UNIT 3

Chemical pathways
Chemical analysis
AR EA OF STUDY 2 Organic chemical pathways
AR EA OF STUDY 1

AR E A OF STUDY 1
CHaPTeR 1

Introduction chemical analysis

CHaPTeR 2

Gravimetric analysis

CHaPTeR 3

Volumetric analysis

CHaPTeR 4

Instrumental methods of analysis chromatography

CHaPTeR 5

Instrumental methods of analysis spectroscopy

AR E A OF STUDY 2
CHaPTeR 6

Organic chemistry naming compounds

CHaPTeR 7

Organic pathways

CHaPTeR 8

Living chemistry

CHAPTER

Introduction chemical
analysis

You will examine:

the broad range of applications for chemical analysis

the difference between qualitative and quantitative analysis.
You will revise:

writing chemical equations

acidbase reactions
redox reactions
precipitation reactions
the mole
calculations based on chemical equations (stoichiometry)
dilution of solutions.

Explosives, weapons and drugs pose a

serious threat to the security of our airports
and the community. Samples and swabs
of the clothing and skin of passengers are
taken by airport security and analysed
using instrumental chemical analysis. One
machine, Ionscan, can trace minute
amounts of explosives and drugs. The
machine also tests for the starting materials
used in the production of these dangerous
chemicals. The qualitative analysis positively
identifies which dangerous chemicals
are discovered. The quantitative analysis
accurately determines how much of the
substances are present.

Where is chemical analysis

important?
To know accurately what chemicals are in something is a right that today is
taken for granted. This ranges from products that we buy to substances that
are found in the environment. Chemical analysis is used to provide us with
this information. It should be remembered, however, that these applications
of analytical chemistry are not exhaustive new areas and methods of
analysis are continually being discovered and developed.

Analysing consumer products

The Ionscan machine analyses

samples from clothing and skin
for illicit substances. It signals an
alarm if these substances are
found in sufficient quantities.

Todays consumers are much better educated and much more demanding
about the products that they buy. Consumers want high-quality products that
meet their specific wants and needs. For example, there is a wide range of
sports drinks and smoothies, each one designed to meet a particular dietary
requirement. The exact contents of each drink should be carefully analysed
and monitored for purity and quality.
Research and development in many areas continues to have an
impact. New prescription drugs, for example, are constantly being
evaluated and released for public consumption. Older ones are being
monitored as drug companies strive to obtain a competitive edge over
their rivals. Medical research may often lead to the realisation that
smaller amounts of a drug can perform the same function, usually
with fewer side effects.
Quality itself, or at least the perception of quality, has always been
a powerful selling point. Products such as Dynamo laundry powder
and Cussons Morning Fresh dishwashing liquid compete in their
respective markets on the basis of their quality. The consumer is
asked to evaluate such claims and decide between these and the multitude of other brands available in supermarkets. The competitive
nature of the marketplace means that a product must live up to the
claims made for it, and do so consistently, for it to become popular
with consumers. At the other end of the scale, the past few years have seen the
rise of the so-called budget brands, competing on a value for money basis.
In either case, both the manufacturer and the consumer have an obvious
interest in the chemical composition of the product, and would expect control
measures to be adequate and appropriate for maintaining its composition.
Control measures include process control (monitoring the steps in a chemical
manufacturing process) and quality control (monitoring the final product).

The environment
The word quality has also come to have an environmental meaning as
consumers become increasingly aware of the effects that their actions and
their numbers have on their surroundings. Governments have responded
to this pressure by enacting legislation and setting up agencies such as the
Environment Protection Authority (EPA). This means that many products now
have to meet stringent standards.
For example, manufacturers of detergents must now ensure that their products are biodegradable. The history of detergents shows that earlier products
were almost too good at producing a lather. Unused detergents in waste water
were often responsible for fouling rivers and sewage treatment plants with
large amounts of froth. This was because they could not be broken down by
the enzymes in bacteria, fungi and other organisms. Biodegradability is now
also a big advertising point as well as being a legal requirement.
CHAPTER 1 Introduction chemical analysis

Sport
A product is not always something that we buy in a bottle or a tube. The
International Olympic Federation (IOF) sells the Olympic Games as its
product, the Australian Football League (AFL) sells football, the Victorian
Racing Club (VRC) sells horseracing, and so on. For their own credibility, and
to gain public confidence, as well as to attract sponsors, it is in the interest of
these bodies to market a quality product. In recent years this has also come to
mean a drug-free product.

Table 1.1 Caffeine concentrations of doping samples from a recent

Olympic Games

Concentration (mg L1)

Distribution (%)

<0.01
0.011.000
1.0002.000
2.0003.000
3.0004.000
4.0005.000
5.0006.000
6.0007.000
7.0008.000
8.0009.000
9.00010.000
10.00011.000
11.00012.000
greater than 12.000

612 (38.2%)
427 (26.7%)
296 (18.5%)
124 (7.7%)
64 (4.0%)
30 (1.9%)
23 (1.4%)
8 (0.5%)
7 (0.4%)
4 (0.2%)
2 (0.1%)
2 (0.1%)
0
2 (0.1%)

Total

1601

Urine and swab analysis tests using instrumental analysis are routinely used to check
for banned substances and masking agents. Racehorses are tested before and after a
race.

UNIT 3 Chemical pathways

Law and government

Chemical analysis is important
in many areas including the
food and drugs industries,
environmental protection, sport
and forensics.

Government agencies employ chemists who check the quality of products

and the environment to make sure that the products conform to legislative
requirements that ultimately protect the community. The work of these chemists consists of analysis determining what is in a product and, in many
cases, how much. Just as importantly, they may also have to verify that certain
substances are not present in a product, or, if they are, that they do not exceed
prescribed maximum limits.
Chemistry and other sciences have many forensic applications (that is,
applications in resolving legal problems). In recent times, with advances
such as DNA analysis and the perfection of techniques requiring very small
samples, the area of forensic analysis has made spectacular headlines relating
to paternity cases and criminal investigations.

Types of chemical analysis

A technician injects a sample into a

gas chromatograph. This sensitive
instrument can analyse samples as
small as a microlitre (106 L).

The analytical chemist uses methods that range from sophisticated to

very simple. Techniques such as gravimetric analysis (analysing by
mass) and volumetric analysis (analysing with accurate concentrations and volumes of solution) may be used. These techniques may
already be familiar to you through your laboratory work. More likely,
however, the analyst will use advanced instrumental techniques such
as atomic absorption spectroscopy (AAS) and various types of chromatography. Due to advances in computer-chip technology,
instruments for these techniques and many others have become
cheaper, more powerful and more user-friendly. For example, a
common instrumental set-up today is to have a gas chromatograph
(GC) connected to a mass spectrometer (MS) and a computer. Once
the instrument has been configured and calibrated, a sample can be
injected, its components identified and measured, and accurate
results printed out quickly and reliably. Previously, chemists would
have had to manually measure and interpret gas chromatographs from a
paper printout one peak at a time, then run a separate mass spectrum.

Qualitative and quantitative analysis are important in forensic science.

CHAPTER 1 Introduction chemical analysis

Two types of analysis are performed in an analytical laboratory: qualitative

analysis and quantitative analysis.

Qualitative analysis
Qualitative analysis finds
what substances are present.
Quantitative analysis measures
the quantity of substance
present.

In qualitative analysis, the chemist is merely interested in what is present.

In testing a urine sample from a racehorse, for example, the mere presence
of a banned drug (or its metabolised products) is all that is necessary. In the
confectionery industry, a sample of imported food dye might be tested to see
whether or not it contains chemicals that are banned in this country.

Quantitative analysis
On the other hand, the question of how much may need to be answered this
is quantitative analysis. A brewer of a low alcohol beer, for example, will need
to know whether its alcohol content is below a certain limit. Health authorities might need to know whether the level of mercury in samples of fish is
below the allowed level.
A logical sequence often used in many analytical procedures is to perform
a qualitative analysis first to find out what is present, then to perform a
quantitative analysis to find the various amounts of substances present.

