Che181t Study Guide

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CONTENTS
Page
Learning unit 1: Matter1
1.1 Introduction1
1.2 Properties and changes of matter 2
1.3 Classification of matter 2
1.3.1 Element2
1.3.2 Compound3
1.3.3 Substances3
1.3.4 Mixtures3
1.4 Classification of matter as an element, compound or mixture 3
1.4.1 Solubility3
1.4.2 Distillation4
1.4.3 Heat4
1.4.4 Magnetic properties 4
1.5 Energy4
1.6 The periodic table 4
1.7 Properties of ionic and molecular compounds 6
Learning unit 2: Scientific measurements8
2.1 Measurement8
2.2 Measuring length and volume 10
2.3 Measuring mass 13
2.4 Density and specific gravity 13
2.5 Accuracy and precision 14
2.6 Significant figures 14
Learning unit 3: Atomic structure18
3.1 Atoms18
3.2 Atoms, protons, neutrons and electrons 19
3.3 Isotopes19
3.4 The mole concept 19
3.5 Electron configuration 21
3.6 The pauli exclusion principle 22
3.7 Hund’s rule 22
3.8 More about the periodic table 22
Learning unit 4: Chemical bonding26
4.1 An introduction to chemical bonding 26
4.2 The octet rule 27
4.3 Electronegativity29
4.4 The ionic bond 29
4.5 The covalent bond 29
4.6 The polarity of bonds 30
4.7 Valence shell electron pair repulsion theory (vsepr theory) 30
4.8 The structures and shapes of molecules and ions 33
4.9 Resonance and polarity of molecules 35
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CO N T EN T S
Learning unit 5: Gases, liquids and solids37

5.1 The properties of gases 37
5.1.1 5The kinetic-molecular theory 37
5.1.2 The particles of gases 37
5.1.3 Molecular motion and gaseous pressure 38
5.1.4 5Elasticity of molecular collisions 38
5.1.5 Temperature and kinetic energy 38
5.1.6 The postulates for the kinetic-molecular theory 39
5.1.7 The behaviour of gases 39
5.1.8 Boyle’s law 39
5.1.9 Charles’s law 39
5.1.10 The pressure -temperature relationship 40
5.1.11 Avogadro’s law 40
5.1.12 The ideal gas law equation40
5.1.13 The measurement of the pressure of gases 41
5.2 The properties of liquids 42
5.2.1 Surface tension 43
5.2.2 Viscosity43
5.2.3 Evaporation43
5.2.4 Vapour pressure 43
5.2.5 Boiling point 44
5.3 The properties of solids 44
5.3.1 Freezing point and melting point 45
5.3.2 Sublimation46
5.3.3 Phase diagrams 47
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iv
Co nte nt s
LEARNING UNIT
1 1
1 MATTER
LE ARNING OUTCOMES
After studying this learning unit, you should be able to:
•• define matter, mass and weight

•• define each and distinguish between the different physical states of matter
•• distinguish between physical and chemical properties and changes
•• classify matter
•• describe an element, compound, substance and a mixture
•• define energy
•• demonstrate an understanding of the layout of the periodic table
•• demonstrate knowledge of symbols, names and atomic numbers of the first
36 elements on the periodic table
•• distinguish between ionic and molecular compounds
1.1 INTRODUCTION
Chemistry is the science of substances or matter – their properties, composi-
tion, structure and the changes they undergo. Matter is everything that takes
up space and has mass. Mass is a measure of the quantity of the matter of an
object, while weight refers to the force that gravity exerts on an object. The
mass of an object is always constant but the weight will depend on its location.
Matter is continually changing, and being changed, to form other substances.
In these changes or chemical reactions the original substances (reactants)
lose their identity and are changed to new substances (products) with new
properties. For example, table salt (sodium chloride) is produced in a chemical
reaction between a very reactive metal (sodium) and a toxic gas (chlorine).
The science of chemistry is concerned not only with the conditions that bring
about chemical reactions, but also with the factors affecting these reactions
and the energy involved in these reactions.
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1 CH E181T/1

1.2 PROPERTIES AND CHANGES OF MATTER

The physical state of matter can be divided into three phases, namely the:
•• solid phase: rigid; relatively incompressible; definite shape and volume;

the atoms or molecules are in close contact with each other, arranged in
a rigid pattern.
•• liquid phase: fluid; relatively incompressible; definite volume; no definite
shape; the atoms or molecules are further apart from each other than in a
solid, and are free to move, giving a liquid the ability to flow.
•• gas phase: easily compressible fluid; no definite volume or shape; the atoms
or molecules are very far apart from each other; are free to move, giving
a gas the ability to flow.
The properties of matter and the changes it can undergo can be classified
into two groups, namely:
•• Physical properties and changes: the properties and changes that can be
observed without changing the object into another kind of matter
Examples of the properties are: colour, odour, solubility, lustre, melting point,
boiling point, crystal structure, hardness, elasticity, malleability, ductility,
tensile strength, density, thermal conductivity, electrical conductivity
•• Chemical properties and changes: the properties changes that can be

observed only when a substance undergoes a change in composition and
forms a new substance or new substances,
Examples of the changes are: hydrolysis, electrolysis, combustion, neutralisa-

tion, the cooking process.
1.3 CLASSIFICATION OF MATTER

Matter can be classified as either substances or mixtures. Substances can
be classified as either elements or compounds. Mixtures can be classified as
either homogeneous mixtures or heterogeneous mixtures.
FIGURE 1.1
The classification of matter
1.3.1 Element
•• An element is a kind of matter, composed of only one chemically distinct
kind of atom; a substance that cannot be decomposed by any chemical
reaction into simpler substances
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2
L E AR N I N G U N I T 1: M at te r
•• All the elements are presented by the periodic table; 109 elements are
known today; an element cannot be separated into other kinds of matter
by physical means. Examples: carbon (as a black solid or as a diamond),
oxygen (as 02 gas), copper, vanadium, mercury.
1.3.2 Compound
•• A compound is composed of more than one element (chemically bonded)
to form in some cases, a molecule, in other cases, an ionic compound
•• A compound is a chemical composition of more than one element
•• A pure compound, whatever its source, always contains defined and constant
proportions of the elements by mass
•• A compound cannot be separated into other kinds of matter by physical
means; e.g. sodium chloride, sucrose (cane sugar), benzene, methane,
carbon dioxide
1.3.3 Substances
•• A substance can either be an element or a compound
•• A substance cannot be separated into other kinds of matter by physical means
•• A pure substance has a constant composition and definite physical and
chemical properties
1.3.4 Mixtures
•• A mixture can be separated by physical means into two or more substances
•• A mixture consists of two or more substances, in which the substances
retain their identity
•• A heterogeneous mixture consists of physically distinct parts each with
different properties; for example sand and water, sodium chloride and sugar
•• A homogeneous mixture is uniform in composition and properties throughout
a given mixture, but the composition and properties may vary from one
mixture to another; for example a sugar solution, steel, brass
1.4 CLASSIFICATION OF MATTER AS AN ELEMENT, COMPOUND OR

MIXTURE
Matter can be classified according to composition as elements, compounds,
homogeneous mixtures or heterogeneous mixtures. Substances cannot be
separated into other kinds of matter by physical means; it can only be broken
up into elements by chemical means. Mixtures can be separated by physical
means into two or more substances. These physical means include a variety
of methods, depending on the requirements of the exercise.
1.4.1 Solubility
For heterogeneous mixtures, where the one component is soluble in a liquid
phase and the other component is insoluble in the liquid, the two components
of the heterogeneous mixture can be separated from each other by selective
filtration of the insoluble component. The soluble component can be collected
by the evaporation of the liquid phase.
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1.4.2 Distillation
For homogeneous mixtures where a solid component is dissolved in a liquid,
distillation can be used to remove the liquid to leave the solid behind. For
homogeneous mixtures of liquids with different boiling points, fractional distil-
lation can be used to separate the components from each other.
1.4.3 Heat
This method depends on the components having widely different melting points
and/or densities. For example, where a mixture of zinc and lead is melted,
the zinc, which has the lower density, will float on top of the lead and can be
decanted. A mixture of graphite and iodine can be separated by heat, as the
iodine will undergo sublimation.
1.4.4 Magnetic properties

If any of the components of a mixture are magnetic, they can be removed by
drawing a magnet through the mixture. Example: iron filings and sugar.
1.5 ENERGY
Matter, in addition to mass, also possesses energy. Energy is the ability of
matter to do work. There are two different forms of energy: kinetic energy
and potential energy.
Kinetic energy is the energy of motion; potential energy is the energy of posi-
tion, also referred to as stored energy. Energy can be transformed from one
form of energy to another, but can never be lost. The total amount of energy
in the universe is constant or conserved.
This leads us to the law of conservation of energy: energy can never be cre-
ated or destroyed; it can, however. be converted from one form to another,
or transferred from one body to another.
Chemical and physical changes of matter are accompanied by energy transfers.

