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UNIT I Syllabus : THE SOLID STATE Marks-4 Classification of Solids based on different binding forces : molecular, Ionic, covalent and metallic solids, Amorphous and crystalline solids (elementary idea), unit cell in two dimensional and three dimensional lattices, calculation of density of unit cell, packing in solids, voids number of atoms per unit cell in a cubic unit cell, point defects, electrical and magnetic properties. 1. Gystalline and Amorphous solids (comparison) Crystalline Solids Definite characteristic shape. temperature Amorphous Solids Irregular shape range of temperature Property * Shape * point *Cleavage property
Melting Melt at a sharp and characteristic Gradually soften over a When cut with a sharpedged tool, When cut with a sharp they split into two pieces and the edged tool, they cut into newly generated surfaces are two pieces with Irregular plane and smooth. They have a definite and They do not have definite heat of fusion. Isotropic in nature. Pseudo solids or super cooled liquids They have only short range order. surfaces.
* Heat of characteristic heat of fusion. fusion * Anisotropy * Nature * Order in the arrangement All solid elements and solid of constituent particles Examples 2. compds : eg. Cu, Al, NaCl, Sugar etc. They are anisotropic in nature. True-solids They have long range order.
charcoal, lamp black etc.
Classification of solids on the basis of different binding forces.
Type solid 1.
of Constituent particles
2 Nature of Examples bond
Molecular Solids (i) Polar Polar molecules (ii) Polar H-bonded molecules (iii) Hydrogen bonded 2. Ionic Ions Solids Coulomic forces NaCl, Mgo, Hard but Insulator ZnS, CaF2 brittle in High Non polar Dispersion Non molecules forces Dipoledipole force Hydrogen bonding Ar., CO2, I2 HCl, SO2 H2o (ice) NH3(S) HF (S) Hard Insulator Low HBr, Soft Insulator Low CCl4, Soft Solid Insulator Very low or London H2,
solid state but conductors in molten state and aqueous
3. Metallic Positive solids ions in a sea of delocalized electrons 4. Covalent Atoms or Network solids
Fe, Cu, Ag, Hard but Mg malleable and ductile SiO2(quartz) Hard SiC ; C (diamond) graphite Soft
state Conductor in Fairly solid as well high. as in molten state. Insulator Conductor (exception) Very high
*Some Important Terminology. Space lattice/Crystal lattice : A well defined ordered and regular arrangement of atoms, molecules or ions in the three dimensional space is called crystal or space lattice. There are fourteen types of space lattices possible, they are also called bravais lattices.
Lattice Point : The atoms, molecules or ions in a crystalline substance are shown by points in its space lattice and are called lattice points.
8x1/8=1 1 2 4 5. Body Lengths a=b=c £=ß=γ=900 NaCl. Body centre. Face Centred Cubic U. Cu Axial angles Examples .of atoms at body centre 0 1 0 Total at at face centres 0 0 6x1/2=3 corners Primitive/Simple 8x1/8 = 1 Cubic U. * Unit Cell : The smallest part of the crystal lattice which when repeated over and over again produces the complete crystal is called unit cell.3 * Lattice Site : The position occupied by a constituent particle in a space lattice is called lattice site. Seven Primitive unit cells and their possible variations as centred unit cells: Crystal System Possible Variations Axial distances or Edge * Cubic Primitive. ZnS. Eg. Body centered 8x1/8=1 Cubic U.C. Calculation of number of atoms (z) per unit cell/rank of Unit Cell of a Cubic crystal system : Unit Cell No. 4.C.C. Corner. of atoms No. Face centre etc. atoms of No.
face * Tetragonal centred Primitive. CuSO4. ZnO. Body centred *Orthorhom -bic Primitive. HgS £=ß= r=900 Graphite. Square close Packing Hexagonal Close Packing Clinic £=ß=r=900 a=b=c £=r=900 ß = 1200 Calcite (CaCO3). CdS £=ß=900 r=1200 a=b = c £= ß=r=900 RhombicSulphur. Na2SO4. BaSO4 a=b=c £=ß=r=900 White Tin. SnO2.5 H2O. TiO2. Face * Hexagonal Centred. Close Packing in Crystals : Two dimensional close packing in metallic crystals. Body Centred.4 centred. End a=b = c Centred *Rhombohe Primitive d -ral or Trigonal *Monoclinic Primitive Tridinic End Centred Primitive a=b=c Primitive a=b=c Mono Sulphur. KNO3.10 H2O K2Cr207. CaSO4 . H3BO3 6.
