The Solid State Solids are the chemical substances which are characterised by definite shape and volume, rigidity, high density, low compressibility. The constituent particles (atoms, molecules or ions) are closely packed and held together by strong interparticle forces. Types of Solids The solids are of two types : Crystalline solids and amorphous solids. Distinction Between Crystalline and Amorphous Solids S.No. | Crystalline solids | Amorphous solids: 1. | These have definite and regular | These doesn't have any regular arrangement of the constituent arrangement of the constituent particles in space. | patticles in space. 2. | These are true solids | These are super cooled liquids or | pseudo solids | These have long order in arrangement | These have short order in arrangement w [: the particles, of particles 4. | These are anisotropic in nature, ie. | These are isotrapic in nature ie. their their physical properties are different | physical properties are same in all the in different directions. | directions. 5. | They have sharp melting paints. | They melt over a certain range of | temperature. 6. | They undergo a clean cleavage when | They undergo irregular cleavage when cut | cut 7. | They have a defirite and characteristic | They do not have definite heat of heat of fusion | fusionTypes of Crystalline Solids Covalent or Character tome network — Molecular etaliic solids solids solids solids Constituent Positive and Atoms Molecules | Positive metal Particles negative ions ions (kernels) and free electrons Bonding forces | Electrostatic or | Covalent van der Metallic bonding coulombic Waals’ attraction Dipole-dipole Melting point High melting Very high Low melting | Moderate to high point melting point | point melting poirt Physical nature | Hard and brittle | Very hard Very soft | Hard but malleable and ductile Conductance Conductors in Non-conductor | Insulator | Good conductor aqueous solution or in molten state but insulators in solid state Examples NaCl, CaF, MgO, | Diamond, H,0, CO,, | Cu, Fe, Ag, Mg. ZnS Silica, SiC CCl, HCl, SO, Note Molecular solids are further subdivided into non-polar molecular solids, polar molecular solids and hydrogen bonded molecular solids Structure Determination by X-ray Diffraction (Bragg's Equation) When a beam of X-rays falls on a crystal plane composed of regularly arranged atoms or ions, the X-rays are diffracted. If the waves are in phase after reflection, the difference in distance travelled by the two rays (ie. path difference) must be equal to an integral number of wavelength, ni for constructive interference. Thus, path difference = WY + YZ = XY sin@+ XY sin@ = 2XY sin@ = 2d sin® nk = 2d sin®This equation is called Bragg’s equation. where, n = 1, 2,3... (diffraction order), 2. = wavelength of X-rays incident on crystal and d = distance between atomic planes @= angle at which interference occurs. Crystal Lattices In three dimensional space, a regular arrangement and repeating pattern of the constituent particles of a crystal in which each particle is depicted as a point is known as crystal lattice or space lattice. Unit Cell The smallest geometrical portion of the crystal lattice which can be used as repetitive unit to build up the whole crystal is called unit cell. Types of Unit Cell 1. Simple or primitive unit cell In which the particles are present at the corners of unit cell only. 2. Face centred unit cell In which the particles are present at the corners as well as at the centre of each of six faces of unit cell. LI 3. Body centred unit cell In which the particles are present at the corners as well as at the centre of unit cell.4. End centred unit cell In which the particles are present at the corners and at the centre of two opposite faces of unit cell. Number of Particles Per Unit Cell No. of particles and their contribution Unit cell [incense eee eal uaaneeel Total Corner Face | Centre Simple cubic axl _ _ 1 8 Face centred 8x 6xz — 4 8 2 Body centred gxi = 1 2 8 End centred axl axl - 2 8 2 Seven Crystal Systems and Possible Variations There are about 230 crystal forms, which have been grouped into 14 types of space lattices, called Bravais Lattices, on the basis of their symmetry and seven different crystal systems on the basis of interfacial angles and axial distances. Seven Crystal Systems Parameters of unit cell Crystal axial distances Possible variation ied or edge Angles lengths 1. |Cubic a=b=c a =B=7=90° Primitive, body | | |centred, face centred. 