The kinetic energy of the particles of an object can be expressed by either heat
or temperature. The heat of an object is equal to the total kinetic energy of
all its particles. The temperature of an object is equal to the average kinetic
energy of the particles of the object.
Heat or molecular kinetic energy can cause two types of physical changes:
a change in temperature and a change in the physical state of matter (e.g.
melting, boiling).
1.6 THE PERIODIC TABLE

The Russian chemist Dmitri Mendeleev (1836–1907) grouped all the elements
according to atomic mass and the periodic properties found in the elements.
Our present periodic table, in which elements are grouped according to
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4
atomic number and corresponding periodic chemical properties, was derived

from Mendeleev’s work.
Symbols are used to represent the elements in the periodic table. The first
letter of the symbol is always a capital letter, while the others are always small
letters. For example, Co is the symbol for cobalt, while CO is carbon monox-
ide and consists of the symbols for carbon and oxygen. The symbols of some
elements are derived from their Latin names, such as Au for aurum (gold) and
Fe for ferrum (iron) while many are similar to their English names, e.g. AI for
aluminum and O for oxygen.
TABLE 1.1
The first 36 elements in the periodic table.
VERY IMPORTANT:
The first 20 elements of the periodic table, each with their atomic number
and symbol, must be memorised
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1.7 PROPERTIES OF IONIC AND MOLECULAR COMPOUNDS

Ionic compounds consist of ions of opposite charge, such as Na+Cl- and are
therefore held together by electrostatic attractive forces between the positively
and negatively charged ions. In the solid phase of these ionic compounds the
positively charged ions and the negatively charged ions are all mixed in a
very orderly manner. The ions are arranged in such a way that the oppositely
charged ions (their attractive forces are very high) are closest to each other
and the like charged ions (they repel each other) are furthest from each other.
Ionic compounds have very high melting points, are brittle and relatively hard.
Ionic compounds in the solid state do not conduct electricity, but when they
are melted or dissolved in a liquid they do conduct electricity.
The atoms within molecular compounds are held together by strong attractive
forces because they are sharing electrons. The attractive forces between the
molecules of molecular compounds are not so strong. Molecular compounds
usually have lower melting points and are soft. Molecular compounds usually
do not conduct electricity when melted or dissolved in a molecular liquid,
such as water.
1. 8 Q U E S T I O N S F O R S E L F - E VA LUAT I O N
(1) Define the following concepts:
1.1 matter 1.2 mass

1.3 weight 1.4 solid phase
1.5 liquid phase 1.6 gas phase
1.7 physical properties and 1.8 chemical properties and
changes changes
1.9 element 1.10 compound
1.11 substance 1.12 mixture
1.13 kinetic energy 1.14 potential energy
1.15 heat 1.16 temperature
(2) Draw a schematic diagram to illustrate the classification of matter.

(3) Classify the following as either a physical property change or a chemical
property change:
3.1 The normal boiling point of water is 100 °C
3.2 The density of nickel at 25.0 °C is 8.9 g.cm-3
3.3 Iron corrodes in the presence of moisture
3.4 Formation of dew
3.5 Burning of paper
3.6 Baking of a cake
3.7 Reduction of copper
3.8 Crushing of stones
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6
3.9 Melting of lead at 327.4 °C

3.10 Souring of milk
(4) Classify the following as either an element, a compound, a homogeneous

mixture or a heterogeneous mixture:
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LEARNING UNIT
2 2
2 SCIENTIFIC MEASUREMENTS
LE ARNING OUTCOMES
•• define and distinguish between quantitative and qualitative analysis

•• illustrate the conversion between different units
•• define the difference between accuracy and precision
•• calculate the number of significant figures using scientific notation
2.1 MEASUREMENT
In Chemistry we can study matter either qualitatively or quantitatively. When
we make a qualitative analysis study, we come to know what is present in a
sample of a substance. When we make a quantitative analysis study, we come
to know how much of what is present in a sample of a substance. (A sample
of a substance or a mixture is a representative part of the whole amount of
substance or mixture.)
When we study matter and the changes it undergoes, we need to make measure-
ments to be able to quantify our conclusions. A measurement is the comparison
of the observed property to a standard with a known value of the property.
The measurement is expressed as a product of a numerical value and a unit.
For example: 10 m
The unit indicates the standard of the property. The numerical value, given
to a certain number of significant figures, gives the factor with which the ob-
served property differs from the standard of the property. For example, if we
measure the height of a mercury column, and we note that it is 14,5 m, then
we mean that the height is 14,5 times as high as the standard of 1 m for the
property length.
We can use many units to describe the standard of the property. These different
units are all related to each other. For example, we can use the units millimetre,
centimetre, or metre to describe the property length. But these units are all
related to each other in such a way that 10 mm is equivalent to 1 m, and 100
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L E AR N I N G U N I T 2: S c i e nt i f i c m e asu r e m e nt s
m is equivalent to 1 m. The system used to determine the base units for the
measurement of the standards of the properties is the International System of
Units, abbreviated as the SI System. The SI has determined seven base SI units
to be used to determine the standards of the seven basic properties.
TABLE 2.1
The seven base SI units
Property Symbol Unit Symbol
Length l metre m
Mass m kilogram kg
Time t second s
Electric current ⧯ ampere A
Temperature T kelvin K
Amount of n mole mol

substance
Luminous candela cd
intensity
area A square metre m2
volume v cubic metre m3
density p gram per cubic kg.m–3 or org.cm–3

centimetre
velocity v metre per m.s-1

second
acceleration a metre per sec- m.s-2
ond squared
force F newton N = kg.m.s-2
pressure p pascal Pa = N.m-2 =

kg.m-1s-2 11111.s-2
energy E joule J = N.m = kg.m2 .s-2
power p watts w = J .s-1 =

K g.m2.s-3
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2.2 MEASURING LENGTH AND VOLUME

The base SI unit for length is metre (m). The unit “metre” can be converted
to decimetre and centimetre when smaller lengths are measured. Volume is
the amount of space occupied by matter. The SI unit of volume is cubic me-
tre (generally volume is measured in cubic decimetres or cubic centimetres).
Volume can also be measured in millilitres or litres.
The most common containers measuring liquids are a beaker, graduated

cylinder, volumetric flask, burette and a pipette, shown in figure 2.1. These
containers are calibrated with liquids of known volumes. The volume of a
liquid is determined by reading the position of the bottom of the meniscus of
the liquid (see figure 2.2).
When measuring volume, the accuracy of measurement required will deter-

mine the apparatus to be used.
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FIGURE 2.1
Some common measuring devices for liquids
Burette Pipette
Graduated measuring cylinder
Volumetric flask Graduated beaker
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11 CH E181T/1

FIGURE 2.2
Reading the level of the meniscus of a liquid
For general purposes, when only a rough indication of the volume is necessary,
the graduated beaker and graduated measuring cylinder are usually used. A
beaker and measuring cylinder can never be used to measure a volume ac-
curately; these apparatuses are not accurately calibrated.
When transferring specific volumes of fluid accurately, a pipette is used. A

pipette holds a specific volume if the pipette is filled to the mark showing the
specific volume. Typical pipette volumes are 1, 2, 3, 4, 5, 10, 15, 20, 25, 50,
100 cm3, and so forth. These volumes are accurate to two decimal places
and are calibrated at a fixed temperature. A bulb or propipette is used to suck
fluids into the pipette. This bulb is a rubber ball with two intakes (each with
a value) – one is coupled to the pipette and one is open to the atmosphere.
When the ball is compressed, the air inside the bulb is forced out, creating a
negative pressure inside. When the intake joined to the pipet is opened, the
atmospheric pressure outside forces the fluid into the pipette. The other intake
can be used to regulate the pressure in the bulb in order to get the meniscus
to the mark.
A volumetric flask is a flask accurately calibrated at a fixed temperature to

a specific volume with a well-fitted stopper. The calibrated volume (e.g. 10,
15, 20, 50, 100, 150, 200, 500ml, etc.) is indicated on the flask with a mark.
The volumetric flask is used to prepare solutions of known concentrations. A
known amount of substance is put into the flask with a funnel. Water is then
added through the funnel to rinse off all the solid from the funnel into the
flask. The solid is dissolved in the flask by gently swirling the flask. The flask
is then filled with water, while swirling continuously. When the mark on the
neck of the flask is approached, water is added slower – until the bottom of
the meniscus of the water just touches the mark. This is the volume the flask
is calibrated for. Remember that the flask is calibrated at a specific tempera-
ture, such as 20.0 °C or 25.0 °C and the liquid in the flask must be as close
as possible to the calibrated temperature.
The burette is a very accurate apparatus for measuring volume, especially if

a non-constant volume must be measured. The burette is also calibrated at
a specific temperature. Any volume of liquid can be measured accurately to
two decimal places with a burette. The burette is calibrated in such a way that
zero is at the top and 50.00 cm3 is at the bottom. The burette is filled with
the specific liquid and some liquid is let out until the meniscus is at zero. The
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required amount of liquid is then let out to the reaction vessel and the volume
of liquid let out is read off the burette. The burette is usually used for titrations.
2.3 MEASURING MASS

Mass is the measure of the quantity of matter in an object. The terms “mass”
and “weight” are often used interchangeable, although they refer to different
quantities. The term “weight” refers to the force that gravity exerts on an object.
The mass of an object always remains the same, but the weight depends on
the location in a gravitational field.
Chemists use a chemical balance to measure mass. An open pan balance

is used for less accurate measurements and an analytical balance is used to
measure masses accurately to up to four decimal places.
2.4 DENSITY AND SPECIFIC GRAVITY