C. and its unit cell is the primitive cubic unit cell.5 * The particles of adjacent rows show vertical as well as horizontal alignment. Hence H. is more stable arrangement in two dimensions. Three dimensional close packing is metallic crystal. (i) Three dimensional close packing from two dimensional square Closepacked layers :In this packing the square close-packed layers of particles are stacked one over the other so that all the atoms are vertically as well as horizontally aligned. Packing fraction or packing efficiency is about 60. . * Coordination number of each particle is four. * The shape of void is tetraangular As the packing efficiency of hexagonal close packing is more than square close packing.P. * Packing fraction or packing efficiency is about 52.4% The particles in every alternate row are vertically aligned Coordination number of each particle is six.4% The shape of void is triangular. The lattice thus generated is the simple cubic lattice.
P.C.Packing ABC ABC…. Ag. Cu. Packing efficiency is 74% .g.-layers one over the other generated by stacking such that spheres in each alternate layer are H. Al.Packing ABAB…. Mg. Au.P.C.P.6 (ii) Three dimensional close packing from two dimensional hexagonal In three dimentional close packed structures the arrangement of close-packed layers : hexagonal layers can be done in two ways : ABAB…. Ni.C. Packing efficiency is 74% Cubic close packing. Mo. layers one over vertically aligned the layer aligned other are such that spheres in every fourth vertically Hexagonal close packing. Be etc.P. etc.g.or H.C. Fe. packing is generated by ABC ABC or C. e. is stacking H. e.
per particle is 2. of atoms x Mass of each atom = Volume of Unit cell d = Z x M /a3 x NA Z – No. and NA—Avogadro’s No. . Donsity ‘d’ of unit cell = Mass of Unit cell Volume of unit cell No. VOIDS : The hollow or vacant spaces among the constituent particles in close packed structures are called voids or interstitials.C.7 7.225. 0. M – Molar mass of element a—edge length of U. of atom/U.C.. * The number of tetra hedral voids The number of octahedral voids per Radius ratio in tetrahedral void is Radius ratio in octahedral void is 0. Relation ship between density and edge length of a unit Cell of a crystal. hadral void is 4.414. particle is one. Two types of voids in crystals : Tetrahedral void Octa-hedral void *The void is surrounded by four The void is surrounded by size spheres spheres arranged tetrahedral arranged octahedrally *Coordination number of letra Coordination number of octahedral void is 6. 8.
8 9. Important Questions (Sold) 1. why ? . = one Packing fraction = 1 x 4/3 kk r3x100 ---------------------(2r)3 = 52.C.C.C. of spheres per U. Packing efficiency = Volume occupied by all the spheres in the unit cell x 100 / volume of U.4% For body centered Cubic system :BC = 2 a CD = 4 r = 3 a or a = 4r/3 No. For simple cubic system :a=2r No. Some glass objects from ancient civilizations are found to become milky in appearance. Packing efficiency in case of metal crystals with the assumption that atoms are touching each other. of spheres/U.C. of spheres per U. = 4 Packing efficiency = 4x4/3 kk r3 x 100 ------------------(2 2 r)3 = 74% 10. = 2 Rocking efficiency = 2 x 4/3 kk r3 x 100 ---------------------(4r/ 3)3 = 68% For Face centered cubic system : AC = 2 a AC = 4r = 2a or a = 2 2 r No.