2. [Tetragonal a=bec a =B=7=90° Primitive, body centred 3. |Rhombohedral |a=b=c ia =B=y# 90° Primitive or trigonalParameters of unit cell Crystal ayial distances Possible variation system or edge Angles lengths 1. |Cubic a=b=¢ ia =B = y= 90° Primitive, body centred, face centred 4. |Orthorhombic ae bec ln =B=y= 90° Primitive, body, face 4 4 jand end centred. 5. |Monoctinic arbec ‘a = 7 = 90°, B + 90° [Primitive and end centred, 6. Triclinic azbec la #B +74 90° Primitive 7. |Hexagonal a=bec ‘a = B = 90°, y = 120° Primitive Coordination Number (CN) It is defined as the number of particles immediately adjacent to each particle in the crystal lattice. In simple cubic lattice, CN is 6, in body centred lattice, CN is 8 and in face centred cubic lattice, CN is 12. High pressure increases CN and high temperature decreases the CN. Close Packing in Crystals Packing in solids may be divided into the following categories : One Dimensional packing of constituent particles In one dimensional close packing arrangement, the coordination number is 2. Two Dimensional Packing of Constituent Particles @) Square Close Packing When atoms arranged in a row is stacked with atoms arranged in another row exactly one over another is known as square close packing. Coordination number in square close packing is 4. This is also known as AAA...type arrangement space occupied by spheres is 52.4%.(i) Hexagonal Close Packing This is generated by placing spheres of the second row in the depressions of first row. Coordination number in hexagonal closed packing is 6. This is also known as ABAB...type arrangement space occupied by spheres is 60.4%. Hence, it is more efficient. Three Dimensional Packing of Constituent Particles (a) Three dimensional closed packing from two dimensional square close packed layers When two dimensional square close packed layers are arranged exactly one over the other they constitute a three dimensional close packing. The arrangement is known as AAA arrangement. (b) Three dimensional close packing from two dimensional hexagonal close packed layers When hexagonal close packed layers are stacked kone over another, they form three dimensional close packing. (i) Hexagonal close packing When third layer is placed over second layer in such a way that they constitute tetrahedral void. The arrangement is called ABAB pattern. (ii) Cubie close packing When the third layer is placed over second layer in such a way that sphere covers octahedral voids. The arrangement is called ABABC pattern. In both these arrangements 74% space is occupied. Coordination number in hep and ccp arrangement is 12 while in bee arrangement, it is 8. Close packing of atoms in cubic structure = fec> bee> sec All noble gases have cep structure except He (hep structure).Void or Space or Holes Empty or vacant space present between spheres of a unit cell, is called void or space or hole or interstitial void. When particles are close packed resulting in either ccp or hep structure, three types of voids are generated: Trigonal voids exist in two dimensional arrangement. Trigonal voids ‘Tetrahedral voids are holes or voids surrounded by four spheres present at the corner of a tetrahedron. Coordination number of a tetrahedral void is 4. =D Tetrahedral void JM Tyoid = 0-225 X Pyphere (for tetrahedral voids) Octahedral voids are holes surrounded by six spheres located on a regular tetrahedron. Coordination number of octahedral void is 6. Octahedral void Tyoid = 0-414 X Tophere (for octahedral voids) lhe number of octahedral voids present in a lattice is equal to the number of close packed particles. The number of tetrahedral voids present in a lattice is twice to the number of close packed particles. IPacking Efficiency or Packing Fraction The percentage of total space filled by the particles. (i) Primitive cubic unit cell Atoms touch each other along edges. Hence, d=a or r= : (r= radius of atom and a = edge length) Therefore, sa Volume of one atom _ 3 = 0.524 or 52.4% ~ Volume of cubic unit cell (ary Simple cubic unit cell, the spheres are in contact with each other along the edge of the cube (i) Face centred cubic unit cell Atoms touch each other along the face diagonal. Cubic close packing, or face centred cubic unit cell other sides are not provided with spheres for sake of clarity Hence, d=alv2 or r= 2al4 ¢: Length of face diagonal = (2a) 4x4 ne Therefore, PF = — 0.74 or 74% 4ry (=) ‘The packing efficiency of hep and ccp structures is also 74%.