Density (p) is the relationship between the mass and the volume of a sub-
stance at a specific temperature (because volume varies with temperature). In
other words, it is the mass of a substance present, per unit volume. We can
use various units to express the density of substances, of which g.cm-3 and
kg.m-3 are the most common.
Eq 2.1
mX is mass and VX is volume
Density, which is a physical property, is not dependent on the amount of

substance present. The density of gold is 19.3 g.cm-3 or 19.3 x 103 kg.m-3. This
means that the mass of 1 cm3 of gold is 19.3 g, or the mass of 5 cm3 of gold is
=5 cm3 x 19.3 g.cm-3

=96.5 g
Densities can be expressed in a variety of different units. These different ex-

pressions for the density of the same substance at the same temperature, have
different numerical values for different units.
To avoid all these densities in different units, specific gravity (SG) has been
defined. The specific gravity of a substance is defined as the ratio of the density
of the substance to the density of water, at the same temperature:
Eq 2.2
The specific density of a substance indicates how much denser the substance
is than water. For example, if the specific density of a substance is 2, it means
that the substance is twice as dense as water. Specific density has no units and
therefore can be multiplied with the density of water in the appropriate units,
to obtain the density of the substance in the required units:
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13 CH E181T/1

Eq 2.3
2.5 ACCURACY AND PRECISION

When we measure properties we can obtain various values for the same
property, depending on the instrument we use to make the measurement.
There is, however, only one true value for the specific property; this is the
actual value, which we not always know the value of. Only when we use
instruments, carefully calibrated, against standards, will we obtain the true or
actual values of properties.
There are two terms that describe the measurements made.
(1) The first one is accuracy. Accuracy refers to the closeness of the meas-
ured value to the true value. The closer it is to the true value, the more
accurate the measured value is; the further the measured value is from
the true value, the less accurate the measured value is.
(2) The second one is precision. Precision refers to how close the measure-
ments of the property are to each other. It indicates the degree of repro-
ducibility of the measured quantity. The closer the measured values are
to each other, the higher the precision; the further the measured values
are from each other, the lower the precision. In other words, when the
precision of a number of measured values are high, it means that each of
the measured values deviate only a small amount from the average value;
when there is a wide deviation among the measurements, the precision
is low. Measurements with a high precision does not necessarily have a
high accuracy. It is, however, more likely that measurements with a high
precision will be more accurate, and values with a low precision will be
less accurate.
2.6 SIGNIFICANT FIGURES

The numerical value of a measurement consists of a number of digits. For
example, 15.25 consists of four digits, 0.00175 consists of six digits and 150
consists of three digits. Some of these digits are significant and others are not.
The number of significant digits in a numerical value determines the certainty
of the numerical value.
The following points are important to be able to determine the number of

significant figures of a numerical value:
(1) To determine the number of significant figures of a numerical value, we

must count all the significant figures.
(2) In a numerical value there can be digits to the left and to the right of the
decimal point.
(3) All nonzero digits appearing in a numerical value are significant.
(4) Some of the zeros appearing in the numerical value are significant, some
are not.
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14
Zeros that precede the first nonzero digit are not significant. Zeros between
nonzero digits are significant. Zeros at the end of the numerical value are
significant.
A numerical value is written in scientific notation when the value is written as

a number from 1 to 10, multiplied by 10 raised to some power. For example,
0.074010 is equal to 7.4010 x 10-2 when written in scientific notation. A value
written in scientific notation, therefore, must have only one nonzero figure
on the left of the comma.
We can best illustrate with examples which zeros are significant – as listed
in table 2.6.
TABLE 2.6
Examples indicate the number of significant figures.
Numerical Scientific notation Total number of

value significant figures
120 = 1.20 x 102 3
= 1.2 x 102 2
120.0 = 1.200 x 102 4
40120 = 4.0120 x 104 5
400.8 = 4.008 x 102 4
0.012 = 1.2 x 10 -2 2
0.0120 = 1.20 x 10 -2 3
0.001805 = 1.805 x 10 -3 4
7000 = 7.000 x 103 4
46.020 = 4.6020 x 101 5
30.0 = 3.00 x 101 3
0.1890 = 1.890 x 10 -1 4
40.03 = 4.003 x 101 4
40.030 = 4.0030 x 101 5
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15 CH E181T/1

When multiplying and dividing numerical values, the final answer has as many
significant figures as there are in the measurement with the least number of
significant digits.
Example:2.546 x 0.20 = 0.5092 = 0.51
When adding and subtracting numerical values, the final answer has the same
number of decimal places as there are in the measurement with the least
number of decimal places.
Example: 1848.17 – 25.8 = 1822.37 = 1822.4
Sometimes we want to reduce the number of significant figures of a numerical

value. We then have to drop some of the digits on the right of the numerical
value. We refer to this procedure as “rounding off” numerical values. To “round
off” numerical values to a lesser number OR less numbers? of significant figures
, one must look at the left-most digit to be dropped (that is “e” in the following
example: a b c d e f g .....).
The “rounding off” procedure is as follows:
If “e” < 5 then just drop “e”, “f”, “g”, and so on.
If “e” > 5 then drop “e”, “f”, “g”, and so on, and increase “d” by 1.
Examples: Round the following values off to:
1 significant figure: 0.0054 = 0.005
2 significant figures : 0.08253 = 0.083
2 significant figures: 0.0744 = 0.074
2 significant figures: 0.04750 = 0.048
3 significant figures: 30704 = 307 x 102
2.7 Q U E S T I O N S F O R S E L F - E VA LUAT I O N
(1) Convert the following units:
1.1 10 ml = cm3 1.2 250 nm = _______mm
1.3 40dm3 = m3 1.4 kPa.dm3 = _______Pa.m3
1.5 Pa.m3 = J 1.6 1.25 g.cm-3 = _______kg.m3
1.7 50 kg = lb 1.8 23.45 cm3+ _______dm3
(2) Convert the following, given that density of Au = 19.3 g.cm-3.

2.1 5.0 g Au = cm3 2.2 1.25 cm3 _______Au g
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16
(3) Given the information in table 2.5 and the SG copper = 8.9863, calculate
the density of copper at 25.0 °C, in the units g.cm-3.
(4) Express each of the following in scientific notation:
4.1 52.65 4.2 0.42500
4.3 0.0045 x 104 4.4 0.000672
4.5 124.45 x 10 –5 4.6 62500.20
4.7 200 4.8 122.25 x 102
(5) How many significant figures does each of the following contain?
5.1 80.045 5.2 0.054200
5.3 0.1000 5.4 12.25 x 10 - 4
5.5 0.016 5.6 2.48 x 103
5.7 0.20047 5.8 468.00
(6) Round off each of the following to three significant figures:
6.1 543.21 6.2 88.4500
6.3 21.09 6.4 25.555
6.5 94658.00 6.6 0.5249
6.7 0.005583 6.8 5000.00
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17 CH E181T/1

LEARNING UNIT
3 3
3 ATOMIC STRUCTURE
LE ARNING OUTCOMES
•• describe the structure of an atom

•• describe the difference between mass number and atomic number
•• define an isotope
•• explain the mole concept and its application in calculations
3.1 ATOMS
Matter can be classified according to composition as elements, compounds
or mixtures. Compounds and mixtures can both be broken up into elements,
which are composed of only one chemically distinct kind of atom. Before we
define an atom, we first need to consider Dalton’s Atomic Theory. In 1808,
the English chemist John Dalton (1766–1844) formulated a definition of the
indivisible building blocks of matter, called atoms. Dalton’s Atomic Theory
can be summarised as follows:
(1) All elements are made up of very small, discrete, indivisible particles
called atoms.
(2) All atoms of a given element are identical in mass, chemical and physical
properties, and atoms of different elements differ in this respect.
(3) Compounds, the chemical combination between two or more elements,
consist of the combination of atoms in simple numerical ratios.
(4) A chemical reaction involves only the separation, combination or rear-
rangement of atoms, and does not result in their creation or destruction.
We can now define an atom as the smallest fundamental particle of an ele-

ment that has all the properties of that element; it is the smallest representative
sample of an element.
Further investigation led to the discovery that atoms possess an internal struc-
ture. The atom consists of a very small, extremely dense centre, called the
nucleus and a relatively large surrounding area, low in density, in which the
electrons move. To summarise, the atom consists of the nucleus and surround-
...........
18
L E AR N I N G U N I T 3: Ato m i c s t r u c t u r e
ing electrons, and the nucleus consists of protons and neutrons. An atom is
always electrically neutral because the number of electrons in the atom is
always equal to the number of protons in the atom.
3.2 ATOMS, PROTONS, NEUTRONS AND ELECTRONS

To describe the atoms of a specific element, we use the following symbols,
written in this specific way:
E Represents the symbol of the specific element

A Represents the mass number of the atom of the element
Z Represents the atomic number of the atom of the element
3.3 ISOTOPES
In most cases not all atoms of a given element have the same mass number.
This means that not all atoms of a given element have the same number of
neutrons. (For atoms of the same element, they must all have the same number
of protons. For mass number of the atoms of the same element to differ, they
must have different numbers of neutrons.)
For example, in the element hydrogen, there are three distinct types of atoms, all
with the same number of protons, but different numbers of neutrons. These are:
hydrogen (protium) deuterium tritium
Atoms that have the same number of protons (and therefore are of the same
element) with different numbers of neutrons are called isotopes.
The mass number (A) of an atom of an element is the total number of protons
and neutrons in the nucleus of the atom. The mass number of an atom is
always an integer.
The atomic mass of an element, as found on the periodic table, is not an integer.
The atomic mass is the mean value of the mass numbers of all the different
isotopes of the element.
3.4 THE MOLE CONCEPT