Deciding on an analytical method

The type of analysis used

will be determined by the
properties of the substance
to be analysed. For example,
atomic absorption spectroscopy
can be used for metal ions.
Gas chromatography is used
to analyse volatile organic
molecules.

UNIT 3 Chemical pathways

When deciding on a method of analysis, the properties of the substance under

investigation must be considered. A chemist will therefore give careful thought
to such physical properties as melting and boiling temperature, colour and
solubility. The way the substance reacts chemically will also be considered.
Acidbase reactions will often be important, while in other cases, redox
reactions might be chosen as the basis for analysis. For example, to analyse
a sample of oven cleaner containing the base sodium hydroxide, an acid
might be used. However, a sample of bleach containing the oxidant sodium
hypochlorite would most likely be analysed by reaction against a suitable
reductant. In other cases, the most appropriate method for identifying and
determining a substance may be through adding something that will form a
precipitate, or alternatively, something that will produce a colour that can be
matched against a set of standards (colorimetric analysis).
Similarly, if instrumental analysis is being considered, the properties of the
substance under test will also be critical to the final choice. Many metals, for
example, lend themselves to atomic absorption spectroscopy. The boiling
temperature of a substance will be important in distinguishing between gas
chromatography and high performance liquid chromatography if chromatographic instruments are being considered.
Another important consideration for the analyst will be the degree of
accuracy required. This could mean the difference between choosing a
tedious but accurate method in preference to a faster but less accurate one. Is
a qualitative determination all that is needed, or is a quantitative one called
for? An appreciation of the strengths and weaknesses of common analytical
techniques will therefore be necessary, so that the most appropriate method
is chosen.
Standard tests to identify substances will also be important. In the analysis
of an unknown compound, for example, it would be important to establish
that an evolved gas is carbon dioxide rather than oxygen or hydrogen.
All the above considerations are important in designing a method of
analysis. If no particular standard method suits, the chemical analyst may have
to display initiative and creativity in designing a new, and maybe innovative,
method to get the job done.

Revision questions
1. Classify the following analyses as either qualitative or quantitative.
(a) A pregnancy test in which a chemical is added to a sample of urine and
a colour change is sought

(b) A chlorine test in which the colour of a chemical is compared against

reference standards to estimate the chlorine level in a home swimming

pool
(c) Placement of a detector in the exhaust pipe of a car during a tune-up
procedure to measure the level of carbon monoxide emissions
(d) Testing for monosodium glutamate, MSG, in a sample of food claimed to
be MSG free

2. Oil tankers need to clean residual oil from their tanks before they load with

new cargo. The washings are supposed to be stored on board but unscrupulous captains sometimes dump these wastes at sea to reduce costs.
In Victoria, there have been numerous cases of such wastes washing
ashore and polluting beaches. Sometimes this has occurred in the vicinity of
Phillip Island and has affected its colony of fairy penguins.
There have been instances where the analysis of such material has led to
the prosecution of offending tanker captains.
(a) Describe how qualitative analysis might assist in such cases.
(b) Given that such oil is usually a complicated mixture, describe how
quantitative analysis could lead to the identification of the ship causing
such pollution.

The landing of astronauts on the

Moon is still regarded as one
of the greatest technological
achievements of all time.
In order for them to get to
the Moon and home again,
vital chemical calculations were
performed to determine the amount
of fuel required. Also, to keep the
air in their spacecraft breathable,
it was critical that the amount of
lithium hydroxide to carry in order
to remove the exhaled carbon
dioxide was calculated correctly.

CHAPTER 1 Introduction chemical analysis

Chemical equations revisited

WeblINK
Chemical equations

An analytical chemist must have a thorough knowledge of chemical reaction

types, including a sound understanding of acidbase, redox and precipitation
reactions. Skills such as equation writing and the ability to do calculations
from equations (stoichiometry) are also essential.
The remainder of this chapter will outline some of these important ideas. As
you have already encountered some of them in your earlier work, a revision or
review is presented, rather than a more in-depth discussion.
As in most other areas of chemistry, chemical equations are essential to
the work of the chemical analyst. In many cases an ionic equation is appropriate when we want to know exactly what is reacting. In others a full formula
equation (also called a molecular equation) is useful.

Writing chemical equations

Chemical equations summarise
chemical reactions by
indicating the substances
present before the reaction
(reactants) and the new
substances produced by the
reaction (products). They also
indicate the relative amounts
of these substances, as well as
their physical states.

Sample problem:

The law of conservation of mass states that matter can neither be created
nor destroyed in a chemical reaction. In effect, this means that all chemical
reactions are merely rearrangements of existing atoms, and that chemical
equations must therefore be balanced.
To write a chemical equation, we must know the names and formulae of the
original substances (the reactants) and the new substances (the products).
The chemical equation is then derived by using the following steps.
Write out the word equation (names of reactants on the left, products on
the right, and an arrow between them).
Replace the name of each substance with its correct chemical formula.
Insert coefficients to balance the equation and thus indicate the relative proportions of the substances involved. (This step reflects the law of
conservation of mass.)
Add the correct symbol of state for each substance.

1.1 Writing chemical equations

To analyse the sodium hydroxide content of some drain cleaner, an analytical
chemist chose to react it with sulfuric acid. Determine the equation for the
resulting reaction, given that sodium sulfate was the salt formed under the
conditions of the analysis.
Solution:
Following the above steps, we get:
sulfuric acid + sodium hydroxide
H2SO4 + NaOH
H2SO4 + 2NaOH

sodium sulfate + water

Na2SO4 + H2O
Na2SO4 + 2H2O

H2SO4(aq) + 2NaOH(aq)

Na2SO4(aq) + 2H2O(l)

Revision questions
3. Under different conditions, the reaction in the above example can produce

sodium hydrogen sulfate (instead of sodium sulfate). Write the equation for
this reaction.
4. When methane, CH4, is burnt in air, carbon dioxide and water are produced.
Write the equation for this reaction.

UNIT 3 Chemical pathways

Table 1.2 Table of ions for use in writing ionic formulae

Cations
+1
lithium
sodium
potassium
caesium
silver
copper (I)
ammonium

+2

Li+
Na+
K+
Cs+
Ag+
Cu+
NH4+

+3
Mg2+
Ca2+
Ba2+
Fe2+
Ni2+
Cu2+
Zn2+
Sn2+
Pb2+
Mn2+
Hg2+
Sr2+

magnesium
calcium
barium
iron (II)
nickel
copper (II)
zinc
tin (II)
lead (II)
manganese (II)
mercury (II)
strontium

Al3+
Cr3+
Fe3+

aluminium
chromium (III)
iron (III)

Anions
1
hydride
fluoride
chloride
bromide
iodide
hydroxide
nitrate
hydrogen carbonate
hydrogen sulfate
chlorate
hydrogen sulfite
nitrite
permanganate

2
HFClBrIOHNO3HCO3HSO4ClO3HSO3NO2MnO4-

oxide
sulfide
sulfate
carbonate
sulfite
dichromate
chromate
thiosulfate

O2S2SO42CO32SO32Cr2O72CrO42S2O32-

3
nitride
phosphate

N3PO43-

An important note
When balancing an equation, the numbers in the formulae must not be
altered. To do so would change the substance to a new one, perhaps one that
does not even exist. Instead, numbers (or coefficients) are inserted in front of
the whole formula. These coefficients then tell us the relative proportions of
moles (or molecules) of the substances that are involved in the reaction.

