A SIMPLE MODEL FOR ATOMS AND BONDS

THE NATURE OF THE PARTICLES OF MATTER

It seems quite evident that different substances must be built with different particles.
These particles have been studied and both chemical and physical evidence show that
all of them are formed by what we will call atoms. Under normal conditions just a few
substances are formed by loose atoms as particles. Most substances are formed by
atoms that bond to each other in different ways forming molecules or ionic sets.

Atoms: are electrically balanced particles that consist in one positively charged centre
called the nucleus surrounded by a “cloud” of negatively charged particles called the
electrons, to exactly balance the nuclear charge.

Molecules: are electrically balanced particles with more than one positive centre
(nuclei). Molecules are sets of bonded atoms that act as a unit.

Ions: atoms (or groups of atoms) with unbalanced charges. Atoms with excess positive
charge are called cations and atoms with excess negative charge are called anions

Atoms can be classified in some 100 different classes (according to their chemical
behaviour). What makes these classes different is related to the internal structure of
these tiny particles. Let us introduce the sub-atomic particles

The sub-atomic particles

Protons, neutrons and electrons.

relative mass relative charge
proton 1 +1
neutron 1 0
electron 1/1836 -1

THE NUCLEUS

The nucleus is at the centre of the atom and contains the protons and neutrons. Protons
and neutrons are collectively known as nucleons.
Virtually all the mass of the atom is concentrated in the nucleus, because the electrons
weigh so little.

Working out the numbers of protons and neutrons

Nr of protons = ATOMIC NUMBER of the atom (Z)

The atomic number is also given the more descriptive name of proton number. The
number of protons will determine the number of electrons necessary to balance the
atom’s charge.
No of protons + no of neutrons = MASS NUMBER of the atom (A)
The mass number is also called the nucleon number.

This information can be given simply in the form:

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How many protons and neutrons has this atom got?
The atomic number counts the number of protons (9); the mass number counts protons
+ neutrons (19). If there are 9 protons, there must be 10 neutrons for the total to add up
to 19.
Elements: an element is formed by all the atoms that have the same number of protons
in their nuclei and hence the same number of electrons around them. Elements show
distinct and specific chemical and physical properties and are given different names and
symbols. There are 92 different natural elements: the lightest element (Z = 1) is
hydrogen and the heaviest (Z= 92) is uranium. Scientists have synthesised some 20
transuranic elements but their nuclei are unstable and decay to lighter atoms.
The atomic number is tied to the position of the element in the Periodic Table (the
system used by chemists to classify atoms) and therefore the number of protons defines
what sort of element you are talking about. So if an atom has 8 protons (atomic number
= 8), it must be oxygen. If an atom has 12 protons (atomic number = 12), it must be
magnesium.
Similarly, every chlorine atom (atomic number = 17) has 17 protons; every uranium
atom (atomic number = 92) has 92 protons.

THE PERIODIC TABLE

Classification criterion

The periodic table is a chart where scientists have arranged the elements according
to their increasing proton or atomic number Z. It was first proposed by Dimitri
Mendelejeff around the 1860’s although he actually used the mass number as a
classification criterion. He stated that if elements were arranged according to increasing
atomic masses, chemical and physical similarities would appear every eight elements.
Following this, elements should form eight columns or groups, divided in sub-groups.
Each row of eight members was called a period. He had to allow for some oddities that
could not be clearly explained by his time (atoms were supposed to be kind of balls with
no internal structure and nobody suspected the existence of protons, electrons etc.) so
many scientists didn’t quite agree with him. Further advances suggested that the
classification should be based on the number of charges of the nuclei rather than their
masses, and finally the groups were separated in different blocks.

Current aspect of the Periodic Table

The current shape of the Periodic Table is shown below this paragraph. All elements in
the same column belong to the same group and have similar behaviour. These properties
vary “smoothly” from group to group. The first two columns are called the reactive
metals. The rest of the dark grey (or pink) elements are all metals too. They are
classified as the transition, poor and rare earth metals. The pale grey (or yellow)
elements are the non metals. The last column elements (usually included in this set)
are called the noble gases (because they show low to almost no reactivity at all, as
noble metals do). Metals as pure substances are all good conductors of electricity and
heat, malleable, ductile, sonorous, form high melting point solid oxides with oxygen.
All but three of them are solid at room temperature and most are hard and very dense.

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The non metals are poor conductors of heat and electricity (except for a form of carbon
called graphite), half of them are gaseous, one is liquid and the rest are dull, brittle
solids. Their oxides, if solid, have low melting points. The pale green zigzagging set
between metals and non metals share properties with both main groupings.

