1. THE SOLID STATE Solids are substances having definite shape and definite volume. In solids, the particles are closely packed and the force of attraction between the particles is strong. So solids are rigid and incompressible. Their constituent particles (atoms, molecules or ions) have fixed positions and can only vibrate about their mean po: Classification of solids On the basis of orderly arrangement of particles, solids can be classified into two— Crystalline solids and Amorphous solids 1. Crystalline solids In these solids, the constituent particles have a well ordered arrangement throughout the solid, i.e., they have a long range order. They consist ofa large number of small crystals They have a definite geometrical shape, melting point and heat of fusion. E.g.: Quartz, Diamond, Graphite, fullerene, NaCl, CuSQs.5H.O, ice, naphthalene, SiC etc. ions. 2. Amorphous solids In these solids, the ordered arrangement of constituent particles is only at some portions of the solid, ie., they have only a short range order. The structure of these solids is similar to that of liquids. They have no definite geometrical shape, melting point and heat of fusion. E.g.: Plastic, Glass (quartz glass), Rubber, amorphous silica, coal, charcoal, coke, PVC ete. * Like liquids amorphous solids have a tendency to flow, though very slowly. Therefore, sometimes these are also called pseudo solids or super cooled liquids. *Glass panes fixed to windows or doors of old buildings are slightly thicker at the bottom than at the top. This is because the glass flows down very slawly and makes the bottom portion slightly thicker. * Amorphous solids on heating become crystalline at some temperature. Some glass objects from ancient civilizations are found to become milky in appearance due to some crystallization, Anisotropic and isotropic substances *Solids in which the physical properties like electrical conductance, refractive index etc are different when measured in different directions are said to be anisotropic in nature. This is due to the different arrangement of particles in different directions. Crystalline solids are anisotropic. *Solids in which the physical properties are same along any direction are said to be isotropic in nature. This is due to the irregular arrangement of particles along different directions. Amorphous solids are isotropic.Differences between Crystalline solids and Amorphous solids Orderlyarrangement Properties Crystalline solids. Amorphous solids. Of Particle Long range order Only short range order Geometrical Definite characteristic No definite Geometrical shape geometrical shape shape Melting point Definite m.p No definite mp Heat of fusion Defini Not definite Mode of cleavage | Give regular cleavage en cutting | Give irregular cleavage on cutting Nature True solids Pseudo solids Isotropy/anisotropy | Anisotropic in nature Isotropic in nature Classification Based on the nature of particles and binding force On the basis of nature of particles and binding force between the particles, crystal 12 solids are classified into four types- molecular solids, ionic solids, metallic solids and covalent solids. Types of solid | Constituent | Attractive forces | Examples Physical | Electrical Melting particles nature | conductivity | point T]Molecular | Motecutes solids Dispersion or Soft Insulator Very low (a) Non-polar London forces {b) Polar Dipols-dipots Soft Insulator Low interactions (c)Hydrogen HO (ice) bonded Hydrogen Hard Insulator Low bonding Ty Tonic Tons ‘Coulombic or | NaC, Hard but | tnsulatorin High solids electrostatic brittle | solid state but conductors in molten state and in aqueous solutions [3] Metallic | Positive | Nfewallic Fe, Cu, Ag, | Hardbut | Conductorsin | Fairly high solids ions bonding, Mg malleable | solid state ina sea of and as well as in delocalised ductile | molten state electrons [a]Covatent | Atoms Covalent ‘SiO: (quartz), | Hard Tnsulator or bonding SIC, Diamond network solid Graphite Soft (Conductor Graphite has exceptional propertie itis soft and good conductor of electricity. In graphite carbon atoms are arranged in different layers and each atom is covalently bonded to 2three adjacent carbon atoms. The fourth electron is free to move about between different layers. So Graphite is a good conductor of electricity. The different layers are held together by weak van der Waal's force of attractions, So cach layer can slide over the other and hence itis soft and used as a good lubricant. Crystal lattice The regular three dimensional arrangements of constituent particles of a crystal in space is called crystal fattice or space Lattice. s of a crystal lattice are The important characteristi (a) Each point ina lattice is called lattice point of lattice site, (b) E: molecule (group of atoms) or an ion, (c) Lattice points ate joined by straight lines to bring out the geometey of the laltice. There are only 14 pos ensional lattices, These are called Bravais La Unit cell A unit cell is the smallest repeating unit of a ery dimension we geta whole crystal, Or, itis the building block of a cry: A unit cell is characterised by i) its dimensions along the three edges , (a,b and e) ii) angle between the edges ~ a (between b and ¢),B (between a and ¢) and y (between a and b), Thus a unit cell is characterised by 6 parameters ~ a, b,c, a, Band y. Unit cells can be broadly divided into two - primitive and centred unit cells. 