BONDING AND STRUCTURE

We are living in a world with millions of substances having properties vastly different from one another. It is the way the atoms
are held together (bonding) and how they are arranged in space (structure) that accounts for the quite distinct properties of these
different substances.

When elements form compounds, they either lose, gain or share electrons so as to achieve stable electron configurations. This
simple idea forms the basis of the electronic theory of bonding : a chemical bond is a special arrangement of electrons between
atoms by which the resulting nuclei and electrons become more stable.

There are three main types of bonding - ionic, covalent and metallic - which involves respectively transfer, sharing and pooling of
electrons between atoms to achieve stable electronic arrangements.

Type of bonds IONIC BOND COVALENT BOND METALLIC BOND

formed between metals and non-metals

way to achieve stable

electronic arrangement

non-directional
nature of bonds
electrostatic attraction between
nuclei and shared electrons

structure adopted

example sodium chloride iodine diamond sodium

nature of forces strong metallic bond

holding particles between ions and
together sea of electrons

properties :

(1) m.p. / b.p.

(2) electrical
conductivity

(3) solubility

IONIC BONDING
A simple model of ionic bonding where electrons are being transferred from metal atoms to non-metal atoms so that the resulting
ions obtained a full outer shell of electrons :
 Bonding 2

Ionic Radii
The electron cloud of any atom or ion has no definite limit, thus the size
of an atom cannot be defined in a simple and unique manner. We could,
however, measure very precisely the distance between two nuclei by
means of electron density maps.

Class Work
The figure shows the electron density map for sodium chloride.
(a) Decide which is the sodium ion and which is chloride ion.

(b) Use a ruler and the map scale to obtain approximate values for the
ionic radii of sodium and chloride ions.

The sizes of ions can be conveniently compared by measuring their ionic radii from electron density maps.
1 Comparison of sizes of ions with their parent atoms :
(i) cations are smaller than their parent atoms (removal of a complete outer shell leads to a contraction of electron cloud)
(ii) anions are larger than their parent atoms (affinity of incoming electrons results in an expansion of electron cloud)
cations are usually smaller than anions

2 Comparison of sizes of isoelectronic particles :

In any isoelectronic series, all the particles carry the same number of
electrons but have a progressively increasing number of protons.
Along an isoelectronic series
the p/e ratio (no. of protons / no. of electrons) increase
effective nuclear charge increase
result in a contraction of the electron cloud of the ion
ionic radii decrease along an isoelectronic series

Structure of Ionic Lattices

There are two common arrangements for most ionic compounds, namely the sodium chloride and caesium chloride structures.
They can be conveniently represented by unit cell, defined as the smallest portion of structure which when repeatedly stacked
together at all directions, can reproduce the entire lattice.

It is made up of two inter-

penetrating face-centered It is made up of two
cubic lattices (f.c.c.) of inter-penetrating simple
each type of ion (Na+, Cl-) lattices of each type of
to form a simple cubic ion (Cs+, Cl-) to form a
lattice with each type of body-centered cubic
ion occupying alternate lattice (b.c.c.)
corners

NaCl structure CsCl structure

Class Work
(a) Sketch the unit cell of the two different structures.
 Bonding 3
(b) Deduce the number of each type of ion per unit cell for each structure.
NaCl structure : CsCl structure :

(c) State the respective co-ordination numbers of each type of ion in the two structures.
NaCl structure : CsCl structure :

Theoretically, ionic structures tend to have as higher co-ordination numbers as possible, because it allows maximum attractive forces operate
between oppositely charged ions, making the resulting lattices more stable. Sodium chloride, however, does not adopt the caesium chloride
+ +
structure because of the difference in relative ionic sizes. However, Na ions, being much smaller than Cs ions, cannot accommodate more than
-
6 Cl ions before these anions repel each other too strongly for a stable arrangement.

Class Work
Study the following two unit cells and deduce which one belong to calcium fluoride and which one to zinc sulphide.