VICTORIA
Once assigned, a registration number uniquely identifies a car. In a similar way, once
determined, the symbols and numbers in a formula uniquely identify a particular chemical. In either case they cannot be changed without referring to something different. For
example, H2O is safe to drink, but H2O2 is not. (H2O2 is a strong oxidant.)
CHAPTER 1 Introduction chemical analysis

Ionic equations
Unit: 3
aOS: 1
Topic: 1

Do more
Ionic equations

Concept: 8

Sample problem:

While full formula equations are very useful and in all respects correct, they
sometimes make a reaction appear more complicated than it actually is. This is
especially true of reactions occurring in water, where the reaction may be only
between a few different ions. In such situations it may be more informative to
write the ionic equation, rather than the full equation.
To write an ionic equation, we usually begin with the full equation. We
then use our knowledge of dissociation and ionisation to write down the ions
that are present. Dissociation is the process in which ions from an ionic solid
separate as the solid dissolves in water. The end result is that mobile ions are
produced from ions that were originally static. Ionisation is a process that produces ions. A common way that this occurs is when an acid reacts with water.
The end result is that mobile ions are produced from a substance which did
not originally contain ions.
Any ions that remain unchanged (called spectator ions) may then be
cancelled out, leaving behind the ionic equation.

1.2 Deriving an ionic equation (1)

Silver bromide is an important chemical in photography. It can be made in
the laboratory by mixing silver nitrate and potassium bromide solutions. The
silver bromide forms as a precipitate.
Derive the ionic equation for this reaction, given that the full equation for
this reaction is:
AgNO3(aq) + KBr(aq)

AgBr(s) + KNO3(aq)

Solution:
As the three aqueous-phase substances will dissociate into their constituent
ions upon dissolving, the above equation may be rewritten:
Ag+(aq) + NO3-(aq) + K+(aq) + Br-(aq)

AgBr(s) + K+(aq) + NO3-(aq)

As the potassium and the nitrate ions remain unchanged (they are spectator
ions), they may be cancelled out to leave the ionic equation:
Ag+(aq) + Br-(aq)

Sample problem:

AgBr(s)

1.3 Deriving an ionic equation (2)

Derive the ionic equation for the acidbase reaction shown in sample
problem 1.1 on page 8.

To write an ionic equation,

rewrite the formula equation
to show all the aqueous ions
that are present. Take care to
preserve their relative amounts.
Then simply cancel out all
ions that occur on both sides
of the equation (the so-called
spectator ions). The ionic
equation is what remains.

Solution:
H2SO4(aq) + 2NaOH(aq)

Rewriting to show the actual ions present, we get:

2H+(aq) + SO42-(aq) + 2Na+(aq) + 2OH-(aq)
2Na+(aq) + SO42-(aq) + 2H2O(l)
After cancelling out the spectator ions, we get:
2H+(aq) + 2OH-(aq)
or
H+(aq) + OH-(aq)

10

UNIT 3 Chemical pathways

Na2SO4(aq) + 2H2O(l)

2H2O(l)
H2O(l)

Revision question
5. The equation for the reaction between silver nitrate and calcium chloride
is:

2AgNO3(aq) + CaCl2(aq)

2AgCl(s) + Ca(NO3)2(aq)

Derive the ionic equation for this reaction.

Reaction patterns
Unit: 3
aOS: 1
Topic: 1
Concept: 7

Do more
Reaction types

It can be dangerous to generalise too much in chemistry, but there are

many obvious patterns that present themselves when a large range of different reactions are examined. Knowledge of these patterns can often make
the writing of equations much easier. However, it should always be remembered that exceptions can exist and that all reactants and products should be
identified by suitable analysis to avoid any possible uncertainty.
Here is a list of patterns that you will find useful.
1.

acid + base

salt + water

Example: Nitric acid is added to calcium hydroxide solution. The salt

formed will be calcium nitrate. The equation is
2HNO3(aq) + Ca(OH)2(aq)

Ca(NO3)2(aq) + 2H2O(l)

This pattern also applies to an acid reacting with a basic oxide, as well as
to an acidic oxide reacting with a base. (Remember that a salt is any ionic
compound, not only NaCl.)
2.

acid + reactive metal

salt + hydrogen

Example: Zinc metal is added to hydrochloric acid. This will produce zinc
chloride as the salt. The equation is
ZnCl2(aq) + H2(g)

Zn(s) + 2HCl(aq)
3.

salt + carbon dioxide + water

acid + metal carbonate

Example: Some marble chips containing calcium carbonate are analysed

by adding hydrochloric acid. The salt produced will be calcium chloride.
The equation is
CaCO3(s) + 2HCl(aq)

CaCl2(aq) + CO2(g) + H2O(l)

This pattern also applies to an acid reacting with a metal hydrogen

carbonate.
4.

metal carbonate

metal oxide + carbon dioxide

Example: Some calcium carbonate is heated strongly to decompose it.

Calcium oxide and carbon dioxide will be formed. The equation is
CaCO3(s)
5.

CaO(s) + CO2(g)

hydrocarbon + oxygen

carbon dioxide + water

Example: Some propane from a camp stove is burnt. The chemical

products will be carbon dioxide and water. The equation is
C3H8(g) + 5O2(g)

3CO2(g) + 4H2O(g)

Special note: A hydrocarbon is a compound that contains only carbon

and hydrogen. The following general equation is very useful for balancing
reactions of this type.
CxHy + (x +

y
) O2
4

xCO2 +

y
H2O
2

If this formula leads to any halves, the coefficients can be doubled.

CHAPTER 1 Introduction chemical analysis

11

Revision question
6. Write chemical equations for the following reactions.
(a) Hydrochloric acid reacting with potassium hydroxide
(b) Carbon dioxide (an acidic oxide) reacting with lithium hydroxide
(c) Zinc carbonate being decomposed by heating
(d) Sodium carbonate solution reacting with nitric acid
(e) Ethyne, C2H2 (also known as acetylene), being burnt during some oxyacetylene welding

Some common types of chemical

reactions
Acidbase reactions involve
the transfer of H+ ions. The
substance that donates the
H+ ion is the acid, and the
substance that accepts the H+
ion is the base.

We will now look at some of the more common types of chemical reactions
used in the analytical laboratory. As mentioned previously in this chapter,
these are:
1. acidbase reactions
2. redox reactions
3. precipitation reactions.
You have probably studied acidbase reactions in some detail already as
part of your work in unit 2. The revision box on the opposite page contains a
summary of the important points relevant to these types of reactions.

Redox reactions
1.1 Iron content of
steel wool

voltmeter

iron

zinc

salt
bridge

Zn2+ solution

Redox reactions involve

the transfer of electrons. In
particular, adding electrons
to a substance is the process
of reduction, and removing
electrons is the process of
oxidation.
These processes may be
represented by ionic equations.
Remember that, for
reduction, the electrons will
be on the left side of the halfequation (just like red- being
on the left of redox). For
oxidation, the electrons will be
on the right side of the halfequation (just like -ox being on
the right of redox).

Oxidation and reduction reactions (or redox reactions as they are often
called) form another very large group of important reactions. Since the
beginnings of human history, these reactions have played an important role
in daily life. The use of fire is a simple example of an oxidation process. The
production of metals from their ores is an example of an important reduction
process.

Fe2+ solution

The generation of an electric current between half-cells shows that redox reactions
involve electron transfer. In this case the electrons flow from the more reactive zinc
electrode to the less reactive iron electrode.

Redox reactions are involved in many common corrosion reactions.

Protection of metals from corrosion also often involves redox reactions. For
example, the protection of iron by a thin coating of zinc (galvanising) involves
redox reactions between dissolved oxygen, water and zinc metal and relies on
the fact that zinc is easier to oxidise than iron. Today, we recognise that
12

UNIT 3 Chemical pathways

all redox reactions involve the transfer of electrons from one substance to
another. The reactions occurring on the galvanised iron may be represented
by ionic half-equations that demonstrate this transfer.