The mass number of an atom of an element gives the total mass of the protons
and neutrons in the atom. To understand the unit in which this mass number
of an atom is measured, we have to use the following explanation:
The carbon-12 atom was taken to start with. This is the 12C atom.
This atom consists of 6 protons and 6 neutrons in the nucleus. Because it is

neutral, it also contains 6 electrons. They have assigned a mass of 12 atomic
mass units (abbreviated as amu) to this carbon atom. 1 amu will then be ex-
actly 1/12 of the mass of one carbon-12 atom.
...........
19 CH E181T/1

To summarise:
Mass of 1 12C atom = 12 amu
1 amu = 1/12 mass of 12C atom
Mass of 6.022169 x 1023 12C atoms = 6.022169 x 1023 x 12 amu
The mass of 6.022169 x 1023 12C atoms were found to be equal to 12 g. This
means that we can now say that:
Mass of 6.022169 x 1023 12C atoms = 6.022169 x 1023 x 12 amu= 12 g
This means that: 6.022169 x 1023 x 12 amu = 12 g

1 amu = (1/(6.022169 x 1023) g
1 amu = 1.66053128 x 10 -24
Consider the following again:
Mass of 6.022169 x 1023 12C atoms = 12 g
The quantity of one mole is assigned to the value of 6.022169 x 1023. This
simply means that 6.022169 x 1023 of anything whatsoever, is called one mole
of that specific thing.
Therefore:
1 mol of particles 6.022169 x 1023 particles

1 mol of particles 6.022169 x 1023 particles
1 mol of atoms 6.022169 x 1023 atoms
or
1 mol of molecules 6.022169 x 1023 molecules
1 mol of ions 6.022169 x 1023 ions
This constant value of 6.022169 x 1023 is called Avogadro’s number, abbrevi-

ated as NA.
Note that mol is the abbreviation for mole. To conclude we can now say that:
Mass of 1 12C atom = 12 amu

= 12 x (1 I (6.022169 x 1023) g
Mass of 6.022169 x 1023 12C atoms = 12g
Mass of 1 mol of 12C atoms = 12
...........
20
We can now say that the mass of 1 mol of 12C atoms is 12 g. In nature, how-
ever, not only 12C atoms appear and therefore we must use the atomic mass
(average mass number) for the mass of 1 mol of carbon atoms. The atomic
mass for carbon on the periodic table is 12.01115. The molar mass of carbon
is therefore 12.01115 g for 1 mol, that is 12.01115 g.mo -1
We can now say that the molar mass of an element is equal to the atomic
mass of the element, and define the molar mass as the mass of 1 mol
(6.022169 x1023 of atoms of that specific element, measured in g.mol-1).
3.5 ELECTRON CONFIGURATION

The way electrons are located around the nucleus of an atom of an element
is known as the element’s electron configuration or electron structure. The
electron configuration of an element is therefore the designation of all the
electrons of an atom into specific shells and subshells around the nucleus. The
electron structure of the atoms of an element is of great importance because
it determines the chemical properties of the element. Electrons always occupy
the orbitals around the nucleus of an atom in such a way that the energy of
the atom is minimised. Therefore, the order in which the electrons occupy
the orbital is as follows:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 4s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, 7p, .......
A diagrammatic representation of this order is as follows:
Remember that:
•• an s-orbital can occupy a maximum of 2 electrons

•• the three p-orbitals can occupy a maximum of 6 electrons
•• the five d-orbitals can occupy a maximum of 10 electrons
The location of each electron of an atom can be described by four quantum

numbers. When we write down the electron configuration of the atoms of an
element we only refer to two of the four quantum numbers, n and l, that is the
description of the shell and the subshell of the orbitals of the electrons. We
also indicate the number of electrons in each of the subshells.
...........
21 CH E181T/1

The “3” indicates the first quantum number: n = 3

The “d” indicates the second quantum number: l = 2 for the d-orbital
The “5” indicates the number of electrons in the d-subshell.
TABLE 3.1
The electron configuration of various elements
H 1s1
He 1s2
Li 1s2 2s1
Be 1s2 2s2
B 1s2 2s2 2p1
C 1s2 2s2 2p2
N 1s2 2s2 2p3
0 1s2 2s2 2p4
3.6 THE PAULI EXCLUSION PRINCIPLE

The location of each electron occupying an orbital around the nucleus of an
atom can be described by four quantum numbers. No two electrons in the
same atom of an element can have the same set of four quantum numbers.
This phenomenon is called the Pauli’s exclusion principle. When the set of
four quantum numbers for an electron in an atom is for example ( n, l, ml,
ms) = (2, 1, -1, +1/2), then no other electron in the same atom can have the
same set of four quantum numbers. Another electron can have the same first
three quantum numbers but with opposite spin its fourth quantum number
will be -1/2; the four quantum numbers of this electron being (2, 1, -1, -1/2).
The Pauli exclusion principle states therefore that no more than two electrons
can fit into any atomic orbital.
3.7 HUND’S RULE

Electrons occupy orbitals around the nucleus of an atom in such a way that
the energy of the atom is minimised. The electrons occupy the orbitals in the
order: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, … . In the same subshell electrons acquire
the same amount of energy. Electrons occupy the orbitals in the same subshell
in such a way that as many electrons in the same subshell remain unpaired
as possible.
3.8 MORE ABOUT THE PERIODIC TABLE

The periodic table is structured according to columns and rows. There are
eighteen (18) vertical columns and seven (7) horizontal rows in the periodic
...........
22
table. The elements in a vertical column of the periodic table is known as a

group and the elements in a horizontal row of the periodic table is known
as a period.
The elements in certain regions of the periodic table bear similarities concerning
their properties. These regions are called families of elements. There are three
main regions on the periodic table: the metals, metalloids and the nonmetals.
The areas for these three regions are:
•• metals: all the elements from the left side of the periodic table, except for
hydrogen, through to group 12 as well as AI, Ga, In, Sn, Tl, Pb, Bi and Po
•• metalloids: B, Si, Ge, As, Sb, Te
•• nonmetals: C, N, P, 0, S, Se, group 17 and group 18.
The other families are the:
•• alkali metals: all the elements in group 1, except for hydrogen

•• alkaline earth metals: all the elements in group 2
•• halogens: all the elements in group 17
•• noble gases: all the elements in group 18
•• transition metals: all the metals in group 3 through to group 12, that is all
elements with atomic numbers 21 through to 30; 39 through to 48; 57; 72
through to 80; 89; and 104 through to 111
•• inner transition metals: they are normally shown in two rows below all
the other elements on the periodic table. They include elements 51–57
(lanthanides) and 89–103 (actinides).
•• lanthanide elements or rare earths: all the elements with atomic numbers
58 through to 71
•• actinide elements: all the elements with atomic numbers 90 through to 103
The lanthanide and actinide elements are set aside from the main body of the
periodic table to avoid making the table too wide.
The position of an element on the periodic table gives an indication of the

electron structure or configuration of the element. It tells us specifically more
about those electrons in the highest energy level of the atoms of the element.
The electrons in the highest occupied energy level of the atoms of an ele-
ment are also called the valence electrons of atoms of the element. It is all
those electrons with the highest value of n, the principal quantum number.
The valence electrons are all in the valence shell of the atoms of the element.
The atoms of the elements in groups 1 and 2 have their valence electrons in
s-orbitals. Groups 3 through to 12 have their valence electrons in d-orbitals.
Groups 13 through to 18 have their valence electrons in p-orbitals. The lan-
thanide and actinide elements have their valence electrons in f-orbitals.
...........
23 CH E181T/1

(1) Briefly describe or define the following:
1.1 proton 1.2 neutron

1.3 electron 1.4 isotope
1.5 mass number 1.6 atomic mass
1.7 atomic number 1.8 one mole
1.9 orbital 1.10 electron configuration
1.11 Pauli exclusion principle 1.12 Hund’s rule
1.13 first ionisation energy 1.14 electron affinity
(2) Complete the following table:
Number of Number of Number of

protons neutrons electrons
1
H
118
16
0
1602-
19
F
19 -
F
24
Mg2+
197
Au+
210
Pb
207
Pb
(3) Calculate the mass of one hydrogen atom. What is the mass of one hy-
drogen molecule?
(4) How many atoms are present in 5.0 g of aluminum?
(5) Calculate the molar masses of the following:
5.1 NH4Cl 5.2 Na2C03

5.3 Ca3(P04)2 5.4 (NH4)2C03
5.5 O2 5.5 OH-
...........
24
(1) Give all possible sets of four quantum numbers for the following energy
levels:
6.1 The first energy level

6.2 The third energy level
(2) Give full electron configurations for the following:
7.1 u 7.2 U+
7.3 F 7.4 F-
2 3
7.5 Mg + 7.6 Mn +
2
7.7 O- 7.8 H
...........
25 CH E181T/1

LEARNING UNIT
4 4
4 CHEMICAL BONDING
LE ARNING OUTCOMES
•• define chemical bonding

•• draw Lewis symbols of elements
•• draw Lewis structures of compounds
•• define electronegativity
4.1 AN INTRODUCTION TO CHEMICAL BONDING

