V.C.E Chemistry

Year 11 Revision Notes

Structure of Solids

Structure of Solids

Relate the structure of solids to their Physical properties.

Ionic Solids

Atomic (Covalent) Solids

Metallic Solids

Molecular Solids

Allotropes

Allotrophy of Carbon

Structure of Solids

Relate the structure of solids to their Physical properties.

Ionic Solids

Crystals such as NaCl are hard and brittle. They have a high melting point (801C) and are very poor conductors of electricity in the solid state, but conduct electricity well in the molten state.

 

 

The lines in the diagram help to show the arrangement of the ions in the lattice, and must not be taken as chemical bonds. The number of atoms in a tiny crystal of NaCl is enormous and the diagram should be imagined as extending in all three directions. It should be noted that each ion is bonded by six ions of opposite charge. This structure of NaCl is consistent with the observed hardness of the crystal (ie showing each ions surrounded by six strongly attracted oppositely charged ions).

The brittleness of NaCl is also consistent with the diagram of its structure. So if a deforming force acts on a crystal of sodium chloride and the ions are made to slide past one another, strong repulsive forces come into play and these forces rupture the crystal, eg

The structures above suggest that the ions are stationary in the crystal but this is no so. They are in a state of constant vibration. If the temperature is increased, the ions vibrate more violently. If the temperature is increased the ions vibrate more violently, because the additional heat energy absorbed increases the kinetic energy of vibration in the ions. If the temperature becomes high enough, the vibrations will become so violent that the crystal lattice will be destroyed. So even though oppositely charged ions still attract one another, they are free enough to slide past each other, ie the solid melts. When the forces between particles comprising a solid are strong, considerable energy will be needed to disrupt the crystal lattice and melt the solid. So the stronger he force holding the particles of a substance in the crystal lattice, the higher the melting point.

 

Atomic (Covalent) Solids

These solids have the following properties

i)                    non conductors of electricity in solid and liquid states

ii)                   high melting and boiling points

iii)                 insoluble in water and most other solvents

iv)                 they are chemically inert

v)                  extremely hard

vi)                 brittle

Clearly, the forces holding the particles of these substances together are extremely strong. Since the substances are non-conductors in the liquid state the constituent particles must be uncharged, so that the ionic model is inappropriate to explain the observed properties. Common examples of these solids are diamond, silicon dioxide, silicon carbide and tungsten carbide.

In the case of the diamond lattice it can be seen that each carbon atom is surrounded by four others (tetrahedral arrangement). The structure consists of a tetrahedral extending in all dimensions, which suggests covalent bonding between adjacent atoms. This in turn explains the observed properties of diamond. The strength of the bonding and the fact that it exists throughout the crystal accounts for the extreme hardness and high sublimation temperature of diamond. (as well as the high melting and boiling points of these solids in general). This is quite understandable since boiling, melting and or sublimation, requires the rupturing of covalent bonds and very high temperatures are required to do this.

The brittleness of diamond is explained by the directional nature of the covalent bonds, which makes it possible for the atoms to move relative to one another without the attractive forces between them being drastically weakened. Consequently the crystal is unable to deform, but shatters if subjected to too great a force.

 

Metallic Solids

The physical properties of metals include the following

i)                    metals are usually good conductors of heat and electricity

ii)                   most metals are malleable, (can be hammered into sheets) and ductile (can be drawn into wire)

iii)                 their hardness ranges from soft to very hard (Na is so soft it can be cut with a knife whereas Cr is very hard

iv)                 their densities range from very high to low, although the densities are usually fairly high

v)                  they are lustrous (shiny surface) although most metals tarnish and must be scraped to show lustre

vi)                 melting points range from low to high e.g. Hg (–39°C) to W (3870°C)

In discussing the structure of metallic solids, sodium will be examined. It is generally believed that metal consist of a lattice of positive ions through which moves a cloud of electrons. These electrons are the valency electrons of the metal and for sodium are the outermost electron from each atom. The positive ions tends to repel each other however they held together by the cloud of negatively charged electrons. All the valency electrons move freely throughout the whole of the crystal lattice and so bind the whole set of particles into a single unit. A particular valency electron does not belong to any particular ion, but belongs to the whole crystal.

Electric current in a metal can be shown to consist of a flow of electrons. If an electrical potential is applied to the ends of a metallic wire, a general movement of the electrons the wires is superimposed on their random movement within the lattice. This results in a number of electrons being forced into one end of the wire while a similar number of electrons are forced out the other end. So the electric current passes along the wire. Heat energy can also be carried by the mobile electrons.

The positive ions in a metal are not held by rigid bonds but are capable of sliding past one another if the metal is deformed. This rearrangement of the ions doesn’t alter the general attractive force in any significant way, so the metal doesn’t shatter. So metals are generally not brittle.