Unit: 3
aOS: 1
Topic: 2

See more
BrnstedLowry
acids and bases

Zn2+(aq) + 2e-

Zn(s)
and

Concept: 1

O2(aq) + H2O(l) + 4e-

4OH-(aq)

Revision a summary of acidbase reactions

BrnstedLowry theory
Acids are substances that donate hydrogen ions (protons) to another substance.
Bases are proton acceptors.
Conjugate pairs
A conjugate pair is the original acid/base and the consequent base/acid that it turns into.
For example, HNO3(aq) + H2O(l)
NO3-(aq) + H3O+(aq).
The conjugate pairs are HNO3/NO3- and H3O+/H2O.
Note the convention of stating the acid first then the base.
Amphiprotic or amphoteric substances
These can act as acids in some reactions and as bases in others. Water is an example of such a substance.
For example,
CH3COOH(aq) + H2O(l)
H3O+(aq) + CH3COO-(aq)
NH3(g) + H2O(l)
NH4+(aq) + OH-(aq)
Polyprotic acids
These are acids that can donate more than one proton (per molecule). Orthophosphoric acid, for example,
is triprotic.
H3PO4(l) + H2O(l)
H3O+(aq) + H2PO4-(aq)
H2PO4 (aq) + H2O(l)
H3O+(aq) + HPO42-(aq)
2HPO4 (aq) + H2O(l)
H3O+(aq) + PO43-(aq)
Acid/base strength
The strength of an acid or base is a measure of how readily it donates or accepts H+ ions. In water, for
example, a strong acid/base will react extensively with the water to produce a large number of ions. A
weak acid/base in the same situation will react only slightly and hence only a few ions will be formed.
Experimentally, this will be reflected in the different conductivities of solutions that have the same
concentration.
The pH scale
This is used to measure how acidic or how basic a solution is.

vinegar
soft drink
hair conditioner

rain
water
pure water

10

toothpaste
hair
shampoo

11

12

13

14

machine
dishwashing
powder
cloudy
ammonia
detergent

Values less than 7 are acidic. Values higher than 7 are basic. A value of 7 is neutral.
pH is discussed in more detail in chapter 10.

CHAPTER 1 Introduction chemical analysis

13

Oxidation is the process of

losing electrons. Reduction is
the process of gaining electrons.
This may be remembered by
using the mnemonic OIL RIG.

Oxidants and reductants are

substances, not processes.
An oxidant causes another
substance to be oxidised, and
is itself reduced. In a similar
way, a reductant causes another
substance to be reduced, and is
itself oxidised.

Such equations allow us to make the following definitions:

oxidation is the process of losing electrons.
reduction is the process of gaining electrons
Note that there are also some older definitions of redox reactions that
involve the elements oxygen and hydrogen. These older definitions of reduction and oxidation are as follows:
Oxidation involves the addition of oxygen or the removal of hydrogen from
a substance.
Reduction involves the removal of oxygen or the addition of hydrogen to a
substance.
In some circumstances it might be more appropriate to use these instead of
the modern definitions.
As the above half-equations show, the processes of oxidation and reduction
are complementary. One process cannot occur without the other. This fact
leads to two further definitions.
An oxidant is a substance that causes something else to be oxidised. In so
doing, the substance itself is reduced. Oxidants are also called oxidising
agents.
A reductant is a substance that causes another substance to be reduced.
In so doing, the substance itself is oxidised. Reductants are also called
reducing agents.
Note that in these definitions, oxidation and reduction are both processes.
As such, they are best described by their half-equations. Oxidants and reductants, however, are substances and are best represented by their formulae.

Writing half-equations
Reactants

Products
right

left

REDOX
e on the left

e on the right

To balance redox halfequations: write down the

reactants and products and
balance the equation; add water
molecules; add hydrogen ions;
balance charges with electrons.

14

UNIT 3 Chemical pathways

In the example mentioned on page 13, the half-equation involving the zinc
was quite simple and easy to deduce. In many redox processes, however, the
situation is not quite so simple. A good example is the reduction of orange
dichromate ions, Cr2O72-, to green chromium(III) ions, Cr3+.
To deduce these more complicated types of half-equations, we use the
following rules.
1. Write down the substance and what it turns into (i.e. its conjugate).
2. Balance all atoms, except for oxygen and hydrogen.
3. Balance oxygen atoms by adding water molecules.
4. Balance hydrogen atoms by adding hydrogen ions.
5. Balance charge by adding electrons.
Ensure both half-equations have the same number of electrons on either
side. (If they do not, multiply through the half-equation.) Once both halfequations have been obtained, the overall ionic equation may be produced
by adding the two half-equations together so that the electrons cancel out.
With these more complicated equations, water and hydrogen ions may also
cancel out (at least partially) when this is done. The appropriate symbols of
state should also be added.
As an example, let us consider the reaction mentioned above. In testing for
alcohol levels, dichromate ions oxidise ethanol. The resulting products are
chromium(III) ions and acetic acid.
If we apply the five rules to the reduction of the dichromate, we get, step by
step:
Step 1.

Cr2O72-

Cr3+

Step 2.

Cr2O72-

2Cr3+

Step 3.

Cr2O72-

2Cr3+ + 7H2O

Step 4.

Cr2O72- + 14H+

2Cr3+ + 7H2O

Step 5.

Cr2O72- + 14H+ + 6e-

2Cr3+ + 7H2O

For the oxidation of the ethanol, the sequence is:

WeblINK
Redox half-equations

Step 1.

CH3CH2OH

CH3COOH

Step 2.

CH3CH2OH

CH3COOH

Step 3.

CH3CH2OH + H2O

CH3COOH

Step 4.

CH3CH2OH + H2O

CH3COOH + 4H+

Step 5.

CH3CH2OH + H2O

CH3COOH + 4H+ + 4e-

To obtain the overall ionic equation, all that is now necessary is to multiply
the first half-equation by 2 and the second one by 3. This will ensure that the
electrons cancel out when the two are added together. A number of water
molecules and H+ ions will also cancel out at this stage.
Doing this, and adding these symbols, we finally get
2Cr2O72-(aq) + 3CH3CH2OH(g) + 16H+(aq)
4Cr3+(aq) + 3CH3COOH(aq) + 11H2O(l)

Oxidation numbers a valuable tool

Oxidation is an increase in
oxidation number.
Reduction is a decrease in
oxidation number.

Unit: 3
aOS: 1
Topic: 2
Concept: 5

Do more
Oxidation
numbers

With simple redox equations, it is often possible to deduce where the electrons
are coming from and where they are going. With more complicated redox
reactions, this task is more difficult. In fact, it may be quite hard to decide
whether a reaction is a redox process or not! For such situations, chemists
have invented a very useful tool oxidation numbers. Their use greatly simplifies the identification of redox reactions and the subsequent identification
of oxidants and reductants. If oxidation numbers change during a reaction, it
indicates that the reaction is a redox reaction.
In particular:
if an oxidation number increases, then oxidation has occurred
if an oxidation number decreases, then reduction has occurred.
To calculate oxidation numbers, the following rules are used.
1. The oxidation number of an element is zero, e.g. Zn0, N20, O20.
2. In monatomic ions the oxidation number is the same as the charge on the
ion, e.g. Mg2+, Cl-.
3. In all compounds of hydrogen the oxidation number of hydrogen is +1,
e.g. Na+1O-2H+1.
Exception: In metallic hydrides, the oxidation number is -1, e.g. NaH.
4. In compounds of oxygen the oxidation number of the oxygen is -2.
Exception: In peroxide, the oxidation number of the oxygen is -1, e.g.
H2O2.
After using these rules, the following additional rules may be required.
5. In a neutral molecule the sum of all the oxidation numbers must equal
zero. For example, in K2Cr2O7, the oxidation number of potassium is +1
(total +2) and the oxidation number of oxygen is -2 (total -14), so the
oxidation number of chromium must be +6 (total +12).
6. In a polyatomic ion the sum of the oxidation numbers must equal the
charge on the ion. For example, the oxidation number of the chromate
ion, CrO72-, is -2.
On rare occasions the following rule may be needed.
7. For compounds where there is no oxygen or hydrogen present, the more
electronegative atom is assigned an oxidation number, as if it were a monatomic ion. The electronegativity of an element is a measure of its ability
to attract electrons in a bond.
CHAPTER 1 Introduction chemical analysis