1. Primitive Unit Cells: Here the constituent particles are present only at the corners of the unit cell. 2. Centred Unit Cells Here the constituent particles are present at the comers and other positions of the unit cell ch point in a crystal lative represents one constituent particle which may be an atom, a ible three din al lattice whieh, when repeated in three I. These are of three types: . Body-centred anit cell the corners of the unit cell. ii, Face-centred unit cells: Here the constituent part faces and at the corners of the unit cell. iii, End-centred unit celts: Here the constituent particles are present at the centre of any two opposite faces and at the comers of the unit cell, Seven types of erystal systems and their possible variations ( Refer th pg no.8) Iere the constituent particles are present at the bady centre and at cles are present at the centre of cach Calculation of Number of atoms in a unit cell (2) 1. Primitive cubie (Simple Cubic) unit cell:Here atoms are present only at the corners of the cube. cells. Therefore, contribution to one unit cell = 1/8 Since each unit cell has 8 atoms at the corners, the total number of atoms in one unit cell = 8x1/8= 1 So for a primitive (simple cubic) unit cell, z= 1 2. Body-centred cubic (bec) unit cells Here the particles are p The number of atoms at the corner = 8*1/8 = | The atom present at the centre of the body is not shared by other atoms. So the number of atoms at the bady-centre = | ich corer atom is shared by & unit ‘sent at the corners of the cube and also one atom at the body centre. Therefore, total number of atoms in the unit cel So, fora bee. z= 2 3. Face-centred cubic (fec) unit cell: Here the atoms are present at the corners and also at the centre of each faces. Each corner atom is shared by 8 unit cells and each face centr Number of corner atoms = 8*1/8 = | Number of fa Therefore. total number of atoms So, for an feo, z= 4 Close packing in solids 1-2 atom is shared by 2 unit cells. centre atoms = 6x 1/2 =3 4384 In solids the particles are closely packed leaving minimum vacant space. In close packed structures the particles are considered as hard spheres. Co-ordination Number Ina close packed arrangement the number of nearest neighbours with which a given sphere is in contact is called the co-ordination number of that spher Solids are three dimensional arid the 3 dimensional structure can be obtained by the following three steps: 1. Close packing in One Dimensions Here the spheres are arranged in a row touching cach other. In this arrangement each sphere isin contact with 2 adjacent spheres. Therefore, co-ordination number of each sphere is 2. 2. Close packingin Two Dimensions Here the spheres are arranged in two directions — length-w done in two different ways. i. Square close packing: Here the spheres of second raw are placed exactly above those of the first row(AAA type). So the co-ordination number of each sphere is 4 Hexagonal clase packing: Here (he spheres of the second row are placed in the depressior of the first row (AB AB type). So the co-ordination number of each sphere is 6. Hexagonal close packing is more efficient than square close packing in two dimensions, This is because in Hexagonal close packing maximum space is occupied by spheres. 3. Close packing in Three Dimensions ise and breadth-wise. This can beHere the particles are arranged in layers. This can be possible in two ways. Three dimensional close packing from two dimensional square close=| Here th arrangement of the spheres in the first layer is denoted as ‘A*, all the layers are of "A* type. So this arrangement forms AAA... type pattern, The lattice thus generated is the simple cubic lattice and its unit cell is the primitive cubic unit cell. The co ordination number is 6. Three dimensional close packing from two dimensional hexagonal close-packed layers; Here the first layer is arranged as hexagonal manner, The second layer is placed abowe the depressions of the first layer. On placing the second layer there arises two types of voids (vacant spaces) above the second layer — tetrahedral voids and octahedral voids. Tetrahedral void : Thus when we place the third layer over the second there are two. possibilities: Covering tetrahedral voids: Here the spheres of the third layer