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Chemistry · Ch 11 — The Solid State

Amorphous and Crystalline Solids

11.2

Amorphous and Crystalline Solids

Solids are classified as crystalline or amorphous depending on the nature of the order in which their constituent particles are arranged.

Crystalline solids — long range order

A crystalline solid is usually made up of a very large number of small crystals, each with a definite characteristic geometrical shape. Inside a crystal the particles (atoms, ions or molecules) are arranged in an ordered, repetitive pattern in three dimensions. If you know the arrangement in one small region, you can predict exactly where the particles sit anywhere else in the crystal, however far away. This regular pattern repeating periodically over the whole crystal is called long range order. Sodium chloride and quartz are typical examples.

Amorphous solids — short range order

Substances like glass, rubber and many plastics do not crystallise when their melts cool; they are amorphous solids. The word comes from the Greek amorphos, meaning "no form". Here the arrangement has only short range order — a regular pattern appears over short distances, but these ordered patches are scattered and the arrangement between them is disordered.

As Fig. 1.1 shows, quartz (a) and quartz glass (b) are built from the very same SiO2_2 units joined the same way, yet in the crystalline quartz the rings repeat in a regular lattice while in the amorphous quartz glass the rings are distorted with no repeating pattern. The structure of an amorphous solid is, in fact, very much like that of a liquid.


How their properties differ

Melting behaviour. A crystalline solid has a sharp melting point — at one characteristic temperature it melts abruptly to a liquid. An amorphous solid instead softens and starts to flow over a range of temperature, which is why it can be moulded and blown into shapes. Because amorphous solids resemble liquids and even tend to flow very slowly, they are regarded as extremely viscous liquids, and are sometimes called pseudo solids or super cooled liquids. Over long periods they may even partly crystallise — some ancient glass objects turn milky for exactly this reason.

Isotropy vs anisotropy. Amorphous solids are isotropic: properties such as mechanical strength, refractive index and electrical conductivity are the same in all directions, because there is no long range order to make any direction special. Crystalline solids are anisotropic: physical properties like electrical resistance or refractive index can have different values along different directions. As illustrated in Fig. 1.2, in a two-dimensional pattern of two kinds of atoms, shearing along the CD direction displaces a row containing both types of atoms, while shearing along the AB direction moves rows made of a single type — so the resistance differs with direction.


Distinction between crystalline and amorphous solids (Table 1.1)

PropertyCrystalline solidsAmorphous solids
ShapeDefinite characteristic geometrical shapeIrregular shape
Melting pointMelt at a sharp and characteristic temperatureGradually soften over a range of temperature
Cleavage propertySplit cleanly into pieces with plain, smooth surfacesCut into pieces with irregular surfaces
Heat of fusionDefinite and characteristic enthalpy of fusionNo definite enthalpy of fusion
AnisotropyAnisotropicIsotropic
NatureTrue solidsPseudo solids or super cooled liquids
Table 1.1Distinction between Crystalline and Amorphous Solids
PropertyCrystalline solidsAmorphous solids
ShapeDefinite characteristic geometrical shapeIrregular shape
Melting pointMelt at a sharp and characteristic temperatureGradually soften over a range of temperature
Cleavage propertyWhen cut with a sharp edged tool, they split into two pieces and the newly generated surfaces are plain and smoothWhen cut with a sharp edged tool, they cut into two pieces with irregular surfaces
Heat of fusionThey have a definite and characteristic enthalpy of fusionThey do not have definite enthalpy of fusion
AnisotropyAnisotropic in natureIsotropic in nature
Figure 1.1Two dimensional structure of (a) quartz and (b) quartz glass

What this figure shows. Two side-by-side 2D network diagrams of SiO2 drawn as small circles (atoms) joined by straight bonds. Panel (a) 'quartz' shows a regular, repeating ordered lattice of linked triangles/rings (long-range order). Panel (b) 'quartz glass' shows the same atoms and bonds but arranged irregularly with distorted rings and no repeating pattern (short-range order only). Label (a) under left diagram, (b) under right …

Figure 1.2Anisotropy in crystals is due to different arrangement of particles along different directions.

What this figure shows. A 2D square array of two kinds of atoms (two sizes/shades of circles) arranged in alternating rows. Two diagonal direction lines are drawn across the pattern and labelled with letters A, B, C, D marking two directions (AB and CD). One direction (AB) cuts through rows of a single atom type; the other (CD) cuts through rows containing both atom types, illustrating direction-dependent (anisotropic) properties. …