 1: Molarity of solution Solution
-3
Calculate the concentration, in mol dm , o a n(C 8H5 O 4K) = V  [C 8H5 O 4K]
solution ormed when 0.475 g o magnesium
1 dm 3
chloride, MgCl2 is completely dissolved in water to  = 25 0 cm 3  _  1 .25 mol dm 3
1 000 cm 3
make a solution with a volume o 1 00 cm3 . = 0.3 1 3 mol
Solution m = n( C 8 H 5 O 4K)  M
First calculate n( MgC l 2 ) :
= 0.3 1 3 mol  [8( 1 2 .01 ) + 5 ( 1 .01 ) +
m 0.475 g
n( MgC l2 ) = _ = ___ 4( 1 6.00) + 3 9.1 0] g mol 1
M 24.31 + 2(35.45) g mol 1
= 63 .9 g
= 4.99  1 0 3 mol
Example 4: Concentration of standard
C onvert the volume in cm 3 to dm 3 :
solution
1 dm 3 A standard solution is prepared by dissolving
1 00 cm 3  _3 = 0.1 dm 3
1 000 cm 5 .3 0 g o sodium carbonate, Na 2 C O 3 in 2 5 0 cm 3 o
distilled water in a volumetric fask. A 1 0.0 cm 3
C alculate the concentration o the solution:
sample o this solution is removed by bulb
n 4.99  1 0  3 mol pipette and diluted with water to the nal volume
[MgC l 2 ] = _ = __ 3 o 0.1 00 dm 3 . C alculate the concentration, in
V 0.1 dm
mol dm 3 , o the diluted solution.
= 4.99  1 0  2 mol dm  3
Solution
Example 2: Concentration of ions First calculate n( Na 2 C O 3 ) in a 1 0.0 cm 3 sample o
D etermine the concentration, in mol dm - 3 o the the standard solution:
chloride ions in example 1 above.
m 1 0.0 cm 3
n( Na 2 C O 3 ) = _  _
Solution M 2 5 0 cm 3
5 .3 0 g
When solid MgCl2 is dissolved in water, the = ____
2 ( 2 2 .99) + 1 2 .01 + 3 ( 1 6.00) g mol  1
constituent ions are liberated:
1 0.0 cm 3
MgC l2 ( s)  Mg 2+ ( aq) + 2 C l  ( aq)  _3
2 5 0 cm
n 2 ( 4.99  1 0  3 mol)
[C l ] = _ = __ = 0.002 00 mol
V 0.1 dm 3
Finally calculate the concentration o the diluted
= 9.98  1 0  2 mol dm  3 solution in mol dm 3 :

Example 3: Mass of solute n 0.002 00 mol

[Na 2 C O 3 ] = _ = __
C alculate the mass, in g, o potassium hydrogen V 0.1 00 dm 3
phthalate, C 8 H 5 O 4K ( a primary standard) in
= 0.0200 mol dm  3
2 5 0 cm 3 o a 1 .2 5 mol dm - 3 solution.

32
 1 . 3 re AcTI n g m ASS e S An d vO lu m e S

Titrations
Quantitative analysis includes a range of laboratory techniques used
to determine the amount or concentration of an analyte. The results are An aayt is a substance
expressed as numerical values with units. that is being analysed by a
given analytical procedure.
Volumetric analysis is a quantitative technique used by chemists
involving two solutions. A titration involves a standard solution
of known concentration which is added to a solution of unknown
concentration until the chemical reaction is complete. The reaction
progress is monitored through colour changes using indicators
( topic 8) .

Qik qstios A staa sotio or piay

1 Calculate the mass, in g, o H 2 SO 4 required to prepare 500 cm 3 o a 2.0 mol dm  3 sotio is prepared using a
solution o suluric acid. volumetric fask. Solvent is
added to a high purity sample
2 A solution o aluminium bromide, AlBr3 is to be used in the laboratory during an
until the level o the solution
electrolyte investigation. Calculate the total number o ions present in 2.5 dm 3 o a
reaches the mark on the fask.
1.6 mol dm  3 solution o AlBr3 .