are placed above the tetrahedral voids of the second layer. [f we call the first layer as *A’ and the second layer as “B’, then the third layer will be “A, the fourth layer will be *B* and so on. This will form the pattern ABAB...... This type of close packing is called Hexagonal close packing (leep) in three dimensions, This type of arrangement is found in metals like Mg, Zn etc, Covering octahedral voids: Mere the spheres of the third layer are placed above the octahedral voids of the second layer. If we call the first layer as ‘A’, the second layer as ‘B’, and the third layer as “C°, then the fourth layer will be *A’, the fifth layer will be “B* and so. on. This will form the pattern ABCABC...... This type of close packing is called Cuble close packing (cep) or face-centred cubie(fec) packing in three dimensions. This type of arrangement is found in metals like Cu, Ag ete. Similarities between hep and cep i)In both hep and cep 74% of the available space is occupied by spheres. So both are equally efficient. ii)In both hep and cep each sphere is in contact with [2 adjacent spheres. Thus the co- ordination number in both hep and cep is 12. Interstitial voids The vacant space in close packed arrangement is called voids. These are of two types- tetrahedral voids and octahedral voids. Tetrahedral void: A void surrounded by four spheres in tetrahedral position is called tetrahedral void. In a close packed arrangement the number of tetrahedral voids is double the number of spheres, i.e. there are two tetrahedral voids per sphere. Octahedral voids: A void surrounded by six spheres in octahedral position is called octahedral void. Ina close packed arrangement the number of octahedral voids is equal to the number of spheres, i.e. there is only one octahedral void per sphere. To determine the formuta of a compound: The bigger ions (anions)form the lattice points, cep or hep. The smaller ions (cationsoccupy the voids.Let the number of close packed spheres or atoms be Nhen The number of tetrahedral voids =2N and The number of octahedral voids = N Packing Efficiency The percentage of the total space occupied by spheres (particles) is called packing efficiency, Packing Efficiency Volume occupied by all the spheres in the unit cell x 100 Total volume of the unit cell Calculation of Packing Efficiency i) ln simple cubie structures: Consider a cube with edge length ‘a’ and the radius of the particle “r. Here the edge length Is related to the radius of the particle asa = 2r ‘The volume of the cubic unit cell = a= (2r)'=8rt Asimple cubic unit cell contains only one particle. (4/3) n° Packing Efficiency= Volume occupied by the spheres in the unit cell x 100 Volume of one spher: Total volume of the unit cell = (4/3)nrax100 ars = 52.4% Hl) In hep and cep structures Consider a cube with edge length ‘a’ and face diagonal ‘b’ In BABE, AC? = AB*4BC” He.b?=a%a? or, b?= 2a" or,b= ¥2a If'r Isthe radius of the sphere, then b= 4r Or, a = 4rV2 = 2v2rWe knaw that, volume of a sphere = (4/3)nr° In.ccp (fcc) or hep, there four spheres per unit cell Volume of four spheres = 4x(4/3)tr> Volume of the cube =a? = (2v2n)? Packing Efficiency= Volume occupied by four spheras in the unit cell x 100 Total velume of the unit cell = ax(4/3}nr? x100. Consider a cube with edge length ‘a’, face diagonal ’b’ and body diagonal ‘c” From the figure it is clear that the atom at the centres In contact with the other two atoms diagonally placed, In dEFD, FD? Or, a = 4r/v3 (also r = v3a/4) Ina bce, the no. of atoms present per unit cell = 2 Volume of 2 spheres =2 x (4/3)nr> Volume of the cube = a3= (41/¥3)? Packing Efficiency= Volume occupied by two spheres in the unit cell x 100 % Total volume of the unit cell. = 2x{A/3}rr? 100% (ardv3)* = 6% Calculation of Density of the unit ccll (Soli) Consider a cubic unit cell with edge length ‘a’, Then volume of the unit cell = a’Let *M" be the atomic mass of the element in the unit cell (i.e. mass of Avogadro number (N,) of atoms: Then mass of one atom=M/ Ny. Let the number of particles present per unit cell = z Then mass of the unit cell = zx M/Nx Density of the unit cell = -Masseftheunit cell Volumeoft heunit cell zM a3N i.e, density d= a Relationship between edge length (a) and radius of the sphere (r) in anit cell. 4 For FeC.a=2V2¢ For BCC, at For simple cubic, a=2r Imperfections in solids (Crystal Defects) The deviation from the regular orderly arrangement of particles of a solid is termed as imperfections or crystal defects. The crystal defec defects and line defects. The imperfection around a point (an atom) in a crystalline substance, it is termed as point defect. The imperfect Point defects are broadly classified into two — point along a row is termed as line defect. Point defects can be classified into three types: Stoichiometric defects, Non- stoichiometric defeets and Impurity defects. 