Physical Properties of Ionic Compounds

Compounds of ionic solids are :

1 non-volatile with high melting points and high boiling points
2 good conductors of electricity when molten, but non-conductors when solid
3 soluble in water, but insoluble in non-aqueous solvents such as tetrachloromethane (CCl4)
4 hard and brittle

Ionic crystals are hard because of the

strong attractions between opposite
charged ions. However, they are also very
brittle and may be split clearly (cleaved)
using a sharp-edged razor. When the
crystal is tapped sharply along a particular
plane it is possible to displace one layer of
ions relative to the next. As a result of this
displacement, ions of similar charge come
together. Repulsion then occurs, forcing
apart the two portions of the crystal.
 Bonding 4
COVALENT BONDING
According to valence bond theory, a covalent bond is formed by sharing the valence (outermost) electrons :

This model is inadequate because it suggests a pair of electrons to be fixed between the two nuclei, yet it is impossible to locate the
exact position of electrons. A better model using the idea of overlapping orbitals/charge clouds is adopted :

The actual charge distribution for a covalent molecule could be obtained from an
electron density map, which shows a region of negative charge (shared electrons)
located between two positive charges (nuclei).
The covalent radius of an atom is defined as half the internuclear distance between
two covalently bonded atoms in the molecule of the element.

Class Work
What is the covalent radius of hydrogen ?

Despite the limitation of valence bond theory, it is nevertheless very useful in making predictions about the electronic structures of
covalent molecules by dot-and-cross diagrams.

Class Work
Draw electronic structures for the following species :
(a) NCl3 (b) H2S (c) CHCl3

(d) C2H4 (e) N2 (f) CO2

For polyatomic ions, such as NH4+ and CO32-, it is important to distinguish between the ionic bonding which binds these ions to
other ions, and the covalent bonding which binds the atoms within each ion.

Class Work
Draw electronic structures for the following species :
(a) OH - (b) CO3 2- (c) HCO3 -
 Bonding 5
Dative Covalent Bond
In a normal covalent bond, each atom provides one electron for the shared pair. In a few compounds, however, a bond is formed
by the sharing of an electron pair which are provided by one atom. This kind of bonding is known as dative covalent bond or
co-ordinate bond, since both electrons in the bond are donated by one atom.

Ordinary covalent bonds are represented by a short line as a shorthand for an electron pair. Dative covalent bonds are represented by an arrow
showing the direction of donation. However, once a dative bond is formed, you should not imagine them being different from ordinary bonds,
because electrons are identical irrespective of where they are coming from.

Class Work
Draw electronic structures for the following species : -
+
(a) CO (b) NH4 (c) NO3

Limitation of Octet Rule

So far, we have considered only those covalent compounds which obey the octet rule. However, there are a number of cases
where the rule does not apply.

1 Compounds with more than eight valence electrons per atom

The octet rule always applies for elements in the first two periods of the Periodic Table : each atom cannot hold more than
eight electrons in its valence shell. Starting from period 3, however, elements could make use of their vacant d-orbitals to
accommodate more than 8 valence electrons, apparently breaking the octet rule.

Class Work
Draw electronic structures for the following species :
(a) PCl5 (b) SO4 2- (c) PO4 3-

2 Compounds with fewer than eight valence electrons per atom

When elements with fewer than four outer shell electrons form compounds they usually lose those electrons to form ions. For
small atoms, however, the relevant ionization energies may be so high that covalent bonding occurs instead. Since there are
fewer than four electrons available for sharing, there will then be fewer than eight outer shell electrons per atom in the
resulting compound. Such compounds are often called ‘electron-deficient’.

Class Work
Draw electronic structures for the following species :
(a) BF3 (b) BeCl2 (c) AlCl3

There is a tendency for these electron-deficient compounds to achieve '

stable octet'by accepting a lone pair of electrons from
neighbouring molecules to form a dative covalent bond.