All systems tend to change from a state of high energy (less stable state) to a
state of lower energy (more stable state). Chemical bonding takes place when
atoms combine with each other by sharing or exchanging electrons, especially
the valence electrons. When doing so, atoms achieve more stable electron
configurations.
When two atoms are far apart, their potential energy is arbitrarily taken as zero.
As the distance between two atoms decreases, the attracting force between
the nucleus of the one atom and the electrons of the other atom increases.
The potential energy decreases and the stability increases. As the distance
between the two atoms decreases, more of the potential energy of the two
atoms eventually reaches a minimum and the stability reaches a maximum.
The distance between the two atoms at this point will be the most favourable
distance between two atoms that are chemically bonded to each other.
If the distance between the two atoms decreases more, the repulsion between
the nucleus of the one atom and the electron cloud of the other atom and
vice versa increases. This causes the potential energy of the two atoms to in-
crease and the stability to decrease. This is an unfavourable situation. When
atoms combine to decrease their potential energy, that is increasing their
stability; they can do so through two ways:
•• Electron transfer in ionic bonding: one or more electrons are transferred

from one atom to another, forming cations (the atom that has lost its
electron(s)) and anions (the atom that has gained the electron(s)), and
...........
26
L E AR N I N G U N I T 4: Ch e m i c a l b o n d i n g
•• Electron sharing in covalent bonding: one or more pairs of electrons are

shared between both atoms; the pair(s) of electrons spend time around
both nuclei
4.2 THE OCTET RULE

Chemical bonding takes place when atoms combine with each other by sharing
or exchanging electrons, especially the valence electrons, to achieve more
stable electron configurations. The noble gases generally do not bond; they
must therefore have a stable electron configuration.
The electron configuration of the valence electrons of the noble gases (except
for helium) are in the form of:
There are therefore eight valence electrons in the valence shell of the atoms
of the noble gases. Therefore eight electrons in the valence s- and p-orbitals
form a stable configuration, called the noble gas configuration. The valence
electrons of many compounds have this noble gas configuration and this
phenomenon led to the definition of the octet rule. The octet rule states that
bonded atoms tend to lose, gain or share electrons until they each have a
share in eight valence (outermost) electrons.
For the elements hydrogen, helium, lithium, beryllium, boron and sometimes
carbon, the stable electron configuration is in the form of the electron con-
figuration of helium, and that is:
There are therefore two valence electrons in the valence shell of the atoms
of these elements in their noble gas electron configuration. This is sometimes
referred to as the duet rule. To be able to determine the valence electron
configuration of chemical compounds, one must first find the valence electron
configuration of the individual atoms of the compound. To find this, one can
use the periodic table. The periodic table consists of eighteen groups:
•• The elements in group 1 have 1 valence electron.

•• The elements in group 2 have 2 valence electrons.
•• The elements in group 18 have 8 valence electrons, these being the noble
gases with their stable 8 valence electron configurations.
An atom in a chemical compound obtains a noble gas configuration through

the following ways:
•• the loss of electron(s): the elements in group 1 (with 1 valence electron)

normally lose 1 electron, the elements in group 2 normally lose 2 electrons,
the elements in group 13 normally lose 3 electrons and the elements in
...........
27 CH E181T/1

group 14 sometimes lose 4 electrons to obtain a noble gas valence electron

configuration
•• the gaining of electron(s): the elements in group 14 sometimes gain 4
electrons, the elements in group 15 normally gain 3 electrons, the elements
in group 16 normally gain 2 electrons and the elements in group 17 normally
gain 1 electron to obtain a noble gas valence electron configuration
•• The sharing of electrons: the elements in covalently bonded compounds
very often share electrons with other atoms to obtain access to eight valence
electrons
The valence electrons are those electrons in the outermost shell; that is the
shell of highest principle quantum number.
We use Lewis (dot) symbols to present the arrangement of the valence electrons
around the atom of an element.
A Lewis symbol consists of the symbol of the element surrounded by the va-
lence electrons of the element, indicated by dots(), crosses(x), little circles(o)
or stars(*).
We use Lewis structures to present the arrangement of the atoms and their
valence electrons in the molecule or ions of a chemical compound.
A Lewis structure represents the formula of a compound. It indicates the ar-

rangement of all the atoms present in the molecule of the compound, each
atom surrounded by its valence electrons. Ions in the compound are indicated
by square brackets ([ ]), and electrons shared by atoms (thus forming bonds)
are indicated by circling the specific electrons, as illustrated in figures 4.1 and
4.2. Remember that the octet rule must be obeyed as far as possible, when
constructing Lewis structures.
FIGURE 4.1
The Lewis symbols of various elements and ions. (Note that the amount of elec-
trons is very important; not the position of these electrons around the symbols of
the element.)
...........
28
FIGURE 4.2
The Lewis structures of various molecules, polyatomic ions and compounds.
4.3 ELECTRONEGATIVITY
Electronegativity is the measurement of the ability of an atom to attract
electrons to itself in a chemical bond; electron affinity is the energy released
when an atom gains an electron. Positive numerical values are assigned to all
the elements, indicating their electronegativities. The higher the electronega-
tivity value of an element, the higher its ability to attract electrons to itself.
4.4 THE IONIC BOND

Atoms with low first ionization energies (low electron affinities and low elec-
tronegativities) tend to form cations. Atoms with high first ionisation energies
(high electron affinities and high electronegativities) tend to form anions. The
elements most likely to form cations are those in groups 1 and 2. The elements
in groups 16 and 17 tend to form anions.
4.5 THE COVALENT BOND

The basic principle involved in covalent bonding (in molecular compounds)
is the sharing of electrons between two atoms. We are not going to deal with
all the aspects of covalent bonding; the actual processes involved are far
more complicated than the simple examples used in this text.
Atoms with widely differing electronegativities tend to form ionic bonds where
the atom with the lower electronegativity gives up its electrons and the atom
with the higher electronegativity accepts the electron. This type of bond is
typical between metals and nonmetals. Atoms with little or no difference in
electronegativity tend to form covalent bonds. As the electronegativity de-
termines the attraction an atom has for a shared electron, it stands to reason
that an equal distribution of electrons will occur if the electronegativities of
the atoms are the same and an unequal distribution of electrons will occur
if the electronegativities of the atoms differ. Atoms try to attain the electron
configuration of the nearest noble gas.
...........
29 CH E181T/1

4.6 THE POLARITY OF BONDS

The polarity of the chemical bonds in compounds has a large influence on the
chemical properties of the compounds. The polarity of a bond between two
atoms is determined by the difference in electronegativities of the two atoms
in the bond. The polarity of the bond determines the type of bond that exists
between the two atoms.
The following points summarise the possibilities when two atoms, each with
an electron, come together to form a bond:
(1) Both atoms can have the same electronegativities. They will share the
electron pair equally and form a nonpolar covalent bond.
(2) The atoms can have a slight difference in their electronegativities. The
electron pair will then spend more time in the vicinity of the atom with
the higher electronegativity and less time in the vicinity of the atom with
the smaller electronegativity. The bond between the two atoms will be
a polar covalent bond.
(3) The atoms can have a large difference in electronegativities. The atom
with the smaller electronegativity donates its electron to the atom with
the higher electronegativity. The atom with the higher electronegativity
now has its own electron and has gained an electron from the atom with
the smaller electronegativity. This electron pair belongs completely to
the atom with the higher electronegativity forming an ionic bond, held
together by the electrostatic attraction forces between the negatively and
positively charged ions.
The electronegativities of the elements and the differences in the electron-

egativities of the elements in chemical bonds can help us tell the type of
chemical bond. However, there is no sharp transfer from nonpolar covalent
to polar covalent to ionic bonds; the differences in the electronegativities of
the elements in chemical bonds rather tell us the percentage ionic character of
a chemical bond. The higher the percentage ionic, the more ionic the bond.
4.7 VALENCE SHELL ELECTRON PAIR REPULSION THEORY (VSEPR

THEORY)
The valence electron pairs surrounding an atom are all negatively charged.
The valence shell electron pair repulsion theory states that these electron pairs
repel each other as far as possible. Some of these electron pairs surrounding
the atom will take part in chemical bonds. This implies that this repulsion of
electron pairs will influence the orientations of the chemical bonds which
will at the end influence the shape or geometry of the formed compound.
Electron pairs involved in chemical bonds are called bonding (electron) pairs
(BP). Electron pairs not involved in chemical bonds are called lone (electron)
pairs (LP).
Let us summarise some possibilities:
•• The central atom of a molecule or ion with two bonding pairs of electrons
will have an angle of 180° between each electron pair. The molecule or
ion will have a linear geometry.
...........
30
•• The central atom of a molecule or ion with three bonding pairs of electrons
will have an angle of 120° between each electron pair. The molecule or
ion will have a trigonal planar geometry.
and one lone pair of electrons will have an angle of 120° between each
electron pair. The molecule or ion will have a bent geometry, because only
two of the three electron pairs are involved in bonding.
•• The central atom of a molecule or ion with four bonding pairs of electrons
will have an angle of 109.5° between each electron pair. (Remember that
this is a three-dimensional structure and the angles therefore do not add
up to 360°.) The molecule or ion will have a tetrahedral geometry because
all four electron pairs are involved in bonding.
and one lone pair of electrons will have an angle of 109.5° between each
electron pair. (Remember that this is a three-dimensional structure and the
angles therefore do not add up to 360°.) The molecule or ion will have a
trigonal pyramidal geometry, because only three of the four electron pairs
are involved in bonding.
...........
31 CH E181T/1