1. Stoi metric defects: These are point defects which do not disturb the stoichiometry of the solid. They are also called ittrinsic or drermodynamic defects, because these defects can also develop when a substance is heated, These are of two types — vacancy defects and interstitial defects. a) Vacaney defect: When some of the lattice sites are vacant, the crystal is said to have vacancy defect. This defect decreases the density of the solid. b) Interstitial defect: When some constituent particles occupy an interstitial site, the crystal is said to have interstitial defect. This defect increases the density of the solid The above two types of defects are shown by non-ionic solids. Tonic solids show two types of stoichiometric defects — Schottky defeet and Erenkel defect. i, Schottky defect: It is basically a vacancy defect. It arises due to the missing of equal number of ani ns and cations from the lattice site. It is shown by ionic crystals in which the anionic and cationic sizes are almost equal... Due to this defect the density of the solid decreases. NaCl, KCl, CsCl, AgBretc. show Schottky defect. ii, Frenkel defect: It isa stoichiometric defect arising duc to the misplac (generally a cation) from the lattice site to the intersti g ofan ion al site. [lis also called dislocation 8defect. This type of defect is shown by ionic solids in which there is a large difference in the size of the ions.This defect does not change the density of the solid. . Eg. ZnS, AgCl, AgBr, Agl ete. I) Impurity Defects: It is the defect arising due to the presence of foreign particles ina crystal. For example if molten NaCl containing a litile amount of SrClzis crystallised, some of the sites of Na’ ions are occupied by Sr” Each Sr replaces two Na” ions. It occupies the site of one ion and the other site remains vacant, The cationic vacancies thus produced are ins va equal to the number of Sr ions. Another similar example is a solid solution of CdCb and AgCl. HY Non-Stoichiometric defects: These are point defects which change the stoichiometry of a solid. These defects are of two types: i) Metal excess defect and ii) Metal deficiency defect i) Metal excess Defect Here the number of cations is greater than the number of anions. This arises in two ways: a)Metal excess defect due to anionic vacancies: Here some of the anions are missing from the lattice site, The electrical neutrality is maintained by occupying electrons in the anionic sites. Anionic sites occupied by unpaired electrons are called f-centres and are responsible for colour and paramagnetism of the crystal This defect is shown by alkali metal halides. For example when NaCl is heated in an atmosphere of sodium vapour, some sodium atoms are deposited at the surface of the crystal. The CI ions diffuse to the surface of the crystal and combines with Na atom to form NaCl. Na+Cl- > NaCl + e- The electron so formed diffuse into the crystal and occupies the anion vacancy. These electrons absorb light energy and get excited. As.a result the crystal becomes yellow in colour. Similarly, excess of Li makes LiCl crystals pink and excess of K makes KCL crystals violet. b) Metal excess defect due to extra cations at interstitial sites: Here some cations occupy the interstitial sites. The electrical neutrality is maintained by occupying some electrons in adjacent interstitial sites. Eg. When ZnO crystals are heated, the white coloured crystals becomes yellow. This is because on heating, the crystal loses oxygen as follows: ZnO — Zn + % Ort 2e- The Zn ions now move to the interstitial sites and the electrons to n sites. ii) Metal deficiency Defect: Here the number of cations is smaller than the number of anions. This is mainly arises due to cation vacancies. This type of defect is commonly shown by transition metal compounds. Eg. FeQ.[t may be FeosO(or Fens10 to FeawQ)Some Fe" ions are missing and the loss of positive charge is made up by Fe" ions resulting in metal deficiency. Electrical properties of solids Based on the electrical conductivity, solids are classified into thr: types: i, Conductors: They are solids which allow the passage of electricity through them. Their conductivity ranges from 10'to 10" ohnv'ny!, Metals have canductiv the order of 10” ohnmrim" ii, Semi-conductors: They are solids which allow the passage of electricity only partially, Their conductivity ranges from 10! to 10% ohn! iii. Insulators: They are solids which do not allow the pas: Their conductivity ranges from 10" to 107° ohny'n', Conduction of Electricity in metals— Band theory Metals conduct electricity in solid as well as in molten state. The conductivity of metals ge of electricity through them. depends upon the number of valence electrons. The atomic orbitals of metals combine to form molecular arbitals, which are so closely spaced that they forma band. Conductors: There i conduction band or valence band overlaps with a higher energy conduction band so that the electrons can flow easily . Insulators: The energy gap between filled valence band and the unoccupied conduction band known as forbidden zone. Electrons cannot jump to it and such substances act no energy gap between the valence band and the higher unoccupied is large and is as insulators. Semi-conductors: The energy gap between the valence band and the conduction band is small. So some electron may jump from valence band to conduction band and show some conductivity Th conduction band. Such semiconductors are also called dittrinsic semiconductors. 