NH3 ⋅ BF3 BeCl2 (polymer) Al2Cl6 (dimer)

 Bonding 6
Shapes of Molecules
The electron-pair repulsion theory allows us to make predictions about the shapes of a great many covalent molecules :
1 Each covalent bond is regarded as a pair of electrons. An electron pair may be a shared pair, lone pair, single bond, double
bond or triple bond.
2 Electron pairs around a central atom tend to get as far apart from each other as possible, so as to minimize the electrostatic
repulsion among them.
3 Non-bonding pair of electrons exerts a greater repelling effect than bonding pair of electrons does. Therefore,
lone pair - lone pair lone pair - bond pair bond pair - bond pair
repulsion repulsion repulsion

no. of electron
pairs around Basic skeleton Bond angle examples
central atom
BeCl2 CO2
2

linear
BF3 SO3 SO2

trigonal planar

CH4 NH3 H 2O

tetrahedral
-
PCl5 ClF3 ICl2

trigonal
bipyramidal

SF6 BrF5 XeF4

octahedral
 Bonding 7
Class Work
For each of the following molecules, draw a three-dimensional structure showing the positions of the bond electron pairs and
lone electron pairs (if any) of the central atom.
-
(i) PCl4+ (ii) PCl6 (iii) PCl3

A few comments on bond angles :

1 CH4 molecules are perfectly symmetrical. The bond angle for H-C-H is that of a regular tetrahedron, 109.5° . Although
sharing the same molecular skeleton, NH3 and H2O have different bond angles (107° for H-N-H and 105° for H-O-H).
The region in space occupied by a non-bonding pair of electrons is smaller and closer to the nucleus of an atom than a bonding pair.
Bonded pairs of electrons are drawn out between the nuclei of the two covalently-bonded atoms. This means that a lone pair can exert a
greater repelling effect than a bonded pair and this results in a decreasing bond angle from CH4 to NH3 to H2O.

2 NH3 and PH3 are both pyramidal with four pairs of electrons around the central atom, one of which is a lone-pair. The bond
angle for H-N-H in NH3 is 107° while that for H-P-H is 90°.
N atom is smaller than P. It follows that N-H bond pairs lie much closer to the central atom than P-H bond pairs do. The repulsion among
N-H bond pairs are thus much greater than that among P-H bond pairs, resulting a decrease in bond angle down the group.

Giant Covalent Structures

The sharing of electron pairs does not necessarily result in discrete molecules. In a few cases, covalent bonding is extended
indefinitely in three dimensions. Such giant structure is well illustrated by the two allotropes (different structural forms of the
same element) of carbon, namely diamond and graphite.
The properties of diamond and graphite are in dramatic contrast. Since both solids consists of identical carbon atoms only, the
differences in properties must be entirely due to differences in structures.

DIAMOND GRAPHITE

structure

Each C atom is covalently bonded to 4 other C Each C atom is covalently bonded to 3 other C atoms
atoms in a tetrahedral manner to form a 3-D in trigonal planar to form a multi-layer structure.
giant network Adjacent layers are held by van der Waals'forces
co-ordination no.
4 / sp3 3 / sp2
/ hybridization
3550 °C 3700 °C
m.p. / b.p.
strong C-C covalent bonds have to be broken in melting / boiling

strength hard; strong & directional C-C bonds restrict soft; weak van der Waals' forces allow layers
relative motion between C atoms to slip over each other easily

electrical non-conductor of electricity; good conductor of electricity;

conductivity all electrons are localized in covalent bonds each C atom has a delocalized electron which
can move freely along the same layer
uses jewelries, glass cutters electrodes, lubricants, pencils
 Bonding 8
INTERMEDIATE TYPE OF BONDING
In many compounds, the bonding is intermediate in character between ' pure'
ionic and '
pure'covalent. We can discuss intermediate type of bonding in two
ways, either by seeing :
1 how ordinary ionic bonds can have covalent character; and
2 how ordinary covalent bonds can have ionic character.

Covalent Character of Ionic Bonds

The model of ionic bonding so far assumes the complete transfer of electrons
from one atom to another giving separate spherical ions. However, the
spherical charge cloud in large anions may be easily distorted, or polarized,
by neighbouring small cations, because the nuclear charge of the anion is
insufficient to hold its electron cloud firmly. Such distortion leads to a certain
overlap of charge clouds between cations and anions, and hence a degree of
covalent character. The distortion of an electron cloud by a neighbouring
charged particle is called polarization.

