Chapter 11 Bonding and Structure (2)

Crystal Structures

Two main types of solid structure

molecular structures

giant structure Giant structure can be made up of ions or atoms:

sodium chloride has a giant structure composed of ions; diamond has one composed of atoms.

11.1

Structures of Metals (Giant structures)

close-packed and open

two types:
Coordination Number

The number of atoms adjacent to a single atom is called the coordination number.
A unit cell is the smallest part of the crystal that contains all the characteristics of the structure. The whole structure can be generated by repeating the unit cell in three directions.

Unit Cell

close-packed structure of metal

EXPERIMENT 1 Making models of two metallic structures

cubic close-packing and hexagonal close-packing concepts of close-packing, co-ordination number, and unit cell are illustrated and clarified.
31 expanded polystyrene spheres
Blu-tak or similar adhesive

Step 1

A1

Six spheres touch the central sphere, outlining a regular hexagon.

EXPERIMENT 1 Making models of two metallic structures

Step 3

A4

Nine. These are shown by crosses in Fig. 24.

Step 5
Consider both ways of adding the second layer - adding three spheres or six spheres Q6 (c) If the layers were extended in all directions, could you distinguish between the two ways of adding the second layer? A6 (c) No, the two ways of adding the second layer are indistinguishable. It is only the fact that you are looking at a small part of the structure that makes them seem different.

EXPERIMENT 1 Making models of two metallic structures

Steps 6, 7 & 8

Q9Why the structure known as abc close-packing? A9 The third layer is not directly above the first, but the fourth layer is. The first three layers are referred to as a, b and c, while the fourth is regarded as another a layer. The sequence continues abcabcabcabc... .

EXPERIMENT 1 Making models of two metallic structures

abc close-packing or cubic close-packing or facecentred cubic

EXPERIMENT 1 Making models of two metallic structures

Step 9

EXPERIMENT 1 Making models of two metallic structures

Q12 Where are the close-packed layers in the cube?

A12 Along planes joining any diagonal of a face with one other corner.

Q13 What is the co-ordination number of any sphere in the extended structure?

A13

Twelve.

EXPERIMENT 1 Making models of two metallic structures

Step 10

2nd Part

EXPERIMENT 1 Making models of two metallic structures A14 The stacking of identical cubes side-by-side would not repeat the structure, unless the spheres are regarded as being shared between neighbouring cubes, as in Fig.27. You will do an exercise later which will make clearer the sharing of spheres between neighbouring unit cells.

EXPERIMENT 1 Making models of two metallic structures

Steps 11 & 12 aba close-packing or hexagonal close-packing

Q16 Why is it called aba close-packing?

A16 The third layer is directly above the first. Compare this with cubic close-packing where the fourth layer is directly above the first.

EXPERIMENT 1 Making models of two metallic structures

Step 13

EXPERIMENT 1 Making models of two metallic structures

unit cell of h.c.p.

C.

Octahedral and tetrahedral holes

Tetrahedral hole

Octahedral hole

C.

Octahedral and tetrahedral holes

In sodium chloride structure, sodium ions occupy all the available octahedral holes between the chloride ions. In calcium fluoride structure, the calcium ions form a face-centred cubic arrangement. The fluoride ions occupy tetrahedral holes between the calcium ions.

D.

Open Structures

in the close-packed structures, 74% of the space is occupied by spheres (i.e. 26% empty space). open structures are those with more open space between the atoms. body-centred cubic structure.

Hexagonal close-packed: Mg,

Zn, Ni Au, Al

Cubic close-packed: Cu, Ag, Body-centred cubic: the

alkali metals

Exercise 1
What physical property of the alkali metals, not shared by many other metals, is explained by their adoption of the body-centred cubic structure?

The relatively low density of the alkali metals is accounted for by the more `open nature of the body-centred cubic structure.

E. Sharing of Atoms between Neighbouring Unit Cells

Exercise 2
Look at Fig.11.7, which is a drawing of a space-filling unit cell, and answer the questions which follow. You can see that every sphere is shared with neighouring unit cells.