Group and period numbers

In the table shown above, groups are numbered from 1 to 18. In many tables the “tall”
groups are numbered from 1A to 7A , the noble gases belonging either to group 8A or 0,
and the “short” groups are numbered starting at 3B (headed by Sc) to 8B (Warning!!
Group 8B has three columns headed by Fe, Co and Ni) and ending with Zn in group 2B
(there are historical reasons for this messy numbering). Periods are numbered from 1,
(the H period) a very short period indeed with just two members, up to 7. Elements past
uranium are all man-made elements all of them are radioactive with half lives
sometimes as short as milliseconds or less.

Isotopes

The role of neutrons in the nucleus is to “tie” the protons together. Protons are all
positively charged so they repel each other strongly but between protons and neutrons
there is an attractive force 100-fold stronger than electric repulsion (called the strong
nuclear force) that allows for proton being close to each other. This strong force is a
short range force: it fades with distance much faster than the electric force
The number of neutrons in an atom can vary within narrow limits. For example, there
are three kinds of carbon atom 12C, 13C and 14C. They all have the same number of
protons, but the number of neutrons varies.

protons neutrons mass number

carbon-12 6 6 12
carbon-13 6 7 13
carbon-14 6 8 14

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These different atoms of carbon are called isotopes. The fact that they have varying
numbers of neutrons makes no difference whatsoever to the chemical reactions of the
carbon.
Isotopes are atoms which have the same atomic number but different mass numbers.
They have the same number of protons but different numbers of neutrons. Any element
is a mixture of its different isotopes and the percentage of each of them is fairly constant
throughout the world

THE ELECTRONS

Working out the number of electrons

Atoms are electrically neutral, and the positiveness of the protons is balanced by the
negativeness of the electrons. It follows that in a (neutral) atom:
Nr of electrons = Nr of protons
So, if an oxygen atom (atomic number = 8) has 8 protons, it must also have 8 electrons;
if a chlorine atom (atomic number = 17) has 17 protons, it must also have 17 electrons.

The arrangement of the electrons

The electrons are found at considerable distances from the nucleus in a series of levels
called energy levels. Each energy level can only hold a certain number of electrons. The
first level (nearest the nucleus) will only hold 2 electrons, the second holds 8, and the
third also seems to be full when it has 8 electrons.
These levels can be thought of as getting progressively further from the nucleus.
Electrons will always go into the lowest possible energy level (nearest the nucleus) -
provided there is space (aufbau or construction principle).

To work out the electronic arrangement of an atom

• Look up the atomic number in the Periodic Table - making sure that you choose
the right number if two numbers are given. The atomic number will always be
the smaller one.
• This tells you the number of protons, and hence the number of electrons.
• Arrange the electrons in levels, always filling up an inner level before you go to
an outer one.

E.g. to find the electronic arrangement in chlorine

• The Periodic Table gives you the atomic number of 17.

• Therefore there are 17 protons and 17 electrons.
• The arrangement of the electrons will be 2, 8, and 7 (i.e. 2 in the first level, 8 in
the second, and 7 in the third).

The electronic arrangements of the first 20 elements

The chart on the following page shows the electronic distribution (arrangement) for the
first twenty elements

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After calcium, the pattern alters as you enter the transition series in the Periodic Table.

Two important generalisations

If you look at the patterns in this table:

• The number of electrons in the outer level is the same as the group number.
(Except with helium which has only 2 electrons. The noble gases are also
usually called group 0 - not group 8.) This pattern extends throughout the
Periodic Table for the main groups (i.e. not including the transition elements).
So if you know that barium is in group 2, it has 2 electrons in its outer level;
iodine (group 7) has 7 electrons in its outer level; lead (group 4) has 4 electrons
in its outer level.
• Noble gases have full outer levels.

IONIC (ELECTROVALENT) BONDING

The importance of noble gas structures

If we consider the formation of ions, the metals in group one form monopositive ions,
that is they loose their outer shell electron and become isoelectronic with their closest
noble gas. So do metals in group two, by loosing both electrons in their outer shells.
When we look at the opposite side of the table, non metals easily form ions once again
isoelectronic with the closest noble gas to each of them. On the other hand noble gases
are very unreactive and both their electron affinity and ionisation energy are much
higher than for the rest of the atoms. These and other observations (e. g. carbon always
forms four covalent bonds) led to a powerful generalisation known as Lewis’ rule or the
“rule of the eight”: “An atom bonds to other atoms gaining, loosing or sharing
electrons in order to be isoelectronic with its nearest noble gas”. (Or to have a
complete outer shell, to have eight electrons in its outer shell, etc.)
These noble gas structures are thought of as being in some way a "desirable" thing for
an atom to have.