Evidence of whether an ionic compound has significant covalent character comes from a comparison of the lattice energy values,
one derived from theory and the other determined from experiment.

Assumptions in deriving the theoretical lattice energy of an ionic compound :

1 ions are spherical
2 charge is uniformly distributed throughout the ions
3 forces operating between ions are only electrostatic in nature

theoretical value experimental value

applying Law of Electrostatics applying Hess'Law

underlying

principle

q1 ⋅ q 2
L. E. ∝
r L.E. = B + C + D + E - A

NaCl -777 -781

LiF -1021 -1033
AgCl -769 -890
ZnS -1986 -2435

Cations such as Al3+, Ag+ and Zn2+ have small ionic radii and high nuclear charge, both give rise to a high charge density
(i.e. charge/volume ratio), thus distorting the electron cloud of neighbouring anions to a greater extent. These ions are said to
possess a high polarizing power.

Electrons in larger anions are further away from the nucleus and are less firmly held by the nucleus than smaller anions. Large
anions are said to have a high polarizability (the ability to become polarized).
 Bonding 9
Ionic Character of Covalent Bonds

♦ Polar covalent bond and dipole moment

The model of covalent bonding used so far assumes the equal sharing of a pair of electrons between two atoms. Very often the
electrons are not shared equally, as in the case when a bonding pair of electrons is attracted more to one nucleus than the other (e.g.
Cl atom in H-Cl molecule is more electronegative than the H atom). This makes the centre of negative charge not coincide with
the centre of positive charge, resulting in the formation of a dipole with two equal and opposite charges (+q and -q) separated by a
distance d

This bond is said to be polarized and described as a polar covalent bond. There are four ways of representing bond polarity :

The extent of bond polarization can be measured in terms of dipole moment, µ , which is given by µ = q x d. Dipole moments are
usually expressed in Debye (D) unit (e.g. dipole moment of HCl molecule is 1.1 D)

1 Dipole moments are vector quantities. For a molecule with more than one polar bond,
the dipole moment is given by the vector sum of the dipole moments of various polar bonds. If
the vector sum is zero, the dipole moment of the molecule is zero, and the molecule is described
as non-polar.
2 The greater the overall dipole moment, the more polar the molecule is.
3 Polarity of a liquid can be tested by studying the effect of a charged rod on a stream of
liquid from a burette. Any deflection of the stream indicates that the liquid is polar.
4 Dipole moments can provide useful information about the structure of molecules. As an example, the
zero dipole moment of CO2 shows that the molecule must be linear such that the dipole moment of
each C=O bond cancels each other out. On the other hand, the existence of a net dipole moment for
SO2 molecule indicates that the molecule contains polar bonds which are not linearly arranged.

Class Work
By drawing a 3-D structure showing the bond electron pairs and lone electron pairs (if any), state
whether or not the molecule possesses a dipole moment.
(i) BCl3 (b.p.13°C) (iii) CCl4 (b.p.77°C) (v) CO2 (b.p.-78°C)

(ii) NCl3 (b.p.71°C) (iv) CHCl3 (b.p.62°C) (vi) SO2 (b.p.-10°C)

♦ Electronegativity
In polar covalent bonds, the unequal sharing of the bonded electron pairs is caused by a difference in electron attracting ability of
the bonded atoms. This electron attracting ability of the atom is described as electronegativity of the element.
1 The Pauling's scale is used to measure electronegativities of different elements :
(i) a value of 4.0 is assigned to the most electronegative element, fluorine
(ii) all other elements having a lower electron attracting ability than fluorine are assigned lower electronegativity values
 Bonding 10

2 Smaller atoms with greater charge density tend to attract electrons more tightly than larger ones, i.e. electronegativity
increases across a period and decreases down the group
3 Electronegativity differences govern the nature of chemical bonding
electronegativity difference
bond type of bond
between bonded atoms
ClCl 3.0 - 3.0 = 0 covalent
ClH 3.0 - 2.1 = 0.9 polar covalent
F- Li+ 4.0 - 1.0 = 3.0 ionic
4 Both electronegativity and electron affinity refer to the attraction by an atom for electrons. The essential difference between these terms lies
in the fact that electron affinity refers to the attraction between incoming electrons (external) and isolated atoms; whereas electronegativity
refers to the attraction between bonding electrons (internal) and an atom in a covalent compound.