Fig. 11.7

(a) What structure does Fig. 11.7 represent?

ccp cubic close-packed / fcc face centred cubic

(b) How many neighbouring unit cells share (i) a corner atom, (ii) a centreface atom? (i) 8 (ii) 2
(c) Calculate the total number of spheres in the unit cell by adding the fractions of spheres indicated in the diagram. 1 The 8 corners contain sphere each; the 6 faces

contain sphere each. Total no. of atoms = 4

Exercise 3
Compare and contrast the two close packing atomic arrangements in metals.
(HKAL 1990 IA )

Metals having the hexagonal close packing has the abab arrangement for atoms in different layers. Metals having the face-centred cubic close packing has the abc arrangement for atoms in different layers. Both arrangements have the same packing efficiency. Or Atoms in both close packing arrangements all have the coordination number of 12.

Summary

F. Metallic Radius

One half the distances between the nuclei of adjacent metal atoms is called the metallic radius.

Exercise 4
(a) Fig.11.8 shows an electron density map for aluminium. Use the scale to find the metallic radius for aluminium.

Internuclear distance in Fig= 5.3cm Scale shows 1.9 cm 0.1 nm internuclear distance = 0.28 nm metallic radius = 0.28 nm/2 = 0.14 nm
Fig. 11.8

(b) The ionic radius for Al3+ is 0.045 nm. Why is this so much smaller than the metallic radius.

In the measurement of ionic radius it is assumed that the outer shell electrons have been transferred completely to another ion. The measurement of metallic radius includes the outer shell electrons, even though they are delocalized

G. Recognition of Metallic Structure

(a) (b) (c) (d)

Appearance

Malleability and ductility

Melting point Electrical conductivity

The use of pure metals is limited because

Alloys

they may be too weak or too soft for some purposes may be corroded easily.

Many of the metals used today are not pure metals but alloys.

An alloy is a mixture of two or more metals.

It is made by mixing the metals together as liquids and then allowing them to cool and solidify.

Some alloys contain metals and non-metals too.

Metals will readily form alloys since the metallic bond is nonspecific. The presence of small quantities of a second element in the metal frequently increases its strength.

Why alloys are stronger and harder than pure metals ?

The layers of atoms in a pure metal can slip over one another easily when a force is applied. This is because all the atoms are of the same size. In an alloy, differently sized atoms are present.

This prevents the layers slipping over one another. Thus, an alloy is stronger and harder, and less malleable and ductile than the pure metals from which it is made.

Some common alloys and their uses

Some common alloys and their uses

11.2

Giant Ionic Structures

Ions should come together to an ionic lattice in which attractive and repulsive force are balanced. The particular arrangement of ions depends on their relative charge and sizes.

Many ionic structures are close-packed arrangements of anions, with the smaller cations occupying holes in the structure.

A.

Sodium Chloride Structure

the cations fill in the octahedral holes of the cubic close-packed lattice of anions. a face-centred (cubic close-packed) lattice of chloride ions (radius, 0.181 nm), which is expanded to accommodate sodium ions (radius 0.098 nm) in the lattice of anions.

6:6 coordination. group I halides, hydrides and cyanides, many group II oxides and sulphides (for example, MgO, CaO, MgS).

Sodium Chloride Structure

Sodium Chloride Structure

B.

Caesium Chloride Structure

the caesium and chloride ions are much the same size (caesium, 1.69 , and chloride, 1.81 ).

a simple cubic structure then interpenetrate symmetrically 8:8 coordination

CsCl, CsBr, CsI

Caesium Chloride Structure

Exercise 5
(a)

Explain why sodium chloride could not adopt the caesium chloride structure.

Na+ ions are much smaller than Cl- ions. Eight Cl- ions cannot therefore get close to a Na+ ion before they repel each other too strongly for a stable arrangement.

Exercise 5
(b)

Look up the relevant ionic radii and predict which of these two structures would be adopted by : (i) potassium fluoride, KF (ii) sodium bromide, NaBr (iii) magnesium oxide, MgO

(i) (ii) (iii)

potassium fluoride, KF caesium chloride str. sodium bromide, NaBr sodium chloride str. magnesium oxide, MgO sodium chloride str.

C. Calcium Fluoride Structure

calcium fluoride, CaF2 (Ca2+ (F-)2)

each Ca2+ ion is surrounded by eight F ions

each F- ion is surrounded tetrahedrally by four Ca2+ ions F- ions occupy all the tetrahedral holes of the cubic closepacked lattice of Ca2+ ions.