15

Table 1.3 Electronegativity values of some common elements

H
2.1
Li
1.0

Be
1.6

B
2.0

C
2.5

N
3.0

O
3.5

F
4.0

Na
0.0

Mg
1.3

Al
1.6

Si
1.9

P
2.2

S
2.6

Cl
3.2
Br
2.8
I
2.5

Sample problem:

1.4 Writing a redox equation from half-equations

Permanganate ions, MnO4-, are able to oxidise Fe2+ ions to Fe3+ ions.
Manganese(II) ions are produced in this process.
Write the half-equations for both the oxidation and reduction processes,
and hence obtain the overall redox equation for this reaction.
Solution:
For the oxidation process we get:
Fe2+(aq)

Fe3+(aq) + e-

[1]

If we follow the rules on page 15, we get the following half-equation for the
reduction process:
MnO4-(aq) + 8H+(aq) + 5e-

Mn2+(aq) + 4H2O(l)

[2]

To obtain the overall redox equation, we must multiply equation [1] by 5,

so that the electrons will cancel out when the two half-equations are added
together.
When this is done we obtain:
5Fe2+(aq) + MnO4-(aq) + 8H+(aq)

Sample problem:

5Fe3+(aq) + Mn2+(aq) + 4H2O(l)

1.5 Calculating oxidation numbers

Calculate the oxidation numbers of the atoms shown below:
(a) O in O2
(b) Ca in CaBr2
(c) Cr in Cr2O72(d) S in SF6
(e) O in H2O2
Solution:
(a) O in O2 = 0
(b) Ca in CaBr2 = +2
(c) Cr in Cr2O72- = +6
(d) S in SF6 = +6
(e) O in H2O2 = -1

16

UNIT 3 Chemical pathways

(Rule 1)
(Rule 2)
(Rule 4 followed by rule 6)
(Rule 7, followed by rule 5. The F is
imagined to be F-.)
(Rule 4 an exception!)

Sample problem:

1.6 Using oxidation numbers to identify a redox reaction

Is the reaction represented by the equation
Zn(s) + 2H2SO4(aq)

ZnSO4(aq) + SO2(g) + 2H2O(l)

a redox reaction, and, if so, which substance has been oxidised?

Solution:
Calculating the oxidation numbers for each atom in the above equation
reveals that Zn has an oxidation number of 0, while the Zn in ZnSO4 has an
oxidation number of +2.
This is enough to tell us that the reaction is a redox reaction and that it is the
zinc that has been oxidised.
Note that a change also occurs with the sulfur it is +6 in H2SO4, but only +4
in the SO2. Therefore, we can also say that the sulfuric acid has been reduced.

Revision questions
7. If dichromate ions, Cr2O72-, are mixed with iodide ions, I-, iodine, I2, and
chromium(III) ions are produced.
Write the overall ionic equation for this reaction.

8. Assign oxidation numbers to each atom in the following equation. Decide

whether or not it is a redox reaction.
2MnO2(s) + 12H2O(l) + 3S2O82-(aq)

2MnO4-(aq) + 6SO42-(aq) + 8H3O+(aq)

Precipitation reactions
In precipitation reactions, soluble substances in solution are mixed and
an insoluble product is formed. This appears as a precipitate and is often
collected by filtration.
Such reactions may form part of a qualitative scheme of analysis where the
appearance and nature of the precipitate may be taken as proof for the existence of a particular ion. For example, the owner of a swimming pool using
salt chlorination may simply wish to know if there is any salt left in the pool
water. If a small amount of silver nitrate solution is added to a sample of the
pool water, a white precipitate will indicate that chloride ions are present. The
white precipitate is silver chloride, formed according to the equation:
Ag+(aq) + Cl-(aq)

AgCl(s)

In quantitative analyses we must remember that there is no such thing as

a totally insoluble substance. So-called insoluble precipitates will vary in
their degree of solubility and this must be taken into account in designing
the experimental procedure. What may appear as a precipitate may in fact be
soluble enough to lead to significant losses. The role of temperature and its
subsequent effect on solubility is another crucial factor to consider.

The mole concept

A chemist weighing out a
substance to determine the number
of moles.

Chemists never deal with particles one at a time. In even the smallest-scale
chemical reaction, we would be dealing with huge numbers of atoms and
molecules. To cope with this and be able to make the necessary predictions,
chemists use a special quantity for counting these particles the mole.
CHAPTER 1 Introduction chemical analysis

17

The mole is defined as the amount of substance that contains the same
number of particles as there are atoms in exactly 12 g of pure 12C isotope.
This number has been estimated to be 6.02 1023 and is known as Avogadros
number, a constant with the symbol NA. The abbreviation for the mole is mol.

Single moles of mercury, zinc,

silicon, aluminium, sulfur and
bromine

The molar mass of a pure

substance is the mass of
6.02 1023 particles of that
substance. These particles
may be atoms, molecules or,
in the case of ionic substances,
formula units.
To calculate the molar mass,
simply add together the relative
atomic masses of all the atoms
in its formula and show g mol-1
as the unit.

Chemists therefore count particles such as atoms, molecules and ions using
the mole, in much the same way as an egg farmer might count his production
in dozens, or a manufacturer of copy paper would sell his product in packets
of 500 (called a ream). However, while it may be practical to count eggs and
paper into the above groups, the very size of the Avogadro constant means
that this is not practical when dealing with moles. Instead, chemists count by
weighing. If the mass of a 1 mole amount (called the molar mass symbol M)
is known, then a sample can be weighed and the mass compared to the molar
mass in order to determine the number of moles present.
The molar mass of a substance is obtained by simply adding together the
relative atomic masses of each atom that appears in the formula, and showing
g mol-1 as the unit.
For example, the molar mass of glucose is:
M(C6H12O6) = (6 12.0) + (12 1.0) + (6 16.0)
= 180.0 g mol-1
A useful skill is calculating the percentage composition of a particular
element in a compound. If the formula is known accurately, this can be done
if the molar mass has been calculated. Thus, for the example above, the
percentage of carbon in glucose, by mass, would be:
72.0
100
180.0
= 40.0%

The role of stoichiometry in

quantitative analysis
As mentioned earlier, quantitative analysis involves the determination of
how much is present.
In Unit 2 you saw how it was possible to use balanced chemical equations
to make predictions concerning the components of a chemical reaction.
Such calculations (stoichiometry) are central to the performance of any
quantitative form of analysis.
Although each situation is different, all stoichiometric calculations will
involve, at some stage or another, conversion to and from moles. In most cases
it will also be noted that you will be linking together two of the substances
from the equation, one about which you have some information and one
about which you will be making predictions. Sample problem 1.7 illustrates
both of these points.
18

UNIT 3 Chemical pathways

Formulae for calculating the

number of moles of substance
include:
m
n=
M
V
n=
Vm
pV
n=
RT
n = cV

Unit: 3
aOS: 1
Topic: 1

Do more
The mole

Revision calculating the number of

moles of a substance a review of formulae
When a mass of a known substance is given:
m
n=
M
where m is the mass of the sample (g) and M is the molar mass of the
substance (g mol-1).
When a gas volume at STP or SLC is given:
V
n=
Vm
where Vm is the molar volume, measured in litres. The volume of a
gas can be measured at any temperature and pressure. However, to
standardise such measurements, scientists around the world often
quote such measurements at either standard temperature and pressure (STP 101.3 kPa, 0C) or at standard laboratory conditions
(SLC 101.3 kPa, 25C). Under these conditions, the molar volume of
a gas is 22.4 L mol-1 or 24.5 L mol-1 respectively.
When a gas volume, at conditions other than STP or SLC, is given:
n=

Concept: 1

pV
RT

where p is the pressure measured in kilopascals, V is the volume

measured in litres, T is the temperature in kelvin and R is the general
gas constant (R = 8.31 J K-1 mol-1). Remember that gas pressure can
also be measured in atmospheres (atm) and in millimetres of mercury
(mm Hg), where:
760 mm Hg = 1 atm, and
1 atm = 101.3 kPa
To obtain the kelvin temperature, you must add 273 to the Celsius
temperature.
Mass/volume units (e.g. g L-1, mg L-1) are sometimes used as concentration units for solutions.
For solutions, the relevant formula is:
n = cV
where c is the concentration (mol L-1) and V is the volume of solution
used in litres.

change
into moles

Unit: 3
aOS: 1
Topic: 1
Concept: 4

Do more
Stoichiometry
substance no. 1
(initial known
information)

balanced chemical
equation

change
from moles

substance no. 2
(information being
predicted)

Although each problem is different, this scheme forms part of nearly all stoichiometric
calculations.