INTERMOLECULAR FORCES
There are three major types of interactions operating between simple covalent molecules, depending on the extent of polarity of
the molecules :
1 permanent dipole-dipole interactions
2 dipole-induced dipole interactions
3 temporary (induced) dipole-induced dipole interactions (or van der Waals’ forces in general)

Dipole - Dipole Interaction

Polar molecules, or sometimes called dipoles, are attracted to one another when
- - - - the positive end of one molecule is oriented toward the negative end of its
+ + + + neighbour. Such electrostatic attractions between permanent dipoles are
- - - - considerably strong, and explains why polar compounds usually have
+ + + + relatively higher melting or boiling points than non-polar molecules of
- - - -
similar molecular size.
+ + + +
Dipole - Induced Dipole Interaction
It arises when a polar molecule, in the vicinity of another molecule (which is non-polar), has the effect of polarizing the second
molecule. The induced dipole can then interact with the first molecule.

Induced Dipole - Induced Dipole Interaction

Non-polar molecules, though having no permanent dipole moment, do have temporary, constant changing dipoles due to the
continuous motion of the electrons.

1 Electrostatic attractions between temporary induced dipoles are weaker than that between permanent dipoles.
2 Electron cloud of larger molecules are more readily to be polarized than smaller ones, resulting in a stronger intermolecular
attraction. This is why substances with larger molecular size generally have higher melting and boiling points.
3 Temporary induced dipoles are present in BOTH polar and non-polar molecules (as long as they have polarizable electron
clouds). For large polar molecules, the attractive forces due to temporary induced dipoles may even be greater than those due
to the permanent dipoles.
 Bonding 11
Hydrogen Bonding
Hydrogen bonding is often regarded as a special kind of permanent dipole-dipole attractions. This is formed between a lone pair
of electrons from a highly electronegative element (ie. F, O or N) and a hydrogen atom, which itself bonded to another very
electronegative element.
δ+ δ- δ+ δ- δ+ δ-
FH −−−− F OH −−−− N NH −−−− O

Hydrogen bond is by far the strongest type of intermolecular forces, with strength about one-tenth of an ordinary covalent bond.
This relative strength has some important and interesting consequences :

1 Boiling points of hydrides of group V, VI and VII

In general, boiling point increases down the group, owing to the increase in
molecular size (∴greater v.d.W. forces)
However, the first member of the hydride from Group V, VI & VII have
exceptionally high boiling points, because of the existence of intermolecular
hydrogen bonds
Such abnormal phenomenon does not appear in Group IV hydrides, as the
first member here (i.e. carbon) is obviously not electronegative enough to
form intermolecular H-bonds

2 Structure and density of Ice

Abnormal behaviour of ice :
1 Ice floats on water while solid HF does not float on its own liquid.
2 When liquid water is heated from 0°C, its density increases for a short
while (below 4°C) before decreasing in the usual way.
Explanation :
H2O has two lone pairs of electrons and could form at maximum two hydrogen
bonds per molecule. Each H2O molecule is, therefore, surrounded
tetrahedrally (2 covalent bonds and 2 hydrogen bonds) to form an 'open' cage-
like structure.
As ice melts, some of these hydrogen bonds are broken. The partial collapse
of such an open structure allows water molecules to pack closer to each other
∴density of water > density of ice