1 conductivity increases with rise in temperature, since more electrons can jump to the The conductivity of intrinsic semiconductors is very low. Their conductivity can be incre by adding an appropriat. creates electronic defects in them. Such Doping can be done by the addition of either electron rich impurity or ele: impurity. impurity. The process is called doping. Addition of impurities emiconductors are called extrinsic semiconductors. tron deficit a) Doping by electron rich impurit When a group 14 (which contains 4 electrons in the valence shell) element like Si or Ge is doped with a group 15 element (which contains 5 clectrons in the valence shell) like P or As, four electrons are used for the formation of covalent bonds and the fifth electron becomes 10free. The presence of this delocalised electron increases the conductivity and hence silicon doped with electron rich impurities is called #-type semiconductor, b) Doping by electron deficient impurity: p-type semiconductor Whena group 14 (which contains 4 electrons in the valence shell) element like Si or Ge is doped with a group 13 element (which contains 3 electrons in the yalence shell) like B, Al, or Ga, the three electrons are used for the formation of covalent bonds and the fourth valence electron is missing: This creates an electron hole or electron vacancy. An electron from a neighbouring atom can come and fill the electron hole. So the position of the hole is moved in the direction opposite to that of the electron has moved. Under the influence of electric field, electrons would move towards the positively charged plate through electronic holes. It would appear as if electron holes are positively charged. This type of semiconductors are called p-type senticonductors. A large variety of solids which have lattices similar to Ge or Si have been prepared by the combination of groups 13&15 or 12&16. E.g. for [3and15 group compounds are InSb, AIP & GaAs. They are used as semiconductors. for 12 and 16 group compounds are ZnS, CdS, CdSe & HgTe. Magnetic properties of solids Every solid has some magnetic properties associated with it due to the presence of electrons. Each electron in an atorn behaves like a tiny magnet. [ts magnetic moment arises from two types of motions: (i)its orbital motion around the nucleus and{(ii) its spin around its own axis.. The magnitude of this magnetic moment is very small and is a measured in the unit called Bohr Magneton (4B). Based on the magnetic properties, solids can be classified into fire types. 1. Diamagnetic Substances: These are weakly repelled by an external magnetic field. Diamagnetism arises due to the presence of only paired electrons. Pairing of electrons cancels their magnetic moments and so they have no net magnetic moment. E.g.: H:O, NaCl, Benzene (C.Ha) 2. Paramagnetic Substances: They are weakly attracted by an external magnetic field. Paramagnetism is due to the presence of one or more unpaired electrons. They have anet magnetic moment: They lose their magnetism in the absence of external magnetic field. So they are temporary magnets. Eg: O:, Cu, Fe, Cr ete. 3. Ferromagnetic Substances: They are very strongly attracted by a magnetic field and can be permanently magnetised. In solid state, the metal ions of ferromagnetic substances are grouped together into small regions called domains. In the absence of an external magnetic field, these domains are randomly oriented. When the substance is placed in a magnetic field, all the domains get oriented in the direction of the magnetic field and a strong magnetic effect is produced. This ordering of domains do not change even when the extemal magnetic field is removed and so they become permanent magnets. Eg: Fe, Co, Ni, Gd (Gadolinium), CrO; etc. 14. Anti-ferromagnetic Substances: Here the domains are oppositively oriented and cancel each other. So they have no net magnetic moment. Eg: MnO 5. Ferrimagnetie Substances: Here the domains are arranged in opposite directions but in unequal numbers. So they have a net magnetic moment. Eg: FeO, (magnetite) and ferrites like MgFe.0,, ZnFe,O, ete Alignment of domain Ferromagnetic substance Antiferromagnetic substance DOOOOO ‘sexe substance » ae