Worked example: acidalkali titration Sty tip

When solving quantitative
calculation problems involving
C alculate the volume, in dm 3 , of 0.3 90 mol dm  3 potassium concentrations and volumes
hydroxide, KO H solution that will neutralize 2 5 .0 cm 3 of 0.3 5 0 mol o solutions, the ocus is on
dm 3 sulfuric acid, H 2 S O 4. the amount, in mol, o the
2 KO H( aq) + H 2 S O 4( aq)  K 2 S O 4( aq) + 2 H 2 O ( l) substances reacting and their
relationship as shown by the
Solution mole ratios in the balanced
S tep 1 : C alculate the amount, in mol, of H 2 SO 4: chemical equation.

n( H 2 S O 4) = c  V
= 0.3 5 0 mol dm 3  0.02 5 0 dm 3
= 8.75  1 0 3 mol
S tep 2 : The mole ratio of acid:alkali is 1 :2 . Therefore 8.75  1 0 3 mol
of acid reacts with 2 ( 8.75  1 0 3 mol ) = 1 .75  1 0 2 mol of KO H.
not
S tep 3 : C alculate the volume of KO H:
In topic 9, we will introduce a
n general, simple-to-use ormula.
V=
c This ormula can also be used or
1 .75  1 0  2 mol the type o volumetric chemistry
V( KO H) = __ = 0.0449 dm 3
0.3 90 mol dm  3 question shown above.

33
11 S TO I C H I O M E T R I C R E L AT I O N S H I P S

Questions
1 E psom salts ( magnesium sulate) are commonly f) D etermine the amount, in mol, o
used as bath salts. However, the anhydrous Fe( NH 4) 2 ( S O 4) 2   xH 2 O and hence the
orm o the salt is a drying agent. To determine value o x. [2 ]
the water o hydration o Epsom salts, a 2 .5 0 g IB , May 2 008
sample o the salt was placed in a porcelain
evaporating dish and gently heated over a
B unsen burner fame until no urther changes 3 The equation or a reaction occurring in the
were observed. Table 8 shows the results. synthesis o methanol is:
C O 2 + 3 H2  C H3O H + H2O
description mass/g
mass of evaporating basin 24.10 What is the maximum amount o methanol
that can be ormed rom 2 mol o carbon
mass of evaporating basin + MgSO 4 xH 2 O 26.60 dioxide and 3 mol o hydrogen?
mass of evaporating basin after heating 25.32
A. 1 mol
Table 8 B . 2 mol
a) C alculate the mass, in g, o water C . 3 mol
evaporated rom the sample.
D . 5 mol [1 ]
b) C alculate the amount amount, in mol,
IB , May 2 006
o H 2 O .
c) C alculate the mass, in g, o MgS O 4.
d) C alculate the amount, in mol, o MgS O 4. 4 C alcium carbonate decomposes on heating as
e) C alculate the ratio o amount o shown below.
MgS O 4 : amount o H 2 O and deduce the C aC O 3  C aO + C O 2
value o x.
When 50 g o calcium carbonate are decomposed,
) State the ormula o the hydrated salt. 7 g o calcium oxide are ormed. What is the
percentage yield o calcium oxide?
2 The value o x in Fe( NH 4 ) 2 ( S O 4) 2  xH 2 O can A. 7%
be ound by determining the amount in B. 25%
mol o sulate in the compound. A 0. 982 g
C . 5 0%
sample was dissolved in water and excess
B aC l 2 ( aq) was added. The precipitate o D . 75 % [1 ]
B aS O 4 was separated and dried and ound to IB , November 2 006
weigh 1 . 1 7 g.
a) C alculate the amount, in mol, o B aS O 4 5 E thyne, C 2 H 2 , reacts with oxygen according to
in the 1 .1 7 g o precipitate. [2 ] the equation below. What volume o oxygen
b) C alculate the amount, in mol, o sulate in ( in dm 3 ) reacts with 0.40 dm 3 o C 2 H 2 ?
the 0.982 g sample o Fe( NH 4) 2 ( S O 4) 2   xH 2 O .
2 C 2 H 2 ( g) + 5 O 2 ( g)  4C O 2 ( g) + 2 H 2 O ( g)
[1 ]
c) C alculate the amount, in mol, o iron in the A. 0.40
0.982 g sample o Fe( NH 4) 2 ( S O 4) 2   xH 2 O . [1 ] B . 0.80
d) D etermine the mass, in g, o the ollowing C . 1 .0
present in the 0.982 g sample o D . 2 .0 [1 ]
Fe( NH 4) 2 ( SO 4) 2   xH 2 O :
IB , November 2 007
( i) iron ( ii) ammonium ( iii) sulate. [3 ]
e) Use your answer rom part ( d) to determine
the amount in mol o water present in the
0.982 g sample o Fe( NH 4) 2 ( S O 4) 2   xH 2 O . [2 ]