(iii) Body centred cubic unit cell Atoms touch each other along the body diagonal. Body-centred cubic unit cell (sphere along the body diagonal are shown with solid boundaries) Hence, d= VBal2 or r=~3al4 (¢: Length of body diagonal = 3a) ax 4g Therefore, PF = —3__ = 0.68 or 68% (3) v3. The packing efficiency of hep and ccp structure is also 74%. Density of Unit Cell (d) Density of unit cell = mase-ofunitcell volume of unit cell 2 ee d 3 a a xNq [ats of an atom (m)= #4] Na (The density of the unit cell is same as the density of the substance.) where, d = density of unit cell, M = molecular weight Z = number of atoms per unit cell, N, = Avogadro number a= edge length of unit cell. The Structure of lonic Crystals The ionic radius ratio of cation and anion play a very important role in giving a clue to the nature of the crystal structure of ionic substance.The ratio r, to r_ is called radius ratio. radius of positive ion _ r, Radius ratio = ———_—_—__—_ radius of negative ion r_ Radius Ratio and Crystal Structure S. Radius ratio Coordination Crystal No. WUE) number aaa structure Eanes 1. |< 0.225 20r3 Linear or |Linearor |B,03 | | triangular _| triangular 2. |0.225-0.414 4 Tetrahedral | ZnS type | CuCl, CuBr, HgS, BaS (sphalerite) 3. |0.414-0.732 4or6 Squar NaCl type | MgO, NaBr, CaS, KBr, planar or Ca0, Agcl | | | octahedral _| 4. |0.732 or more 8 Cube CsCl type |Csl, CsBr, NH,Br, TIBr Tonic crystals may be of two types: (i) AB type and (ii) A,B or AB, Structure of lonic Crystals Coordination lonic crystal type Cation occupy Anion form naa ber NaCl (Rock salt All octahedral voids fee unit cell 6:6 structure) type CsCl type | Body centre |simple cubic unit cel | 8: 8 ZnS (Sphalerite Altemate tetrahedral fec unit cell 4:4 structure) type voids | Caf, (Fluorite Alternate body centre simple cubic unit cell 8:4 structure) type Na,0 (Antifluorite All tetrahedral sites foc unit cell 4:8 structure) type On applying pressure, NaCl structure (6 : 6 coordination) changes into CsCl structure (8 : 8 coordination) and reverse of this occur at high temperature (760 K). Imperfections Defects in Solids In a crystalline solid, the atoms, ions and molecules are arranged in a definite repeating pattern, but some defects may occur in the pattern. Deviations from perfect arrangement may occur due to rapid cooling or presence of additional particles. The defects are of two types, namely point defects and line defects.The irregularities or deviations from ideal arrangement in entire rows of lattice points is called line defects. Point defects are the irregularities or deviations from ideal arrangement around a point or an atom in a crystalline substance. Point defects can be classified into three types : (1) stoichiometric defects (2) impurity defects (3) non-stoichiometric defects. 1, Stoichiometric Defect These are point defects that do not disturb the stoichiometry of the solid. They are also called intrinsic or thermodynamic defects. (a) In non ionic solids, two types of defects are present: Vacancy Defect When some of the lattice sites are vacant, crystal is said to have vacancy defect and results in decrease in density of substance. Interstitial Defect When some constituent particles occupy an interstitial site, the crystal is said to have interstitial defect and results in inerease in density of substances. (b) In ionic solids, basically these are of two types, Frenkel defect and Schottky defect. Schottky defect Frenkel defect 1. | It is due to equal number of cations | It is due to the dislocation of ions and anions missing from the lattice | (usually cations) from the lattice sites. sites to cccupy the interstitial sites. 2. | This results in the decrease in It has no effect on the density of density of crystal crystal 3. | This type of defect is found in highly | This type of defect is found in ionic compounds with high crystal where the difference in the coordination number, e.g. NaCl, size of cations and anions is very CsCl, ete. large, e.g. AgCl, ZnS, ete. AgBr has both Schottky and Frenkel defects. Frenkel defects are not found in pure alkali metal halides because cations are of large size. 2. Impurity Defect It arises when foreign atoms or ions are present in the lattice. In case of ionic compounds, the impurity is also ionic in nature. When the impurity has the same charge as the host ion, it just substitutes some of the host ions. Impurity defects can also be introduced by addingimpurity ions having different charge than host ions, e.g. molten NaC] containing a little amount of SrCl, is crystallised. In such cases, cationic