3 Hydrogen bondings in proteins and DNA

Hydrogen bonding plays a crucial role in the structures of many biochemical substances such as proteins and DNA :
Protein chains are held in close In DNA, the two helical strands of nucleic acid chains, which controls
proximity to one another by hydrogen reproduction and inheritance, are linked together by a series of
bonds formed between the N-H and hydrogen bonds
C=O groups of the neighbouring chains
 Bonding 12
4 Relative viscosity
Viscosity of a liquid is related to the ease with which molecules can move past one another in the liquid.
Viscosity of alcohols increases in the following order : propan-1-ol < propane-1,2-diol < propane-1,2,3-triol
Each alcohol molecule forms hydrogen bonds with its neighbours through hydroxyl (-OH) groups. As the number of hydroxyl
groups increases, so does the extent of hydrogen bonding in the liquid; making it more viscous.

5 Pressure-temperature diagram
• vapour pressure of a liquid at a particular temp. is the pressure exerted by the vapour molecules, which are in equilibrium
with the liquid molecules at that temp.

vapour pressure
• graphical representation :
-- at each temp., the vapour pressure of the more
volatile substance is always higher than the less
volatile one
-- boiling point is defined as the temp. at which the
vapour pressure of the substance is equal to the
atmospheric pressure
-- note that liquids with lower vapour pressures (ie.
less volatile) will have correspondingly higher b.p. temperature
external pressure

the curve represents the variation of boiling points with different

pressure and temp. (notice that the y-axis now indicates external
pressure rather than vapour pressure of the substance)

each area included by the curve represents the conditions of temp.

and pressure under which a particular phase is stable (or dominant)

every point on the curve represents the conditions of temp. &

pressure at which the two phases co-exist in equilibrium
temperature

• the concept can be further elaborated to represent equilibria

involving all the 3 phases :

interpretation of phase diagram

AB :
BC :
BD :

B: __________ point (at which all the three phases co-exist in

equilibrium)

C: __________ point (above which the vapour cannot be liquefied

no matter how high the applied pressure will be)

Class Work
Determine each of the following by referring to the above phase diagram of a substance, X :
(a) the m.p. and b.p. of X at atmospheric pressure ;

(b) the state of X at (I) 200°C and 2 atm; (ii) 0°C and 1 atm ;

(c) the condition under which X will sublime.

 Bonding 13
• comparison of phase diagrams between CO2 and H2O

P P

T T
features : (i) triple point for CO2 is above 1 atm while that for water is below 1 atm
(ii) slope of solid-liquid curve for CO2 is +ve while that for water is -ve
consequences : (i) liquid CO2 is not stable under ordinary conditions
solid carbon dioxide sublimes rather than melts
(ii) an increase in P will lower m.p. for H2O
delay freezing or melting occurs earlier than before
water freezes with expansion in volume or ice melts with contraction in volume
water is denser than ice ( formation of open cage structure in ice)

Molecular Crystals
Molecular crystals consist of molecules held in simple cubic or face-centred cubic lattice by weak intermolecular forces such as
van der Waals' forces (e.g. iodine) or hydrogen bonds (e.g. ice) :
Molecular solids are :
1 volatile with low m.p. / b.p.
2 poor conductor of electricity
3 usually soft and of low densities

Buckministerfullerene, with formula C60, was discovered in 1985 as the third form of carbon
allotrope, which is made from interlocking hexagonal and pentagonal rings of C atoms. It is the
parent of a new family of structures called fullerenes, including C70, C82 and C100, mostly
produced from the sooty flames from burning benzene.

Fullerenes can conduct electricity due to the presence of delocalized electrons on their surface.
By housing various metal atoms (e.g. K), inside the hollow cage, a whole new range of
applications have been found, including catalysts, superconductors, rocket fuels, laser materials
and drugs.