Ionic bonding in sodium chloride

Sodium (2, 8, 1) has 1 electron more than a stable noble gas structure (2, 8). If it gave
away that electron it would become more stable.
Chlorine (2, 8, 7) has 1 electron short of a stable noble gas structure (2, 8, 8). If it could
gain an electron from somewhere it too would become more stable.

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The answer is obvious. If a sodium atom gives an electron to a chlorine atom, both
become more stable.

The sodium has lost an electron, so it no longer has equal numbers of electrons and
protons. Because it has one more proton than electron, it has a charge of 1+. If electrons
are lost from an atom, positive ions are formed. A positive ion is called a cation.
The chlorine has gained an electron, so it now has one more electron than proton. It
therefore has a charge of 1-. If electrons are gained by an atom, negative ions are
formed. A negative ion is called an anion.
The sodium cations and chloride anions are held together by the strong electrostatic
attractions between the positive and negative charges. This electrostatic attraction
between anions and cations is called an electrovalent or ionic bond
You need one sodium atom to provide the extra electron for one chlorine atom, so they
combine together 1:1. The formula is therefore NaCl.

Some other examples of ionic bonding

magnesium oxide

Again, noble gas structures are formed, and the magnesium oxide is held together by
very strong attractions between the ions. The ionic bonding is stronger than in sodium
chloride because this time you have 2+ ions attracting 2- ions. The greater the charge,
the greater the attraction.
The formula of magnesium oxide is MgO.

calcium chloride

This time you need two chlorines to use up the two outer electrons in the calcium. The
formula of calcium chloride is therefore CaCl2.

potassium oxide

Again, noble gas structures are formed. It takes two potassium atoms to supply the
electrons the oxygen needs. The formula of potassium oxide is K2O.

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COVALENT BONDING - SINGLE BONDS

Dots-and-crosses diagrams

We can represent the electronic structures for atoms by means of cross-and-dot

diagrams. The electronic structures of hydrogen and carbon, for example can be drawn
as:

The circles show energy levels - representing increasing distances from the nucleus.
You could straighten the circles out and draw the electronic structure as a simple energy
diagram.
Carbon, for example, would look like this:

This representation of the shells or levels happens to be very useful for the
representation of the covalent bonds formed between non metals

A simple view of covalent bonding

As well as achieving noble gas structures by transferring electrons from one atom to
another as in ionic bonding, it is also possible for atoms to reach these stable structures
by sharing electrons to give covalent bonds. This is most convenient in the case of non
metal atoms bonding between them... Both atoms needing a few electrons to complete
their outer shells will better share pairs than give or take them. A single covalent bond is
formed when two atoms share a pair of electrons. Each of the electrons of the pair is
provided by a different atom. The new particle so formed is called a molecule.

Some very simple covalent molecules

Chlorine
For example, two chlorine atoms could both achieve stable structures by sharing their
single unpaired electron as in the diagram.

The fact that one chlorine has been drawn with electrons marked as crosses and the
other as dots is simply to show where all the electrons come from. In reality there is no
difference between them.

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The two chlorine atoms are said to be joined by a covalent bond. The reason that the
two chlorine atoms stick together is that the shared pair of electrons is attracted to
the nucleus of both chlorine atoms.

Hydrogen

Hydrogen atoms only need two electrons in their outer level to reach the noble gas
structure of helium. Once again, the covalent bond holds the two atoms together
because the pair of electrons is attracted to both nuclei.

Hydrogen chloride

The hydrogen has a helium structure, and the chlorine an argon structure.

Other simple molecules

Most of the simple molecules you draw do in fact have all their atoms with noble gas
structures.
For example:

A SIMPLE VIEW OF MULTIPLE COVALENT BONDS

Double and triple covalent bond is where two or three pairs of electrons are shared
between the atoms rather than just one pair.

Some simple molecules containing double bonds

Oxygen, O2
Two oxygen atoms can both achieve stable structures by sharing two pairs of electrons
as in the diagram.

The double bond is shown conventionally by two lines joining the atoms. Each line
represents one pair of shared electrons.

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Carbon dioxide, CO2

Ethene, C2H4
Ethene has a double bond between the two carbon atoms.

Simple examples for the formation of triple bonds are the nitrogen molecule in which
the N atoms share three pairs of electrons, and the ethyne (acetylene) molecule with a
triple C-C share.

CO-ORDINATE (DATIVE COVALENT) BONDING

Co-ordinate (dative covalent) bonding

In the formation of a simple covalent bond, each atom supplies one electron to the bond
- but that doesn't have to be the case. A co-ordinate bond (also called a dative
covalent bond) is a covalent bond (a shared pair of electrons) in which both
electrons come from the same atom.
We shall use the term co-ordinate bond

The reaction between ammonia and hydrogen chloride

If these colourless gases are allowed to mix, a thick white smoke of solid ammonium
chloride is formed.