and two lone pairs of electrons will have an angle of 109.5° between each
bent geometry, because only two of the four electron pairs are involved
in bonding.
•• The central atom of a molecule or ion with one bonding pair of electrons
and three lone pairs of electrons will have an angle of 109.5° between each
linear geometry, because only one of the four electron pairs is involved in
bonding.
•• The central atom of a molecule or ion with five bonding pairs of electrons
will have angles of 120° between some electron pairs and 90° between
other electron pairs. (Remember that this is a three-dimensional structure
and the angles therefore do not add up to 360°.) The molecule or ion will
have a trigonal bipyramidal geometry, because all five electron pairs are
involved in bonding.
...........
32
•• The central atom of a molecule or ion with four bonding pairs of electrons
and one lone pair of electrons will have angles of 120° between some
electron pairs and 90° between other electron pairs. (Remember that this
is a three-dimensional structure and the angles therefore do not add up
to 360°.) The molecule or ion will have a distorted tetrahedral geometry,
because only four of the five electron pairs are involved in bonding.
and two lone pairs of electrons will have angles of 120° between some
electron pairs and 90° between other electron pairs. (Remember that this
is a three-dimensional structure and the angles therefore do not add up to
3600.)
The molecule or ion will have a T- shaped geometry, because only three
of the five electron pairs are involved in bonding.
4.8 THE STRUCTURES AND SHAPES OF MOLECULES AND IONS

A molecule or ion (a poly-atomic cation or poly-atomic anion) consists, in many
cases, of a central atom that is bonded to surrounded atoms.
...........
33 CH E181T/1

When an atomic orbital of the one atom overlaps with an atomic orbital of
another atom, one pair of electrons (two electrons) is shared and one bond has
formed. These two electrons could have come one each from each atom (in
the bond) to form a covalent bond, or these two electrons could have come
both from one atom (in the bond) to form a dative covalent bond.
Very often, the central atom of this molecule or ion first goes through several
steps before it bonds with the surrounding atoms. These steps include the
excitement of valence electrons, the hybridisation of valence orbitals and then
bond formation.
THE MOLECULE: BEF2

Beryllium (Be) in the ground state has no unpaired valence electrons. The Be
atom in BeF2 is bonded to two F atoms. Beryllium therefore has to have two
unpaired electrons before it can bond with two F atoms. One electron of the
valence electron pair of the Be atom must therefore be excited, to give the Be
atom two unpaired electrons, so that the Be atom can bond atom with two F
atoms after the hybridisation of its two half-filled valence orbitals. Be therefore
undergoes sp hybridisation (sp = 2 orbitals) before it bonds with two F atoms.
The electron pair arrangement of the central atom (that is the arrangement
of the valence electrons of Be, including the bonding electrons of the two F
atoms) is linear. This is because the two pairs of electrons (one pair of electrons
for each of the two bonds) around the central atom repel each other as much
as possible and therefore are linearly arranged (180° between electron pairs).
The geometry of the BeF2 molecule is linear because two F atoms are bonded
to Be atom through both the two sp-orbitals.
The Lewis structure of BeF2 is:
Note: a Lewis structure shows only the valence electrons of all the atoms in
the molecule or ion.
The molecular structure of BeF2 is:
...........
34
4.9 RESONANCE AND POLARITY OF MOLECULES

To illustrate resonance best, one should look at an example. Let us consider
the Lewis structures of N03-:
FIGURE4.3
The Lewis structures of N03-
From figure 4.4 we can see that N03- has three different Lewis structures. If
we calculate the formal charges of the atoms in these Lewis structures, we will
get the same values for the double-bonded oxygen atom, the single-bonded
oxygen atoms and the nitrogen atom in each of the three Lewis structures.
All three Lewis structures for N03- are therefore actually the same. However,
there is clear experimental evidence that all the bonds in N03- are the same.
This does not agree with the Lewis structures drawn in figure 4.2.
This contradictory brings us to the concept of resonance. The concept “reso-

nance” is used in cases where the Lewis structure fails to reflect the electron
distribution of the atoms in the molecule or polyatomic ion.
Resonance is the true structure of a molecule or polyatomic ion, where the

Lewis structure fails to represent the electron distribution of the atoms in the
molecule or polyatomic ion. The true structure or resonance structure is a
mixture or hybrid of the Lewis structures that failed to represent the electron
distribution of the atoms in the molecule or polyatomic ion.
(1) Give the Lewis symbols for the following:
1.1 Be 1.2 C
1.3 N 1.4 0
1.5 O2- 1.6 P
(2) Give the Lewis structures for the following:
2.1 CH4 2.2 OH-

2.3 CO32- 2.4 CN-
2.5 HFO 2.6 HOCN
...........
35 CH E181T/1

(3) Determine the percentage ionic character of the following compounds,

given the electronegativities of H = 2.1, Cl = 3.0, Na = 0.9, Ca = 1.0,
0 = 3.5, F = 4.0 and suggest the type of bond for each compound:
3.1 HCI
3.2 NaCI
3.3 GaO
3.4 HF
(4) Consider the carbonate ion, C032-.
4.1 Draw the Lewis structure of this ion.

4.2 Name all the bonds present.
4.3 Draw the electron distribution of the hybridised central atom.
4.4 What type of hybridisation does the central atom undergo?
4.5 Predict the electronic geometry of the central atom of the ion.
4.6 What is the molecular geometry of the carbonate ion?
(5) Determine the most acceptable Lewis structure for each of the following,
with the aid of formal charges.
5.1 Cl02 5.2 H2S03

5.3 P043- 5.4 OCN-
5.5 NH3 5.6 S042-
...........
36
L E AR N I N G U N I T 5: G as e s , li q u i ds a n d s o li ds
LEARNING UNIT
5 5
5 GASES, LIQUIDS AND SOLIDS
LE ARNING OUTCOMES
•• describe the properties of gases.

•• describe an ideal gas using the kinetic-molecular theory
•• explain the ideal gas law equation and all its symbols
•• calculate unknown parameters of gases using the ideal gas law
5.1 THE PROPERTIES OF GASES

All substances exist, under certain conditions of temperature and pressure,
in any one of the three states of matter: solid, liquid or gas. Water is a solid
phase at temperatures below and equal to 0.0 °C and a pressure of 101.325
kPa, a liquid phase between and including 0.0 to 100.0 °C and 101.325 kPa,
and steam or vapour at 100.0 °C and temperatures above.
It is necessary to distinguish between a gas and vapour. A gas is a substance

that is normally in the gaseous state at ordinary temperatures and pressures,
while a vapour is the gaseous form of any substance that is a liquid or solid
at ordinary temperatures and pressures.
Pressure is one of the most readily measured properties of a gas. Gases exert
pressure because gas molecules are constantly in motion and collide with the
surface of any object, and in doing so exert a force on the surface. Pressure
is an indication of the force exerted on a given surface area.
5.1.1 The kinetic-molecular theory
5.1.1.1 The particles of gases

The expansibility of gases can be accounted for by the assumption that the
gaseous state is discontinuous. Any gas will diffuse into the space occupied
by another gas, and the fact that gases can be compressed strengthens the
theory that gases are made up of minute particles called molecules, the total
volume of which is only a small fraction of the total space occupied by the
...........
37 CH E181T/1

gas. That means that under the normal circumstances in which gases can be
observed, the volume of the particles is very small compared with the volume
occupied by the gas.
5.1.1.2 Molecular motion and gaseous pressure

The molecules of gases are in constant motion, colliding with each other and
the walls of the container in a completely random manner. Moving bodies
exert a force on any object they strike – the impact of each molecule therefore
exerts a force and the pressure is the result of all separate impacts. We as-
sume that the impacts are frequent and that the change of momentum at each
impact is comparatively large, which implies that the molecules are moving
at extremely high velocities.
5.1.1.3 5Elasticity of molecular collisions

The molecular collisions involve no energy loss due to friction – this explains
why gases show no tendency to settle towards the bottom of the container
and why the pressure of a gas does not vary with time at a given temperature.
We can now state that all molecular collisions are perfectly elastic.
5.1.1.4 Temperature and kinetic energy

It has been proved that the pressure (P) exerted by a gas is directly proportional
to the average of the squares of the speeds (U2) of the molecules and indirectly
proportional to the volume (V) of the container.
P ∝ U2 Eq 5.1
P ∝ 1 Eq 5.2
v
Therefore, P ∝ U
2
Eq 5.3
v
PV ∝ U2
But, PV = nRT
Therefore, PV ∝ RT
Therefore, RT ∝ T U2 Eq 5.4
But, Ek ∝ U2
Therefore, Ek ∝ T Eq 5.5
Equation 5.5 means that the temperature of a gas (in Kelvin) is directly pro-
portional to the average kinetic energy (Ek) of the molecules. In other words,
the absolute temperature of a gas is a measure of the kinetic energy of the
molecules of a gas. We further assume that at the same temperature, the mol-
ecules of all gases possess the same average kinetic energy.
...........
38
5.1.2 The postulates for the kinetic-molecular theory