Class Work
Deduce the number of carbon atoms in a unit cell of C60, if it is known to have a face-centred cubic structure.
 Bonding 14
METALLIC BONDING
The structure of a metal can be conveniently illustrated by a model in which a lattice of regularly packed cations is surrounded by
a ‘sea’ of delocalized electrons.
1 The delocalized nature of electrons accounts for their high electrical and thermal conductivity, whereas the flexibility of
packing the cationic lattice accounts for their malleable (pressed easily) and ductile (pulled easily) behaviour
2 Strength of metallic bonding is governed by two factors :
(a) no. of valence electrons − metallic bond strength increases with the number of outermost (valence) electrons ∴m.p./b.p.
increases across the period (i.e. Na < Mg < Al)
(b) metallic radii − ionic radius increases down the group, resulting in a decrease in charge density and, therefore, a
reduction of electrostatic attraction between cations and the valence electrons ∴m.p./b.p. decreases down the group (i.e.
Li > Na > K)
3 When a metal is melted, only a small portion of metallic bonds are broken, resulting in a slight distortion of the entire structure.
On the other hand, all metallic bonds are broken in boiling, making the melting points of metals are usually significantly
lower than their boiling points. (e.g. m.p. & b.p. for Na are 98 and 883°C respectively)

Metallic Crystals
The problem of packing cation together in a lattice is not so very different from the problem of packing ping-pong balls into a box.
There are two different ways of packing spheres within a single layer :

close packing loose packing

1 In building up metal spheres in a 3-D close-packed structure :

a In a close-packed layer, each atom is in contact with six others, resulting a hexagonal arrangement of atoms.
b In the second layer, atoms pack as closely as possible to those in the first layer by 'sitting' in the holes between atoms in
the first layer. (Notice that there are now two different kinds of holes, namely tetrahedral and octahedral, depending on
the shape formed by the neighbouring spheres surrounding the hole)
c The third layer of atoms can now be added in two quite distinct ways so that :
(i) each sphere in the layer is sitting on the tetrahedral holes formed by the previous two layers, resulting in an overall
pattern that repeats itself every alternate layer (denoted by abab... etc.) hexagonal close packing (h.c.p.)

(ii) each sphere in the layer is sitting on the octahedral holes formed by the previous two layers, resulting in an overall
pattern that repeats repeats itself every three layers (denoted by abcabc... etc.) cubic close packing (c.c.p.)
(the word ‘cubic’ is derived from the fact that a c.c.p. pattern could be visualized as a face-centred cubic (f.c.c.)
structure from a different point of view)
 Bonding 15

2 In building up metal spheres in a three-dimensional open (not close-packed) manner, a second layer can be formed by placing
a layer of spheres in the ‘holes’ formed by the first layer, and a third layer formed in a similar way. This produces a
body-centred cubic (b.c.c.) arrangement in which each sphere is in contact with 4 spheres in the layer above and 4 in the
layer below, but in contact with no spheres within its own layer.

Different metals adopt different types of structures depending on their metallic radii.

h.c.p. c.c.p. / f.c.c. b.c.c.

arrangement for atoms

ABAB… ABCABC…
in different layers

unit cell
representation

co-ordination number

packing efficiency closely packed loosely packed

Alloys
An alloy is a mixture of two or more metals (or of a metal with a non-metal) such that the resulting properties are generally more
desirable than the pure metals alone. While some alloys (e.g. Pb-Sn alloy solder) exist in heterogeneous mixtures with separate
solid phases, most alloys are homogeneous solid solutions and can be further classified into:

1 substitutional alloy: some of the metal atoms being substituted by another metal (e.g. 18-carat gold alloy with silver); atomic
radii of the metals in the alloy should match with each other
2 interstitial alloy: the smaller atoms occupy holes among lattice formed by larger atoms (e.g. 1% carbon among iron in steel)

Compared with their constituents, the properties of alloys can be modified in the following ways:
• Alloys are harder and stronger than pure metals. In the case of pure atoms, layers of atoms with identical radius can easily
slide over each other. However, the addition of a small amount of one metal with different atomic radii disrupts the orderly
arrangement of atoms, making it more difficult to slide over each other. (Degree of hardness increase as the relative
motion between particles become more restricted.)
• some alloys are more resistant to corrosion than pure metals (e.g. stainless steel, Al-Mg alloy duralumin)
• many alloys form mixtures with much lower melting points than pure metals (e.g. solder to join metals together)