Ammonium ions, NH4+, are formed by the transfer of a hydrogen ion from the hydrogen
chloride to the lone pair of electrons on the ammonia molecule.

When the ammonium ion, NH4+, is formed, the fourth hydrogen is attached by a dative
covalent bond, because only the hydrogen's nucleus is transferred from the chlorine to
the nitrogen. The hydrogen's electron is left behind on the chlorine to form a negative
chloride ion.
Once the ammonium ion has been formed it is impossible to tell any difference between
the dative covalent and the ordinary covalent bonds. Although the electrons are shown
differently in the diagram, there is no difference between them in reality.

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Representing co-ordinate bonds

In simple diagrams, a co-ordinate bond is shown by an arrow. The arrow points from
the atom donating the lone pair (donor) to the atom accepting it (acceptor).

Dissolving hydrogen chloride in water to make hydrochloric acid

Something similar happens. A hydrogen ion (H+) is transferred from the chlorine to one
of the lone pairs on the oxygen atom.

The H3O+ ion is variously called the hydroxonium ion, the hydronium ion or the
oxonium ion.
Note that once the co-ordinate bond has been set up, all the hydrogens attached to the
oxygen are exactly equivalent. When a hydrogen ion breaks away again, it could be any
of the three.

Other examples for the formation of dative bonds are the sulphur di and tri oxide
molecules, the different oxides of chlorine and other 7 group elements

METALLIC BONDING

What is a metallic bond?

Metallic bonding in sodium

Metals tend to have high melting points and boiling points suggesting strong bonds
between the atoms. Even a metal like sodium (melting point 97.8°C) melts at a
considerably higher temperature than the element (neon) which precedes it in the
Periodic Table.
Sodium has one electron in its outer shell. When sodium atoms come together, the
electron in the outer shell of one sodium atom shares space with the corresponding
electron on a neighbouring atom- in much the same sort of way that a covalent bond
does
The difference, however, is that each sodium atom is being touched by eight other
sodium atoms - and the sharing occurs between the central atom and the shells on all of
the eight other atoms. And each of these eight is in turn being touched by eight sodium
atoms, which in turn are touched by eight atoms - and so on and so on, until you have
taken in all the atoms in that lump of sodium.

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All of the outer shell electrons on all of the atoms overlap to give a vast number of
“movement possibilities” that extends over the whole piece of metal.
The electrons can move freely, and so each electron becomes detached from its parent
atom. The electrons are said to be delocalised in the conductivity band. The metal is
held together by the strong forces of attraction between the positive nuclei and the
delocalised electrons.

This is sometimes described as "an array of positive ions in a sea of electrons".

If you are going to use this view, beware! Is a metal made up of atoms or ions? It is
made of atoms. Remember that the electrons are not taken away from the metal atom.
Each positive centre in the diagram represents all the rest of the atom apart from the
outer electron, but that electron hasn't been lost - it may no longer have an attachment to
a particular atom, but it's still there in the structure. Sodium metal is therefore written as
Na - not Na+.

A SIMPLE MODEL FOR ATOMS AND BONDING: PROBLEMS

1- Find the symbol for the following elements: sodium, potassium, chlorine,
sulphur, magnesium, oxygen, hydrogen, carbon and nitrogen.

2- Tell which of the elements named in (1) are metals and which are non metals.
Suggest an easy test to tell between both classes of elements.

3- Write the electron configuration for the atoms Z = 18, Z = 12 and Z = 15: which
if any belongs to a metal?

4- Suggest a possible mass number for the atoms of exercise (3) and give reasons
for your answers.

5- Write reasonable possible isotopes for each of the following 35Cl17, 31P15, 40Ar18
and 39K19.

6- An atom belongs to the third group and the second period of the periodic table.
Give its atomic number and a reasonable mass number for it.

7- Sketch the bonding between atoms Z = 12 and Z = 9.

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8- Give the formulae for: calcium sulphide, lithium oxide, magnesium chloride and
potassium fluoride.

9- Sketch a cross and dot (Lewis) diagram for the following substances: water,
ammonia (nitrogen and hydrogen), sulphur chloride, sulphur monoxide and
hydrogen peroxide (oxygen and hydrogen but oxygen forming a single bond to a
second oxygen atom).

10- Explain why the substances of exercise (9) are molecular rather than ionic.

11- Work out the Lewis’ diagrams and the structures for the two phosphorus oxides.
Oxygen works always with valence (II) and phosphorus with valences (III) and
(V) respectively.

12- Do as for problem (11) but for the hydrogen chlorates HOXCl . What are the
values for X in the formulae?

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