We want to describe the behaviour of real gases. To be able to do so, we
need a theory (the kinetic-molecular theory) that describes the behaviour
of an ideal gas. An ideal gas under all conditions does not exist; it is only a
theoretical concept. A real gas can behave ideally under certain conditions.
With the kinetic-molecular theory we can compare the behaviour of a real
gas with that of an ideal gas. The postulates for the kinetic-molecular theory
(for an ideal gas) are:
(1) Gases are made up of minute particles called molecules, the total volume
of which is only a small fraction of the entire space occupied by the gas.
The dimensions of the molecules are negligible compared with the aver-
age distance between them, and therefore the volume of the gas.
(2) The attraction forces between gas molecules are negligible.
(3) The molecules of gases are not stationary, but in constant, rapid, chaotic
motion, colliding with each other and with the walls of the container, in
a perfectly random manner.
(4) All molecular collisions are perfectly elastic, resulting in no loss of total
kinetic energy.
(5) The average kinetic energy of the molecules of a gas is proportional to
the absolute temperature of the gas.
(6) At the same temperature, the average kinetic energy of the molecules of
all gases is the same.
(7) Equal volumes of all gases at the same pressure and temperature contain
the same number of molecules.
5.1.3 The behaviour of gases
5.1.3.1 Boyle’s law

The pressure-volume relationship of gases was investigated by Robert Boyle.
It was noticed that at a constant temperature (T), the pressure (P) of a given
amount of gas (n), decreases with an increase in volume (V). Mathematically
this means that,
1 Eq 5.6
v
Or V ∝ 1 Eq 5.7
P
5.1.3.2 Charles’s law

The volume-temperature relationship of gases was investigated by Jacques
Charles. It was noticed that at a constant pressure (P), the volume (V) of a given
amount of gas (n), increases with an increase in temperature (T). Mathemati-
cally this means that,
n and P are constant: V ∝ T Eq 5.8
...........
39 CH E181T/1

5.1.3.3 The pressure -temperature relationship

It was noticed that at a constant volume (V), the pressure (P) of a given amount
of gas (n), increases with an increase in temperature (T). Mathematically this
means that,
n and P are constant: P ∝ T Eq 5.9
5.1.3.4 Avogadro’s law

The volume-moles relationship of gases was investigated by Avogadro. It was
noticed that at a constant volume (V) and constant pressure (P), the volume
(V) increases with an increase in the amount of gas (n). Mathematically this
means that,
P and T are constant: V ∝ n Eq 5.10
5.1.3.5 The ideal gas law equation

We can summarise the various gas laws:
V ∝ 1 Eq 5.7
P
V∝T Eq 5.8
V∝n Eq 5.10
This means that, V ∝ (1) (T)(n) Eq 5.11

P
Then, V = R (1) (T)(n) Eq 5.12

P
Where R is a constant called the ideal gas constant.
We can express the value of R in many different sets of units:
R = 8.3143 kPa.dm3 .mol-1 .K-1
= 8.3143 X 103 Pa X 10 -3 m3.mol-1.K-1
= 8.3143 Pa.m3.mol-1.K-1
= 8.3143 kg.m-1.S -2 .m3.mol-1.K-1
= 8.3143 kg.m2 .S -2 .mol-1.K-1
= 8.3143 kg.m.S -2.mmol-1. K-1
= 8.3143 m.mol-1.K-1
= 8.3143 J .mol-1
Equation 5.12 leads to: PV = nRT Eq 5.13
...........
40
Equation 5.13 is called the ideal gas law or the ideal gas equation. This equa-
tion describes the behaviour of an ideal gas.
The unit for the temperature in the ideal gas law is Kelvin. The Kelvin tem-
perature scale is an absolute zero scale. Zero Kelvin (0 K) is the lowest pos-
sible temperature. Temperature is usually measured in degrees Celsius, and
less often measured in degrees Fahrenheit. The relationships between Kelvin,
degrees Celsius and degreesFahrenheit are:
K = T °C + 273.15 Eq 5.14
T/ °F = (T/°C x 1.8) + 32 Eq 5.15
Very often properties of gases are compared at a specific set of conditions.

Scientists have agreed on 273.15 K and 101.325 kPa, as the temperature (T0)
and pressure (P0) at standard conditions. At standard conditions (at STP) there-
fore means that the temperature is 273.15 K and the pressure is 101.325 kPa.
T0 = 273.15K = 0.00 °C
= 101.325 kPa = 1 atm = 760 mm Hg = 760 torr
EXAMPLE 5.1
Calculate the volume that 0.750 mol of CO2 (g) occupies at STP. Answer:
T = 273.15 K
P = 101.325 kPa
n = 0.750 mol
v = ?
PV = nRT
V = nRT/P
V = (0.750 mol)(8.3143 kPa.dm3 .mol-1.K-1)(273.15 K)/ (101.325 kPa)
V = 16.810 dm3
5.1.4 The measurement of the pressure of gases

Gas molecules collide against the walls of the container and exert a force on
the walls of the container. This force per unit area results in pressure. The
pressure of a gas is therefore the force exerted by the gas molecules per unit
area. Due to gravity the atmospheric gases exert a pressure on the earth’s
surface, called the atmospheric pressure. At sea level, under mild weather
conditions, the height of the mercury of a barometer is equal to 760 mm. This
corresponds to an atmospheric pressure of 101.325 kPa, called the standard
atmospheric pressure.
...........
41 CH E181T/1

Pressure is defined as the force exerted on a unit area. In SI units pressure is

measured in pascal (Pa), which is equal to newton (N) per square meter (m2).
FIGURE 5.1
A simple mercury barometer.
A manometer is used to measure the pressure of a gas enclosed in a container.
The difference in height of the mercury in the two arms of the manometer (h)
indicates the pressure of the gas in the container. The difference in height of
the mercury in the two arms is measured in centimetres or millimetres.
There are three possibilities:
(1) The levels of mercury in the two arms are equal. This means that the
pressure of the gas in the container is equal to the atmospheric pressure
(measured with a barometer).
Pgas = Patm Eq 5.16
(2) The level of mercury in the arm connected to the gas is lower than the
level of mercury in the arm connected to the atmosphere. This means
that the pressure of the gas in the container is larger than the atmospheric
pressure.
Pgas = Patm + P Eq 5.17
(3) The level of mercury in the arm connected to the gas is higher than the
level of mercury in the arm connected to the atmosphere. This means that
the pressure of the gas in the container is smaller than the atmospheric
pressure.
Pgas= Patm–P Eq 5.18
5.2 THE PROPERTIES OF LIQUIDS

The kinetic-molecular theory was developed to explain the behaviour of gases;
it is also of great help in accounting for the behaviour of liquids and solids.
...........
42
There are two types of attraction forces between the molecules of a liquid.
These are cohesion and adhesion forces. Cohesion is the intermolecular attrac-
tion between molecules of the same type and adhesion is the force between
molecules of different types.
Liquids are only slightly compressible and expandable. Even at very high
pressures the volume of a liquid changes only slightly. This implies that there
is relatively little free space between molecules. The kinetic forces between
molecules in liquids are largely overcome by the cohesive forces between them,
and therefore liquid molecules do not have large distances between them.
5.2.1 Surface tension

Molecules in the bulk of liquids are pulled in all directions by intermolecular
forces. The molecules at the surface of the liquid are pulled downwards and
sideways but not upwards. This results in the surface behaving like an elastic
film. This phenomenon is called surface tension. The surface tension of a
liquid is the amount of energy required to stretch or increase the surface by
unit area. In liquids where there are strong intermolecular forces we also find
a greater surface tension. Surface tension also manifests itself in capillary ac-
tion. Water spontaneously rises in a narrow tube. A thin film of water adheres
to the wall of the tube and the surface tension of the water causes this film to
contract. As it does, it pulls water up into the tube.
5.2.2 Viscosity
Viscosity is a measure of a fluid’s resistance to flow. The greater the viscosity,
the slower a fluid flows. Liquids with strong intermolecular forces have greater
viscosity. In general, the viscosity of a fluid decreases as temperature increases.
5.2.3 Evaporation
Evaporation is a surface phenomenon in which the more energetic surface
molecules pass from the liquid to the gaseous phase. As molecules with greater
than average kinetic energy escape during evaporation, the average kinetic
energy of the remaining molecules decreases. This results in a decrease in
temperature unless heat is supplied from an outside source. This principle
is commonly used in air-cooling devices and is also responsible for the regula-
tion of body temperature in mammals that possess sweat glands.
The rate of evaporation will be increased by any factor that tends to facilitate
the escape of the surface molecules, such as an increase in temperature, which
increases the average kinetic energy, and air currents, which sweep vapour
molecules from above the surface.
5.2.4 Vapour pressure

In a closed container, containing a liquid phase, evaporation will take place. The
moment a vapour is formed, condensation starts taking place. Eventually a state
is reached where the rate of evaporation is equal to the rate of condensation.
This is called dynamic equilibrium. Under such conditions it seems as if the
processes of evaporation and condensation have stopped, because no visible
...........
43 CH E181T/1

changes are taking place. However, at molecular level both processes are still
taking place, but at the same rate. The concentration of the vapour and the
amount of the liquid will remain constant in that given set of circumstances.
As temperature increases, the percentage of molecules having sufficient kinetic

energy to escape from the surface of the liquid increases, resulting in an in-
creased vapour concentration and thus an increased vapour pressure. The
vapour pressure of a liquid phase is the pressure exerted by the molecules
in the gaseous phase, when the vapour is in equilibrium with the liquid. The
vapour pressure of different liquids at the same temperature varies widely due
to the difference in intermolecular forces.
5.2.5 Boiling point