CHAPTER 1 Introduction chemical analysis

19

Sample problem:

1.7 A calculation involving the general gas equation

A sample of potassium chlorate is suspected of being contaminated with
potassium chloride. To test the purity of this sample, 7.21 g of it was heated
and the evolved oxygen collected. The volume of oxygen produced was 1.16 L,
measured at 101.3 kPa and 18C.
Assuming that the potassium chlorate was the only source of oxygen
present, calculate its percentage in the original sample.
Solution:
The equation for the reaction involved is:
2KCl(s) + 3O2(g)

2KClO3(s)

From the information in the question, it is obvious that the oxygen is the
known substance and the potassium chlorate is the unknown substance.
As pV = nRT
pV
RT
101.3 1.16
n (O2 ) =
8.31 291
n=

= 0.0486 mol
From the equation:
n (KClO3 ) n ( O 2 )
=
3
2
2
\ n(KClO3) = 3 n(O2)
\ n(KClO3) =

2
3

0.0486

= 0.0324 mol
m(KClO3) = 0.0324 M(KClO3)
= 0.0324 122.6
= 3.97 g
3.97
Percentage purity =
100
7.21
= 55.1%

Calculations involving excess reactants

Unit: 3
aOS: 1
Topic: 1
Concept: 5

20

Do more
Limiting
reactant

UNIT 3 Chemical pathways

In some cases, the amounts of more than one reactant may be known. Before
the amount of product can be predicted, it will therefore be necessary to work
out which reactant is in excess and which reactant is used up. Once the number
of moles of each reactant has been calculated, the mole ratio (determined from
the reaction equation) is used to calculate the number of moles of all reactants
used in the reaction. The excess reactant no longer takes part in the reaction.
The amount of product may then be forecast, based upon the substance
that is completely consumed (this is called the limiting reagent). The moles
of this substance must be used in all future calculations.
Excess reactants are often used to ensure complete reaction of the other
reactants. For example, providing excess air during the combustion of hydrocarbons ensures that all of the hydrocarbon molecules react to produce
carbon dioxide and water. The reaction is therefore cleaner and more efficient
than one that produces uncombusted and partially combusted hydrocarbons
as well as carbon dioxide and water.

Sample problem:

1.8 Determining the limiting and the excess reagents

Calculate the volume of carbon dioxide gas evolved (at SLC) when 20.0 mL
of 0.052 mol L-1 sodium carbonate solution is mixed with 22.0 mL of
0.0980 mol L-1 hydrochloric acid.
Solution:
The equation for this reaction is:
Na2CO3(aq) + 2HCl(aq)

2NaCl(aq) + CO2(g) + H2O(l)

n(Na2CO3) = cV

20.0
1000
= 0.001 04 mol
= 0.0520

n(HCl) = cV

22.0
1000
= 0.002 16 mol

= 0.0980

As every 1 mole of Na2CO3 requires 2 moles of HCl, it follows that 0.001 04 mol
of Na2CO3 will require only 0.002 08 mol of HCl. The HCl is therefore in excess
and Na2CO3 is the limiting reagent.
A table can be used to determine which reactant is in excess and how many
moles of the products are produced.
Substance

Na2CO3

2HCl

2NaCl

CO2

H2O

Mole ratio

No. of mol

0.001 04

0.002 16

No. of mol in reaction

0.001 04

0.002 08

0.002 08

0.001 04

0.001 04

Excess no. of mol

0.000 08

From the equation:

n(CO2) = n(Na2CO3)
\ n(CO2) = 0.001 04 mol
\ V(CO2) at SLC = 0.001 04 24.5
= 0.0255 L (or 25.5 mL)

Dilution of solutions
Laboratory work often involves the preparation of solutions by the dilution of
more concentrated solutions.
For example, sulfuric acid is often purchased at 18 mol L-1 strength. Most
laboratory uses, however, require much lower concentrations than this.
Since only water (or solvent) is added to the original solution, the number
of moles of substance remains the same. Of course, adding water will increase
the volume and decrease the concentration, but the product n = cV will remain
constant. Therefore the equation c1V1 = c2V2 is used to calculate the increased
volume or decreased concentration of the diluted solution.
CHAPTER 1 Introduction chemical analysis

21

Sample problem:

1.9 Determining a volume required for dilution (1)

What volume of 18 mol L-1 sulfuric acid must be used to prepare 2.0 L of
2.0 mol L-1 sulfuric acid solution?
Solution:
We need to work out the number of moles present in the diluted solution,
then calculate the volume of the undiluted solution that is required to supply
this number of moles.
c1V1 = c2V2
18.0 V1 = 2.0 2.0
4.0
\ V(undiluted H2SO4) =
18.0
= 0.22 L
Therefore 220 mL of 18 mol L-1 sulfuric acid will need to be added to
(2000 - 220) = 1780 mL of water to make 2.0 L of diluted solution.

Sample problem:

1.10 Determining a volume required for dilution (2)

What volume of water, in mL, must be added to 30 mL of 10 mol L-1 ammonia
solution to make a 0.25 mol L-1 solution of ammonia?
Solution:
n(undiluted ammonia) = cV
10 30
=
1000
= 0.30 mol
n
V(diluted ammonia) = c
0.30
=
0.25
= 1.2 L
= 1200 mL
Therefore 1170 mL of water must be added (to make a total of 1200 mL of
diluted solution).

Revision questions
9. If

1.26 g of KClO3 is heated according to the equation

2KCl(s) + 3O2(g), calculate the volume of oxygen that
2KClO3(s)
would be evolved at a temperature of 14C and 100.4 kPa pressure.

10. Calculate the volume of CO2 produced at STP if 40.00 mL of 0.052 mol L-1
sodium carbonate solution is mixed with 11.0 mL of 0.0980 mol L-1 hydrochloric acid solution.

11. What volume of 2 mol L-1 sodium hydroxide solution is required to produce
100 mL of 0.1 mol L-1 solution, and what volume of water will be required?

22

UNIT 3 Chemical pathways

Chapter review

Summary
Chemical analysis is the process of determining the
substances present in a test sample. A range of techniques exists for doing this.
The choice of a particular technique depends on
many factors, the most important of which are the
properties of the substance that is being tested for.
Qualitative analysis is the process of determining
what substances are present in a sample.
Quantitative analysis is the process of determining
how much of a substance is present.
Chemical equations are a concise way of summarising a chemical reaction.
Ionic equations are an even more concise way of
summarising a reaction. Ions that remain unchanged
can be cancelled out to leave behind the ionic
equation.
Dissociation and ionisation are two processes that
must be considered when writing an ionic equation.
In order to make sense of the huge range of chemical
reactions that exist, chemists classify them into
groups. Three common types of chemical reaction
are acidbase reactions, redox reactions and precipitation reactions.
Acidbase reactions are characterised by hydrogen
ions (H+ ions) being transferred from one substance
to another. The substance that donates the hydrogen
ion is the acid, and the substance that receives it is
the base.
Important acidbase terms are conjugate pairs,
amphiprotic substances and polyprotic acids.
Applied to acids and bases, strength and concentration mean completely different things.
The pH scale is commonly used to measure the level
of acidity or basicity in a particular solution.
Redox reactions involve the transfer of electrons
from one substance to another.
Redox reactions may be described by special types
of ionic equations called half-equations.
Oxidation is the process of losing electrons, while
reduction is the process of gaining electrons.
An oxidant allows another substance to be oxidised
and is itself reduced. A reductant allows another
substance to be reduced, and is itself oxidised.
Two very useful tools in dealing with redox reactions
are the writing of half-equations, and the calculation
of oxidation numbers. Rules exist for both these
tasks.
Precipitation reactions result from the association
of soluble ions to form an insoluble precipitate.
The mole concept is a very important and useful
idea in chemistry. This concept allows chemists to