34
 QueSTIOn S

6 A fxed mass o an ideal gas has a volume o 1 0 A toxic gas, A, consists o 5 3 .8% nitrogen
800 cm 3 under certain conditions. The pressure and 46.2 % carbon by mass. At 2 73 K and
(in kPa) and temperature (in K) are both doubled. 1 .01  1 0 5 Pa, 1 .048 g o A occupies 462 cm 3 .
What is the volume o the gas ater these changes D etermine the empirical ormula o A.
with other conditions remaining the same? C alculate the molar mass o the compound
and determine its molecular structure. [3 ]
A. 2 00 cm 3
B . 800 cm 3 IB , sp ecimen p ap er 2 009
3
C . 1 600 cm
D . 3 2 00 cm 3 [1 ] 1 1 An oxide o copper was reduced in a stream
IB , May 2 005 o hydrogen. Ater heating, the stream o
hydrogen gas was maintained until the
apparatus had cooled. The ollowing results
7 Assuming complete reaction, what volume o were obtained.
0.2 00 mol dm 3 potassium hydroxide solution,
Mass o empty dish = 1 3 .80 g
KO H( aq) is required to neutralize 2 5 .0 cm 3
Mass o dish and contents beore heating =
o 0.2 00 mol dm 3 aqueous suluric acid,
2 1 .75 g
H 2 S O 4( aq) ?
Mass o dish and contents ater heating and
A. 1 2.5 cm 3 leaving to cool = 2 0.1 5 g
B . 2 5 .0 cm 3
a) Explain why the stream o hydrogen gas was
C . 5 0.0 cm 3 maintained until the apparatus cooled. [1 ]
D . 75 .0 cm 3 [1 ] b) C alculate the empirical ormula o the oxide
IB , May 2 007 o copper using the data above, assuming
complete reduction o the oxide. [3 ]
c) Write an equation or the reaction that
8 C opper metal may be produced by the reaction occurred. [1 ]
o copper( I) oxide and copper( I) sulfde
d) S tate two changes that would be observed
according to the below equation. [1 ]
inside the tube as it was heated. [2 ]
2 C u 2 O + C u 2 S  6C u + SO 2 IB , November 2 004
A mixture o 1 0.0 kg o copper( I) oxide and
5 .00 kg o copper( I) sulfde was heated until no
urther reaction occurred. 1 2 0.5 02 g o an alkali metal sulate is dissolved
in water and excess barium chloride solution,
a) D etermine the limiting reagent in this B aC l2 ( aq) is added to precipitate all the
reaction, showing your working. [3 ] sulate ions as barium sulate, B aSO 4( s) . The
b) C alculate the maximum mass o copper precipitate is fltered and dried and weighs
that could be obtained rom these masses 0.672 g.
o reactants. [2 ]
a) C alculate the amount ( in mol) o barium
IB , May 2 006 sulate ormed. [2 ]
b) D etermine the amount ( in mol) o the
9 An organic compound A contains 62 .0% by alkali metal sulate present. [1 ]
mass o carbon, 2 4.1 % by mass o nitrogen, the c) D etermine the molar mass o the alkali
remainder being hydrogen. metal sulate and state its units. [2 ]