Exercise 6
(a)

Consider the unit cell of calcium fluoride shown below:

(i) State the respective coordination numbers of each calcium ion and each fluoride ion.

Coordination no. of Ca2+ = 8 Coordination no. of F- = 4

Exercise 6
(a)

Consider the unit cell of calcium fluoride shown below:

(ii) Describe the lattice of calcium ions and that of fluoride ions.

Calcium ions : face-centred cubic structure / fcc Fluoride ions : simple (primitive) cubic structure

Exercise 6
(b)

(i) Draw the unit cell of caesium chloride.

(ii) Describe the lattice of caesium ions and that of

chloride ions in caesium chloride.

(i)

(ii)

simple cubic structures; simple cubic structure

Zinc blende structure

D.

Number of Ions in a Unit Cell

An ion at a corner is shared by 8 cells, giving ion per cell An ion on an edge is shared by 4 cells, giving ion per cell. An ion on a face is shared by 2 cells, giving ion per cell. An ion inside the cell is NOT shared, giving 1 ion per cell.

D.

Number of Ions in a Unit Cell

Na+ Cl3 3 4 1

At the corners, 8 ions, charge each On the edges, 12 ions, charge each On the faces, 6 ions, charge each

Inside the cell, 1 ion

1 4

Exercise 7
How many ion pairs of CsCl in a unit cell of caesium chloride.

The unit cell contains 1 Cs+ ion and 1 Cl- ion, i.e., 1 CsCl ion pair.

Exercise 8
The crystal structure of a compound AxBy can be described as a simple cubic lattice of A atoms with B atoms at the middle of all the edges.

(a) What is the empirical formula of this compound? (b) What are the coordination numbers of an A atom and a B atom respectively?
(2 marks)

(HKAL 1994 IA)

(a)

no. of atom A per unit-cell = 8 x 1/8 = 1 no. of atom B per unit-cell = 12 x 1/4 = 3 Empirical formula of the compound is AB3 Coordination number of a A atom : 6 Coordination number of a B atom : 2

(1) ( )

(b)

( )

E.

Cleavage of Crystals

always occurs in preferred directions, along the plane of atoms, molecules or ions which make up the structure. Such planes are often known as cleavage planes.

some planes cleave much more readily than others a slight displacement along the plane, caused by a sharp blow, brings ions of like charge opposite one another so that strong attraction between planes suddenly becomes strong repulsion.

F.

Recognition of Ionic Structure

(a)

Hardness Melting point Solubility in water

(b)

(c)

(d)

Action of electricity on
1) 2)

the molten state an aqueous solution

11.3 Giant Covalent Structures

all atoms are linked by covalent bonds The Structure of Graphite

A.

A.

The Structure of Graphite

Graphite can conduct electricity. Each graphite layer has a network of delocalized electrons extending over the whole layer graphite does not conduct at all well in directions across the layers. Graphite has a very high m.p., even higher than diamond. Graphite is relatively soft and can be used as lubricant.

B.

The Structure of Diamond

Each carbon atom is bonded tetrahedrally to 4 carbon atoms bond angle = 109.5o the coordination number of each carbon atom is 4 a form of a three-dimensional network

B.

The Structure of Diamond

the diamond lattice is a face-centred cubic Diamond is very hard because all the bonds are strong Diamond has a high melting point Diamond cannot conduct electricity

Example
(a)

Look up the densities of diamond and graphite. Comment on the differences. Both graphite and diamond are almost totally insoluble in all kinds of solvent. Why is this?
(a)

(b)

The density of diamond is 3.53 gcm-3 and that of graphite is 2.25 gcm-3. Graphite is less dense than diamond because the long van der Waals bonds give it a more open structure.

(b)

All the bonds in diamond are very strong and no solvent is able to break up the structure. In graphite, although there are weak bonds between layers, each layer is a giant structure with strong bonds which cannot be spilt up by a solvent.

C.

The Structure of Quartz (Silicon dioxide)

The SiO bonds about each silicon atom are tetrahedrally distributed and each oxygen atom is bonded to two other silicon atoms