work with convenient amounts of chemicals, while

never losing sight of the underlying atomic nature of
substances.
The mole can be thought of as a counting unit in
a similar way to the dozen. The number of particles that constitute a mole is called the Avogadro
constant and has a value of 6.02 1023.
A number of formulae exist for estimating the
number of moles present in a given sample. Which
formula is used depends on the form of the sample
and the information that we are presented about
it.
The mass of 1 mole of an element is called the
molar mass (M ). The molar mass of a compound
is obtained by adding together the relative atomic
masses of each atom that appears in the formula.
The calculation of percentage composition is a
useful skill for comparing the amount of an element
in a compound.
Stoichiometry is the use of chemical equations involving moles to perform quantitative
calculations.
In some instances, it is necessary to identify the
excess and the limiting reagents before proceeding
with a stoichiometric calculation. Once identified, the calculation is always based on the limiting
reagent.
Calculations involving the dilution of solutions are
based on the formula for calculating the number of
moles in a solution n = cV or c1V1 = c2V2.

Multiple choice questions

1. Consider the acidbase reaction that is represented
by the following equation:
HCO3-(aq) + H2O(l)

H3O+(aq) + CO32-(aq)

The conjugate pairs present are:

a HCO3-/H3O+, H2O/CO32b HCO3-/H2O, H3O+/CO32C HCO3-/CO32-, H3O+/OHD HCO3-/CO32-, H3O+/H2O.
2. A solution of pH 5 is diluted by adding constant
portions of water to it. After each addition, the new
pH is measured.
Which of the following statements correctly
describes the trend in pH values that is obtained?
a The pH will decrease.
b The pH will increase, but will not go above the
value 7.
C The pH will increase by a constant value after
the addition of each portion of water.
D The pH will remain at a value of 5.
CHAPTER 1 Introduction chemical analysis

23

3. The oxidation number of chromium in potassium

dichromate, K2Cr2O7, is:
a -2
b +1
C +6
D +12.
4. VO2+ ions can act as an oxidising agent. When this
happens, VO2+ ions may be produced.
The half-equation for this reaction may be represented as follows:
yVO2+(aq) + zH2O(l)
vVO2+(aq) + wH+(aq) + xeThe values of v, w, x, y and z are respectively:
a 1, 2, 1, 1, 1
b 1, 2, 1, 1, 2
C 2, 1, 2, 2, 1
D 1, 2, 1, 2, 1.
5. Referring to the equation in question 4, which of
the following statements is correct?
a VO2+ ions have been oxidised.
b The oxidation number of V in VO2+ is +1.
C The equation represents a reduction process.
D The H+ ions have been oxidised to H2O.
6. Caustic soda, NaOH, can be made according to the
equation:
Na2CO3(aq) + Ca(OH)2(s)
2NaOH(aq) + CaCO3(aq)
What mass of caustic soda would be obtained from
1 kilogram of sodium carbonate?
a 377 g
b 755 g
C 1000 g
D 2000 g
7. Uranium may be prepared by reacting uranium
tetrafluoride with magnesium, according to the
equation:
U(s) + 2MgF2(s)
UF4(g) + 2Mg(s)
If 100 g of uranium tetrafluoride is reacted with
10 g of magnesium, what mass of uranium will be
produced?
a 49.0 g
b 75.8 g
C 98.0 g
D 152 g
8. Some of a 12 mol L-1 HCl solution is to be used to
prepare 2.0 L of 0.5 mol L-1 HCl solution.
The volume of 12 mol L-1 HCl that will be
required is closest to:
a 10 mL
b 20 mL
C 70 mL
D 80 mL.
9. The percentage, by mass, of sulfur in sulfuric acid
is:
a 33%
b 65%
24

UNIT 3 Chemical pathways

C 66%
D 75%.
10. A sodium hydroxide solution has a concentration
of 0.10 mol L-1. Expressed in g L-1, this concentration is the same as:
a 0.040 g L-1
b 0.40 g L-1
C 4.0 g L-1
D 40 g L-1.

Review questions
Chemical equations
1. Classify the following analyses as either qualitative
or quantitative.
(a) Analysis of the propellent from a spray can by
an instrument, to check the claim that it does
not contain chlorofluorocarbons, CFCs.
(b) Adding a piece of testape to a diabetics urine
to estimate the glucose level present.
(c) Instrumental checking of the level of mercury
in a sample of fish.
(d) Analysis of a hair-colouring preparation containing less than 1.5% aromatic nitro amines,
to check the claim.
2. A number of qualitative tests are used to identify
various substances. Find out the tests that are used
to identify the following.
(a) Carbon dioxide gas
(b) Starch
(c) Oxygen gas
(d) Protein in a food sample
(e) Hydrogen gas
(f) Water
3. Balance the equations below by inserting the
necessary coefficients.
(a) Mg + HCl
MgCl2 + H2
(b) CH4 + O2
CO2 + H2O
(c) H2S + O2
SO2 + H2O
(d) Fe2O3 + CO
Fe + CO2
(e) CxHy + O2
CO2 + H2O
(f) After you have balanced them, what important
piece of information is still missing from the
above equations?
4. In each of the following reactions, a precipitate is
formed. Write the full balanced equation for each
reaction and then write the corresponding ionic
equation. (The precipitate formed in each case is
shown in brackets.)
(a) Silver nitrate solution is added to sodium chloride solution. (Silver chloride)
(b) Barium chloride solution is added to sodium
sulfate solution. (Barium sulfate)
(c) Lead nitrate solution is added to potassium
chromate solution. (Lead chromate)

(d) Sodium phosphate solution is added to silver

nitrate solution. (Silver phosphate)
(e) Dilute hydrochloric acid is added to lead
nitrate solution. (Lead chloride)
5. A VCE student is planning a formal to celebrate
the end of examinations. After some initial
discussions with the management about the
seating arrangements, she decides to seat her
guests (11 boys and 9 girls), as shown in figure
(i) below.
A few days beforehand, however, the management contact her and advise her that the proposed
seating arrangement is no longer possible. She
therefore works out a second arrangement, which
is shown in figure (ii) below.
(a) In what ways is the rearrangement of the guests
similar to a chemical reaction?
(b) Using appropriate symbols, summarise this
rearrangement as a chemical equation.
(i)

G
B

B
B
B

B
B

G
G
B

(ii)
B G B G B
B
G B G B G
B
G

G
G

8. Identify the conjugate acid/base pairs from the

following equations.
(a) CH3COOH(l) + H2O(aq)
CH3COO-(aq) + H3O+(l)
(b) HCO3 (aq) + OH (aq)
H2O(l) + CO32-(aq)
+
(c) NH3(g) + H2O(l)
NH4 (aq) + OH-(aq)
(d) HSO3 (aq) + H2O(l)
H2SO3(aq) + OH-(aq)
9. Write conjugate acids for the following bases.
(a) NH2(b) Cl(c) HSO4(d) SO4210. Write conjugate bases for the following acids.
(a) HF
(b) HNO3
(c) H2O
(d) HSO311. What is the difference between:
(a) a strong acid and a concentrated acid?
(b) a weak acid and a dilute acid?

Redox reactions

Acidbase reactions

B
G

Mole concept
6. Calculate the amount of substance (in mol), in the
following samples.
(a) 24.7 g of ethanol
(b) 123.6 g of aluminium
(c) 45.5 g of sulfur dioxide
(d) 157.3 g of sodium hydroxide
(e) 2.35 L of methane gas at STP
(f) 42.9 L of CHCl3 at 100 000 Pa and 23C
(g) 24.2 mL of 1.3 mol L-1 sodium chloride
solution
(h) 4.0 L of 2.5 mol L-1 sulfuric acid solution
7. Why is a mole interpretation of a chemical equation the same as a molecule interpretation?

