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 We are mostly surrounded by solids and we use themmore often than liquids and gases. For different applications we need solids with widely different properties. These properties depend upon the nature of constituent particles and the binding forces operating between them. Therefore, study of the structure of solidsis important. The correlation between structure andproperties helps in discovering new solid materials with desired properties like high temperaturesuperconductors, magnetic materials, biodegradablepolymers for packaging, biocompliant solids for surgicalimplants, etc.From our earlier studies, we know that liquids andgases are called
 fluids 
because of their ability to flow. The fluidity in both of these states is due to the fact that the molecules are free to move about. On the contrary,the constituent particles in solids have fixed positionsand can only oscillate about their mean positions. Thisexplains the rigidity in solids. In crystalline solids, theconstituent particles are arranged in regular patterns.In this Unit, we shall discuss different possiblearrangements of particles resulting in several types of structures. The correlation between the nature of interactions within the constituent particles and severalproperties of solids will also be explored. How theseproperties get modified due to the structuralimperfections or by the presence of impurities in minuteamounts would also be discussed.
 After studying this Unit, you will beable to
•
describe general characteristics of solid state;
•
distinguish between amorphousand crystalline solids;
•
classify crystalline solids on the basis of the nature of bindingforces;
•
define crystal lattice and unit cell;
•
explain close packing of particles;
•
describe different types of voidsand close packed structures;
•
calculate the packing efficiency of different types of cubic unit cells;
•
correlate the density of a substance with its unit cellproperties;
•
describe the imperfections insolids and their effect onproperties;
•
correlate the electrical andmagnetic properties of solids andtheir structure.
Objectives
The vast majority of solid substances like high temperature superconductors, biocompatible plastics, silicon chips, etc. are destined to play an ever expanding role in future development of science.
The Solid State
11111
Unit
11111
The Solid State
 
2Chemistry 
In Class XI you have learnt that matter can exist in three states namely,solid, liquid and gas. Under a given set of conditions of temperature andpressure, which of these would be the most stable state of a givensubstance depends upon the net effect of two opposing factors.Intermolecular forces tend to keep the molecules (or atoms or ions) closer, whereas thermal energy tends to keep them apart by making them movefaster. At sufficiently low temperature, the thermal energy is low andintermolecular forces bring them so close that they cling to one another and occupy fixed positions. These can still oscillate about their meanpositions and the substance exists in solid state. The following are thecharacteristic properties of the solid state:(i)They have definite mass, volume and shape.(ii)Intermolecular distances are short.(iii)Intermolecular forces are strong.(iv)Their constituent particles (atoms, molecules or ions) have fixedpositions and can only oscillate about their mean positions.(v)They are incompressible and rigid.Solids can be classified as
crystalline 
or 
amorphous 
on the basis of thenature of order present in the arrangement of their constituent particles. A crystalline solid usually consists of a large number of small crystals,each of them having a definite characteristic geometrical shape. In a crystal,the arrangement of constituent particles (atoms, molecules or ions) isordered. It has long range order which means that there is a regular patternof arrangement of particles which repeats itself periodically over the entirecrystal. Sodium chloride and quartz are typical examples of crystallinesolids. An amorphous solid (Greek 
amorphos 
= no form) consists of particlesof irregular shape. The arrangement of constituent particles (atoms,molecules or ions) in such a solid has only 
short range order 
. In such anarrangement, a regular and periodically repeating pattern is observed over short distances only. Such portionsare scattered and in between thearrangement is disordered. Thestructures of quartz (crystalline) andquartz glass (amorphous) are shownin Fig. 1.1 (a) and (b) respectively. While the two structures are almost identical, yet in the case of amorphous quartz glass there is no
long range order 
. The structure of amorphous solids is similar to that of liquids. Glass, rubber and plasticsare typical examples of amorphoussolids. Due to the differences in thearrangement of the constituent particles, the two types of solids differ in their properties.
1.1GeneralCharacteristicsof Solid State1.2Amorphousand CrystallineSolids
Fig. 1.1: 
Two dimensional structure of (a) quartz and (b) quartz glass 
 
3 The Solid State
Crystalline solids have a sharp melting point. On the other hand,amorphous solids soften over a range of temperature and can bemoulded and blown into various shapes. On heating they becomecrystalline at some temperature. Some glass objects from ancient civilisations are found to become milky inappearance because of some crystallisation. Likeliquids, amorphous solids have a tendency to flow,though very slowly. Therefore, sometimes these arecalled
 pseudo solids 
or 
super cooled 
 
liquids 
. Glasspanes fixed to windows or doors of old buildingsare invariably found to be slightly thicker at the bottom than at the top. This is because the glassflows down very slowly and makes the bottomportion slightly thicker.Crystalline solids are
anisotropic 
in nature, that is, some of their physical properties like electricalresistance or refractive index show different values when measured along different directions in the samecrystals. This arises from different arrangement of particles in different directions. This is illustrated inFig. 1.2. Since the arrangement of particles is different along different directions, the value of same physicalproperty is found to be different along each direction. Amorphous solids on the other hand are
isotropic 
in nature. It is because there is no
long range 
order in them andarrangement is irregular along all the directions. Therefore, value of any physical property would be same along any direction. Thesedifferences are summarised in Table 1.1.
 Table 1.1: Distinctionbetween Crystalline and Amorphous Solids
ShapeMelting point Cleavageproperty Heat of fusion Anisotropy NatureOrder inarrangement of constituent particlesDefinite characteristic geometrical shapeMelt at a sharp and characteristictemperature When cut with a sharp edged tool, they split into two pieces and the newly generated surfaces are plain andsmooth They have a definite and characteristicheat of fusion Anisotropic in nature True solidsLong range order Irregular shapeGradually soften over a range of temperature When cut with a sharp edged tool, they cut into two pieces with irregular surfaces They do not have definite heat of fusionIsotropic in naturePseudo solids or super cooled liquidsOnly short range order.
Property Crystalline solids Amorphous solids
DCB A 
Fig. 1.2: 
 Anisotropy in crystals is due to different arrangement of  particles along different directions.
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