vacancies produced = [number of cations of higher valence x difference in valence of the host cation and cation of higher valence] 3. Non-Stoichiometric Defect Non-stoichiometric crystals are those which do not obey the law of constant proportions. The number of positive and negative ions present in such compounds are different from those expected from their ideal chemical formulae. However, the crystal as a whole is neutral. ‘Types of non-stoichiometric defects are as follows: (@) Metal excess defect due to anionic vacancies Alkali halides like NaC] and KCl show this type of defect. F-centres are the sites from where anions are missing and the vacant sites are occupied by electrons. F-centres contribute colour and paramagnetic nature of the crystal [F stands for German word Farbe meaning colour]. Metal excess defect due to presence of extra cations at interstitial sites, e.g. zinc oxide is white in colour at room temperature. On heating, it loses oxygen and turns yellow. Heatin; Zo —“"8 Zn** + lo, + 2e7 2 (i) Metal deficiency defect due to cation vacancy It is due to the absence of a metal ion from its lattice site and charge is balanced by ion having higher positive charge. Transition metals exhibit this defect, e.g. FeO, which is found in the composition range from Fe, 9,0 to Fey 9,0. In crystal of FeO, some Fe” cations are missing and the loss of positive charge is made up by the presence of required number of Fe** ions.Electrical Properties of Solids Solids can be classified into three types on the basis of their conductivities. Classification of Solids on the Basis of Electrical Conductivity Type of | Conductivity Reason of solid (ohm m~) conductivity a Conductors 10* - 107 (Very high) | Motion of electrons —_| Metals like Ag, Al Insulators 10°7° ta10"*° (Very low) | De not permit electricity | Wood, rubber, bakelite to_pass Semiconductors |10"° - 10* (Moderate) | Motion of interstitial | Si, Ge, etc. electrons or holes or both Coneuenen Conduction Conduction is band band Overlapping band} Forbidden zone {small energy Valence (Large energy gap) 7] gap 7 Partially band ] Valence band /, Valence band filled band A / Conductors Insulator Semiconductor Energy The electricity produced on heating a polar crystal is called ‘pyroelectricity’. When mechanical stress is applied on polar crystals, electricity produced due to displacement of ions is called ‘piezoelectricity’. | Semiconductors Electronic conductors having electrical conductivity in the range of 10‘ -10°° Q"' m™' are known as semiconductors, e.g. Si, Ge, Sn (grey), Cu,0, SiC and GaAs. Intrinsic Semiconductors Pure substances that are semiconductors are known as intrinsic (undoped) semiconductors, e.g. Si, Ge. Extrinsic Semiconductors Their conductivity is due to the presence of impurities. They are formed by doping. It is defined as addition of impurities to asemiconductor to increase the conductivity. Doping of Si or Ge is carried out with P, As, Sb, B, Al or Ga. (i) n-type semiconductors Silicon or germanium doped with 15 group elements like phosphorus is called n-type semiconductor. The conductivity is due to the presence of negative charge (electrons). (ii) p-type semiconductors Silicon or germanium doped with 13 group element like gallium is called p-type semiconductor. The conductivity is due to the presence of positive holes. Some typical 13-15 compounds are InSb, AIP and GaAs and some typical 12-16 compounds are ZnS, CdS, CdSe and HgTe. These exhibit electrical and optical properties of great use in electronic industry. Magnetic Properties of Solids Solids can be divided into different classes depending on their response to magnetic field. Paramagnetic Substances These are attracted by the magnetic field and have unpaired electrons. These lose magnetism in the absence of magnetic field, e.g. 02, Cu”, Fe’*, ete. Diamagnetic Substances These are weakly repelled by the magnetic field and do not have any unpaired electron, e.g. TiO02, V,0; ,CgHg,NaCl, ete. Ferromagnetic Substances These are attracted by the magnetic field and show permanent magnetism even in the absence of magnetic field, e.g. Fe, Co, CrO, and Ni. Anti-ferromagnetic Substances These substances have net magnetic moment zero due to compensatory alignment of magnetic moments, e.g. MnO, MnO, FeO, NiO, Cr,O, ete. Ferrimagnetic Substances These substances have a net dipole moment due to unequal parallel and anti-parallel alignment of magnetic moments, e.g. Fe,O,, ferrites (M**Fe,0,), where M = Mg, Cu, Zn etc.