The evaporation we have discussed so far is a surface phenomenon; that means
that is happens only on the top surface of the liquid phase. As the temperature
of a liquid increases, the vapour pressure of the liquid phase increases. At this
stage the atmospheric pressure (the pressure the earth’s atmosphere exerts on
the surface of the earth) is far higher than the vapour pressure of the liquid
phase, and remains constant. As the temperature of the liquid phase increases
further, a point is eventually reached at which “evaporation” takes place all over
the liquid phase; not only on the top surface of the liquid. Bubbles of vapour
form throughout the liquid phase, and rise to the surface of the liquid phase
where they burst and the vapour escapes. At this stage the liquid is boiling and
the vapour pressure of the liquid phase is equal to the atmospheric pressure.
A liquid reaches boiling point at the temperature at which the vapour pressure
is equal to the pressure on the surface of the liquid. The boiling point tempera-
ture at which a liquid boils at standard atmospheric pressure (101.325 kPa,
at sea level) is called the normal boiling point of a liquid. The boiling point
temperature for a specific liquid will decrease as the external atmospheric
pressure decreases. On the top of Mount Everest water will boil at approxi-
mately 70 °C because the atmospheric pressure is much lower than at sea
level (101.325 kPa).
The energy absorbed by a liquid at boiling point is used to free the molecules
from the attracting forces of the surrounding molecules. For this reason, no
matter how rapidly or how much heat is supplied, the temperature at which a
pure liquid will boil will remain constant as long as the atmospheric pressure
remains constant.
5.3 THE PROPERTIES OF SOLIDS

As a liquid is cooled, the molecules tend to move more slowly and eventu-
ally a temperature is reached where the random motion of the molecules
cease, and the molecules fit themselves into a regular geometric pattern, with
each molecule vibrating in a fixed position. This process is called freezing or
crystallisation.
The particles of a crystalline solid are arranged in an orderly, systematic pat-

tern that is characteristic of that substance. A crystal can be defined as a solid
...........
44
body, bounded by symmetrically arranged plane surfaces. The angles between

corresponding faces of crystals of a given substance are exactly the same in
all crystals of that substance.
Some materials, such as glass, possess certain characteristics of solids, but

do not have any definite crystalline form. When heated they do not melt at a
fixed temperature but gradually soften and become more mobile. Upon be-
ing cooled, they do not solidify at a fixed temperature, but become gradually
harder as the temperature lowers. Such materials can be termed amorphous
materials and can be regarded as greatly undercooled liquids of high viscosity.
5.3.1 Freezing point and melting point

If temperature is sufficiently reduced, the molecules of a pure liquid become
arranged in a definite geometric pattern characteristic of that substance. The
slower molecules attach themselves to the growing crystal and only the faster,
high-energy molecules remain in the liquid phase. Crystallisation can continue
only if the supply of the slower, low-energy molecules can be maintained by
external cooling. The temperature of the freezing substance remains constant
until the entire mass has solidified. The temperature at which this process takes
place is called freezing point.
If a solid is heated to this temperature, the process is reversed. The kinetic

energy of some molecules becomes sufficient to overcome the binding forces
in the crystal and the solid begins to melt.
If heat is neither supplied nor withdrawn at this temperature, the rates of freez-
ing and melting reach a dynamic equilibrium. This temperature is the freezing
point of the liquid of the melting point of the solid . Melting-point values are
characteristic for solids and are widely used in the identification of compounds.
...........
45 CH E181T/1

5.3.2 Sublimation
FIGURE 5.2
The phase diagram of water.
FIGURE 5.3
The phase diagram of carbon dioxide.
Many solids, such as iodine and dry ice (solid carbon dioxide) tend to change
directly from the solid state to the gaseous state without going through the
liquid state.
At the melting point of a substance, equilibrium exists between the solid phase
and the liquid phase. Such equilibrium is possible only if the vapour pressure
of the solid and the liquid phases are equal. In the case of some substances
the vapour pressure of the solid phase reaches a value equal to atmospheric
pressure before it becomes equal to the vapour pressure of the liquid phase,
...........
46
that is, before the melting point is reached. The solid does not melt, as all
the energy supplied is used by molecules to break away from the crystal.
These molecules pass directly into the vapour state. This process is known as
sublimation.
5.3.3 Phase diagrams

The overall relationship between the solid, liquid and vapour phases can be
represented in a phase diagram. This diagram summarises the conditions in
which a substance exists as a solid, liquid or gas.
The phase diagrams of water and carbon dioxide are shown in figure 5.2 and
figure 5.3 respectively.
The solid-liquid equilibrium line of the phase diagram of water (figure 5.4) has
a negative slope. This is the case because liquid water is denser than solid
water. This means that a certain mass of water will occupy less volume in the
liquid phase than in the solid phase. If pressure is applied to a liquid-solid
water mixture, the solid will melt and only the liquid will finally be present. Le
Chatelier states that if an external stress is applied to a system at equilibrium,
the system will adjust in such a way as to partially offset the stress – the liquid
occupies less volume and therefore partially offsets the applied pressure.)
FIGURE 5.4
The solid-liquid equilibrium line of the phase diagram of water
The slope must therefore be negative so that an increase in pressure can favour
the liquid phase. (A positive slope will favour the solid phase, which is not
the case with water.)
(1) Convert the following:
1.1 70 mm Hg to kPa 1.2 70 mm Hg to atm

1.3 2.5 atm to kPa 1.4 43.0 kPa to mm Hg
1.5 25.0 °C to K 1.6 25.0 °C to °F
1.7 180 K to °C 1.8 100 °F to K
...........
47 CH E181T/1

(2) Calculate the pressure of 3.75 mol of N2 (g) in a 4.20 dm3 container at
17.00 °C.
(3) Calculate the number of 02 gas molecules present in a 50.0 cm3 container,
at 23.5 °C and 85.7 kPa.
(4) What is the atmospheric pressure in kPa, if the height of the mercury in
a mercury barometer is 680.0 mm?
(5) Calculate the pressure of a gas in a container connected to a manometer,
if the level of mercury in the arm connected to the gas is 84.0 mm higher
than the level of mercury in the arm connected to the atmosphere. The
barometer reads 705 mm Hg.
(6) Calculate the temperature of 0.82 mol of a gas in a 3.28 dm3 container
at a pressure of 112.4 kPa.
(7) At 4.5 °C and 79.5 kPa a gas occupies 254.6 cm3. What will the volume
of this gas be (in dm3) at STP?
...........
48

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Learning unit 5: Gases, liquids and solids37

After studying this learning unit, you should be able to:

•• define matter, mass and weight

1.2 PROPERTIES AND CHANGES OF MATTER

•• solid phase: rigid; relatively incompressible; definite shape and volume;

•• Chemical properties and changes: the properties changes that can be

Examples of the changes are: hydrolysis, electrolysis, combustion, neutralisa-

1.3 CLASSIFICATION OF MATTER

1.4 CLASSIFICATION OF MATTER AS AN ELEMENT, COMPOUND OR

1.4.4 Magnetic properties

Chemical and physical changes of matter are accompanied by energy transfers.

1.6 THE PERIODIC TABLE

atomic number and corresponding periodic chemical properties, was derived

1.7 PROPERTIES OF IONIC AND MOLECULAR COMPOUNDS

1.1 matter 1.2 mass

(2) Draw a schematic diagram to illustrate the classification of matter.

3.9 Melting of lead at 327.4 °C

(4) Classify the following as either an element, a compound, a homogeneous

After studying this learning unit, you should be able to:

•• define and distinguish between quantitative and qualitative analysis

Property Symbol Unit Symbol

Electric current ⧯ ampere A

Amount of n mole mol

volume v cubic metre m3

density p gram per cubic kg.m–3 or org.cm–3

velocity v metre per m.s-1

pressure p pascal Pa = N.m-2 =

power p watts w = J .s-1 =

2.2 MEASURING LENGTH AND VOLUME

The most common containers measuring liquids are a beaker, graduated

When measuring volume, the accuracy of measurement required will deter-

Graduated measuring cylinder

Volumetric flask Graduated beaker

When transferring specific volumes of fluid accurately, a pipette is used. A

A volumetric flask is a flask accurately calibrated at a fixed temperature to

The burette is a very accurate apparatus for measuring volume, especially if

2.3 MEASURING MASS

Chemists use a chemical balance to measure mass. An open pan balance

2.4 DENSITY AND SPECIFIC GRAVITY

mX is mass and VX is volume

Density, which is a physical property, is not dependent on the amount of

=5 cm3 x 19.3 g.cm-3

Densities can be expressed in a variety of different units. These different ex-

2.5 ACCURACY AND PRECISION

There are two terms that describe the measurements made.

2.6 SIGNIFICANT FIGURES

The following points are important to be able to determine the number of

(1) To determine the number of significant figures of a numerical value, we

A numerical value is written in scientific notation when the value is written as

Numerical Scientific notation Total number of

120 = 1.20 x 102 3

120.0 = 1.200 x 102 4

40120 = 4.0120 x 104 5

400.8 = 4.008 x 102 4

7000 = 7.000 x 103 4

46.020 = 4.6020 x 101 5

30.0 = 3.00 x 101 3

40.03 = 4.003 x 101 4

40.030 = 4.0030 x 101 5

Example:2.546 x 0.20 = 0.5092 = 0.51

Learning unit 5: Gases, liquids and solids37