The bonding forces can vary widely in metals and this explains the wide variation in the hardness of metals.

This wide variation in the bonding forces also accounts for the wide range of melting points in metals.

 

Molecular Solids

The physical properties of molecular solids include

i)                    do not conduct electricity

ii)                   have low melting points

iii)                 they are quite soft

The crystals of many organic substances differ strikingly from salts such as NaCl. Napthalene is a good example of such a compond. Unlike NaCl, the crystals are soft and have a low melting point (~80°C), although like NaCl, naphthalene does not conduct electricity in the solid state. These properties are shared by some inorganic compounds such as hydrogen chloride, oxygen and carbon dioxide in the solid state. The atoms in all of these compounds are held together by covalent bonds. These latter substances are gases under normal room temperatures. All of these substances cann be obtained in the solid state if the temperature is sufficiently low, and this suggests that there is some force tending to hold the molecules together. The fact that these solids are very easily melted and soft suggests that the forces are weak. These intermolecular forces are called Van der Waals forces, after the Dutch physicist who suggested their existence. Weak intermolecular forces are also called dispersion forces.

 

Allotropes

Allotropes have different structural forms of the one element. Some elements have the ability to bond covalently in more than one structural form.

The different structural forms of the element will have different physical properties such as hardness, density, electrical conductivity, melting point, and boiling point. However being of identical atoms, the different allotropes of the one element will form the same compounds and usually undergo similar chemical reactions. Elements forming allotropes include sulphur, carbon, phosphorus, tin and oxygen. Carbon will be investigated in depth

 

Allotrophy of Carbon

Diamond

Diamonds occur naturally or they can be made synthetically by subjecting carbon containing compounds or graphite to very high temperatures and pressures. Synthetic diamonds are quite tiny but are indistinguishable from naturally occurring diamond.

Diamond is one of the hardest substances known. It sublimes at temperatures above 3500°C and is a non conductor of electricity.

One of the properties of diamond that makes it a highly prized gemstone is its property of diffracting light to a very marked extent. The cutting of faces of diamond is designed to use this property to give the gem the greatest possible amount of “fire”.

Diamond is the densest form of carbon and its relatively high density (3.5 g cm-3) reflects the compact nature of the substance. Diamond is extremely resistant to chemical attack, but it will burn in oxygen if heated to 800°C

The industrial uses of diamond depend on its great hardness. Black diamonds are used in rock drills and chips of diamond are used in glass cutters. Industrial diamonds are also used as abrasives for grinding very hard materials. Diamond’s non conductivity can be attributed to all its electrons being used in bonding.

 

Graphite

Graphite occurs naturally in considerable quantities. It is also manufactured in large quantities in electric furnaces. Coke is packed into furnaces together with a little iron (III) oxide as catalyst and then covered with a mixture of sand and coke. The mixture is heated to a temperature of about 3000°C for about 24 hours. Impurities in the coke vapourize and the product is practically pure graphite.

Physical Properties of Graphite

Graphite is a crystalline solid. It has a soft greasy feeling and leaves dark streaks if it is rubbed on paper. Examination of these black streaks shows that they consist of a thin layer minute crystals. Graphite is less dense than diamond, and has a density of 2.2 g cm-3. It has a metallic lustre and is a fairly good conductor of electricity.

The structure of graphite has been determined by x ray crystallography, in the same way as diamond and the structure is shown below.

 

The structure shows that graphite consists of layers. The layers are parallel to one another and there is a relatively wide separation between adjacent layers.

At least three of the four valence electrons of each carbon atom are used in forming bonds with the three adjacent carbon atoms in the layer. The fourth valency electron of each carbon atom is not located by bond formation. The electrical conductivity of graphite can be explained on the basis of the mobility of these electrons. The separate layers are too widely spaced to be bonded together by covalent bonds and are probably bound together by weak Van der Waals forces which explains why graphite is so soft and flaky.

Chemical Properties of Graphite

Graphite is somewhat more reactive than diamond. Thus is burns more readily and is attached by nitric acid and sulphuric acid.

Uses of Graphite

Graphite is used to make “Lead” pencils. The graphite is powdered and mixed with clay, that hardness of the “lead” depending on the properties of the clay. Graphite is a highly refractory material with a melting point of ~ 3500°C. It is widely used for making crucibles to hold molten metals.

The electrical conductivity of graphite makes it suitable as the electrode material in electrical furnaces and arc lights. In addition, graphite is not attacked by chlorine and its is therefore used for electrodes during electrolysis, if chlorine is evolved at the electrode.

Graphite is also a good lubricant, because adjacent layers slide easily over one another. It is particularly useful for lubricating moving parts which are subject to high temperatures, where mineral oils would burn away.

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