a) D etermine the percentage by mass o d) D educe the identity o the alkali metal,
hydrogen and the empirical ormula o A. [3 ] showing your workings. [2 ]

b) Defne the term relative molecular mass. [2 ] e) Write an equation or the precipitation
reaction, including state symbols. [2 ]
c) The relative molecular mass o A is 1 1 6.
D etermine the molecular ormula o A. [1 ] IB , May 2 007

IB , November 2 006
35
11 S TO I C H I O M E T R I C R E L AT I O N S H I P S

1 3 Aspirin, one o the most widely used drugs in B . A student carried out this experiment three
the world, can be prepared according to the times, with three identical small brass nails,
equation given below. and obtained the ollowing results.
OH OCOCH3 Mass o brass = 0.45 6 g  0.001 g
O O H+
+ + CH3COOH Titre 1 2 3
C C
COOH H3C O CH3 COOH
Initial olume o 0.00 0.00 0.00
salicylic acid ethanoic anhydride aspirin ethanoic acid 0.100 mol dm 3
S2 O 3 2 ( 0.05 cm 3 )
A. A student reacted some salicylic acid
with excess ethanoic anhydride. Impure final olume o 28.50 28.60 28.40
solid aspirin was obtained by fltering the 0.100 mol dm 3
reaction mixture. Pure aspirin was obtained S2 O 3 2 ( 0.05 cm 3 )
by recrystallization. Table 9 shows the data volume added o 28.50 28.60 28.40
recorded by the student. 0.100 mol dm 3
Mass of salicylic acid used 3.15  0.02 g S2 O 3 2 ( 0.10 cm 3 )
Aerage olume 28.50
Mass of pure aspirin obtained 2.50  0.02 g
added o 0.100 mol
Table 9 dm 3 S 2 O 3 2
( 0.10 cm 3 )
i) D etermine the amount, in mol, o
salicylic acid, C 6 H 4( O H) C O O H, used. [2 ] Table 10
ii) C alculate the theoretical yield, in g, i) C alculate the average amount, in
o aspirin, C 6 H 4( O C O C H 3 ) C O O H. [2 ] mol, o S 2 O 3 2  added in step 3 . [2 ]
iii) D etermine the percentage yield o ii) C alculate the amount, in mol, o
pure aspirin. [1 ] copper present in the brass. [1 ]
iv) S tate the number o signifcant iii) C alculate the mass o copper in
fgures associated with the mass o the brass. [1 ]
pure aspirin obtained, and calculate
iv) C alculate the percentage by mass
the percentage uncertainty associated
o copper in the brass. [1 ]
with this mass. [2 ]
v) The manuacturers claim that the
v) Another student repeated the experiment
sample o brass contains 44.2 % copper
and obtained an experimental yield
by mass. D etermine the percentage
o 1 50%. The teacher checked the
error in the result. [1 ]
calculations and ound no errors.
C omment on the result. [1 ] IB , May 2 01 0

IB , May 2 009

1 4 B rass is a copper- containing alloy with many

uses. An analysis is carried out to determine the
percentage o copper present in three identical
samples o brass. The reactions involved in this
analysis are shown below.
S tep 1 : C u( s) + 2 HNO 3 ( aq) + 2 H + ( aq) 
C u 2+ ( aq) + 2 NO 2 ( g) + 2 H 2 O ( l)
Step 2: 4I (aq) + 2 C u 2+ (aq)  2 C uI(s) + I2 (aq)
Step 3: I2 (aq) + 2S 2 O 3 2 (aq)  2I (aq) + S 4O 62 (aq)

36