12. The definitions for oxidants and reductants, on

the one hand, and acids and bases on the other,
are sometimes confused by the less careful chemistry student. Prepare a short comparison of these
terms and definitions to assist such a student.
13. In their initial studies of redox reactions, chemistry
students often find it hard to distinguish between
the terms oxidation and oxidant on the one hand,
and reduction and reductant on the other.
Prepare a short paragraph to explain the difference between each pair of terms.
14. Calculate the oxidation number of the bolded
element in each of the following.
(a) Mn2+
(b) N2H4
(c) CrO42(d) MnO4(e) N2
(f) SO32(g) Na
(h) C2H4
15. Calculate the oxidation number of the bolded
element in each of the following.
(a) Na2O
(b) CaCl2
(c) NaClO4
(d) K2Cr2O7
(e) LiH
(f) H2O2
(g) Na2O2
(h) BrF5
CHAPTER 1 Introduction chemical analysis

25

16. Below are shown the equations for a number of

reactions. Which of these are acidbase reactions
and which are redox?
(a) Zn(s) + 2HCl(aq)
ZnCl2(aq) + H2(g)
(b) H-(aq) + H2O(l)
H2(g) + OH-(aq)
(c) HS-(aq) + OH-(aq)
S2-(aq) + H2O(l)
+
(d) Pb(s) + PbO2(s) + 4H (aq) + 2SO42-(aq)
2PbSO4(s) + 2H2O(l)
17. Which of the following equations demonstrates
the redox properties of sulfuric acid?
(a) 2NaOH(aq) + H2SO4(aq)
Na2SO4(aq) + 2H2O(l)
(b) NaCl(s) + H2SO4(aq)
NaHSO4(aq) + HCl(aq)
(c) Zn(s) + 2H2SO4(aq)
ZnSO4(aq) + 2H2O(aq) + SO2(g)
(d) 2NH3(g) + H2SO4(aq)
(NH4)2SO4(aq)
18. Write half-equations for:
(a) the oxidation of NH3 to NO2
(b) the reduction of OCl- to Cl(c) the reduction of SO42- to SO2
(d) the oxidation of CH4 to CO2.
19. Use the half-equation method to derive the overall
equation for the production of nitrogen dioxide
from concentrated nitric acid and copper.
20. Dichromate ions, Cr2O72-, react with iodide ions, I-,
to produce chromium ions, Cr3+, and iodine, I2.
(a) Write the half-equation for the production of
chromium ions from the dichromate ions and
identify this process as oxidation or reduction.
(b) Write the half-equation for the production
of iodine from iodide ions and identify this
process as oxidation or reduction.
(c) From your answers to parts (a) and (b), derive
the overall equation for this reaction.
(d) Which substance is the oxidant?
(e) Which substance is the reductant?

(a) Write the equation for the reaction between

lithium hydroxide and carbon dioxide.
(b) Calculate the mass of carbon dioxide that could
be removed per kilogram of lithium hydroxide.
A possible alternative chemical for this
process might have been the more readily
available sodium hydroxide.
(c) Write the equation for the reaction between
sodium hydroxide and carbon dioxide.
(d) From (c), calculate the mass of carbon dioxide
that can be removed per kilogram of sodium
hydroxide.
(e) Use your answers to (b) and (d) to suggest a
reason for the choice of lithium hydroxide
rather than sodium hydroxide in a spacecraft.
(f) Derive the ionic equations for both the
reactions mentioned in this question.
23. Limestone is an important raw material for
industry. When heated in a kiln, it decomposes to
form quicklime, CaO, and carbon dioxide. A typical
kiln is shown in the figure below.
(a) If limestone containing 83.5% calcium carbonate is used, calculate the mass of quicklime
that would be produced from 100 tonnes of
this limestone.
(b) Calculate the mass of the above limestone that
would be required to produce 60.0 tonnes of
quicklime.
(c) This process is sometimes called lime burning.
Why is this not a correct term to use?

limestone

Stoichiometry

26

UNIT 3 Chemical pathways

gas
burner

gas
burner

Calculate:
(a) the mass of aluminium oxide produced from
5.0 g of aluminium
(b) the volume of oxygen consumed at 15C and
pressure of 101 300 Pa.
22. As an emergency procedure, the Apollo 13 astronauts used lithium hydroxide to remove carbon
dioxide from the interior of their crippled spacecraft as it returned from the Moon. Like all hydroxides, lithium hydroxide forms the appropriate metal
carbonate when it reacts with carbon dioxide.

21. Aluminium can be used in flashbulbs to produce

an intense burst of light. Aluminium oxide is produced in the process. The equation for the reaction
is:
4Al(s) + 3O2(g)
2Al2O3(s)

quicklime

A typical limestone kiln. The production of lime from

such kilns was one of Australias earliest industries.

24. Silicon carbide is used to coat objects such as drill

bits and saw blades in order to make them more
wear resistant. It is produced by reacting carbon
and silicon dioxide in electric furnaces, according
to:
SiC(s) + 2CO(g)
3C(s) + SiO2(s)

If 1 tonne of carbon and 1 tonne of silicon dioxide

are heated, how much silicon carbide will be
produced?
25. Elemental phosphorus is produced by treating rock
phosphate, Ca3(PO4)2, with a mixture of carbon
and silicon dioxide, according to the following
equation:
2Ca3(PO4)2(l) + 6SiO2(l) + 10C(s)
P4(g) + 6CaSiO3(l) + 10CO(g)
In this process, the rock phosphate is rarely pure,
and various unavoidable losses occur, reducing
the efficiency of the process.
(a) If the rock phosphate used contains 90%
calcium phosphate, how much rock phosphate is needed to produce 1 tonne (1000 kg)
of phosphorus, P4?
(b) If the process is only 95% efficient, what is
the total mass of reagents needed to produce
1 tonne of phosphorus?

CHAPTER 1 Introduction chemical analysis

27

Exam practice questions

In a chemistry examination you will be required to write a number
of short and extended response questions. Your answers will be
assessed on how well you:

use your knowledge and the information provided

Unit: 3

communicate using relevant chemistry terminology and

concepts

aOS: 1

present a logical, well-structured answer to the question.

Topic: 1

Practice
VCAA exam
questions

EXTENDED RESPONSE QUESTIONS

1. Give the oxidation number of bromine in each of the

following species.
(a) Br2
(b) Br-

Unit: 3
aOS: 1
Topic: 2

Practice
VCAA exam
questions

(c) OBr-

3 marks

2. Magnesite, MgCO3, is the principal magnesium ore in Australia. This ore can be
analysed by reacting it with hydrochloric acid solution.
(a) Calculate the percentage by weight of magnesium in magnesite.
(b) Write an equation for the reaction of magnesite with the hydrochloric acid.
An ore sample is thought to contain about 0.250 g of magnesium carbonate.
(c) Calculate the volume of 0.100 mol L-1 hydrochloric acid that would be expected to
react with the ore.
(d) Calculate the volume of carbon dioxide that would be produced at STP during the
above analysis.

8 marks

3. Calcium oxide (quicklime) is a useful chemical in agriculture. It is made in large

amounts by heating calcium carbonate (which is found in limestone).
As part of their process controls, companies producing this chemical would
commonly carry out a number of reactions in their laboratories. These would include
reacting both the initial reactant and the final product with hydrochloric acid, as
well as identifying the carbon dioxide gas also produced by reaction with calcium
hydroxide solution (limewater).
(a) Write an equation for the decomposition of the calcium carbonate to produce
calcium oxide.
(b) Write an equation for the reaction of calcium carbonate with hydrochloric acid.
(c) Given that calcium oxide is a basic oxide, write an equation for its reaction with
hydrochloric acid.
(d) Given that carbon dioxide is an acidic oxide, write an equation for its reaction with
calcium hydroxide solution.

28

UNIT 3 Chemical pathways

4 marks