91 6. of atoms of ‘k’ per B. Glass is an amorphous solid. of ‘x’ atoms = 8 x 1/8 = 1 No. Potassium crystallizes in a body centred cubic lattice. What is the formula of the compound ? Ans. d = Z x M / a3 x NA or a3 = 2 x 92.C. 2 A compound is formed by two elements M and N. of moles of ‘k’ = 11.7/39 = 0. Unit Cell = 2 No.55 g cm-3. No. No. At some temperature they under go crystallization. Why ? Ans. of Unit cells = 0. of atoms of ‘k’ = 0.022 x 1023 No. [Atomic mass of Nb = 92. of ‘y’ atoms = 1 No. What is the approximate number of unit cells in 11. The element N forms CCP and atoms of M occupy 1/3rd of tetrahedral voids.91 U ] Ans. of ‘N’ atoms = 8 x 1/8 + 6 x ½ = 4 No. of ‘o’ atoms = 12 x ¼ = 3 Formula of compound = XYO3 4. which has property of fluidity.C.3 x 6.55 . What is the formula of the compound ? Ans.022x1023 = 9.3 x 6. Calculate atomic radius of niobium. which make them milky in appearance.03 x 1022 5.0222 x 1023x8. 2. 3. A solid has a cubic structure in which ‘x’ atoms are located at the corners of the cube ‘y’ atoms are at the cube centres and ‘o’ atoms are at the edge centres.7 g of potassium ? [ At. No. of ‘M’ atoms = 8 x 1/3 = 8/3 Formula of compound = M8/3 N4 = M2N3 6. Glass panes fixed to windows or doors of old buildings are found to be thicker at bottom than at the top. Niobium Crystallizes in body centered cubic structure of density 8.3 No.9 Ans. Mass of k = 39 U ] Ans.
305 x 10-8 cm = 330.C. If the unit cell is cubic with an edge length of 289 pm.C. .011 = 2 Unit Cell is B. if 200 g of this element contains 2. An element crystallizes in a structure having a FCC unit cell of an edge 200 pm.02 x 1023 ] Ans.02 x 1023 or Z = 52 = 2. NA = 6.09 x 10-24 a = 3.4 x 1024 4 x 200 = 41.2 g/cc. Calculate the density.4 x 10 8. Ans.609 x 10-23 = 36.10 = 3. [Atomic mass of Cr = 52 U .2 x (289)3 x (10-10)3 x 6. d= a3 x NA Here we can take d = (200) x (10 ) x 2.732 x 330.4 x 1024 atoms.5 ---------------4 = 143 pm. d= ZxM a3 x NA or Z= d x a3 x NA M 7.67 g/cc The density of chromium metal is 7. determine the type of the unit cell present in its crystals. 7.5 pm 4r = 3 a or r= 1. 3 -10 3 24 ZxM M/NA = 200/2.
What is unit cell ? calculate the number of atoms in a f. What is the radius of an iron atom ? Calculate the density of silver which crystallizes in the F. The distance between the nearest silver atoms is 287 pm.C. . Imperfections in Crystals 11. 8.C.C. A defect in a crystal arise due to Irregularity in the arrangement of particles or presence of impurities or rise in temperature of the crystal. In which case the element would have higher density ? 5. 7. Any deviation from perfectly ordered arrangement of constituent particles in a crystal is called imperfection or defect.c.C.87 g/mol). In a compound. 2.11 Important Questions (Un sold) 1. we can classify the defects into two categories : (i) Point defects or atomic defects (ii) Line defects. (Molar mass of silver = 107. If the radius of bromide ion is 0. The edge length of the unit cell is found to be 286 pm. how large a cation can fit in each of the letrahedral void ? Iron has body centred cubic structure.182 pm. Defects in crystals modify the existing properties or even introduce new properties in a crystal. Two elements P and Q have B. structure. 4. and F. unit cell of an element. structures. Broadly. 3. Cations A are present in one eighth of the tetrahedral voids and cations B occupy half the octahedral voids.C.c. What is the simplest formula of the compound? 6. What will be the number of tetrahendral and octahedral voids per unit cell ? Give the coordination number of tetrahedral and octahedral voids. oxide ions have CCP arrangement. An element exists as hexagonal close packed structures as well as cubic close packed structure.C.
Property Definition Schott Ky defect A point defect which arises due to complete missing of ion pairs.12 Point defects arise due to irregularities from ideal arrangement around a point or an atom in a crystal. where as line defects arise due to deviation from ideal arrangement in the entire rows of lattice point. It remains the same. Density It decreases Conductivity Increases Mechanical Decreases Stress Type of Crystal in which the defect arises NaCl. Stolchiometric defects : A defect in a crystal due to which the stoichiometry of the crystal remains unaltered. Agcl. These defects are of two types. Increases Decreases Ionic crystals with low coordination number and having large difference in ionic radii Zn S. AgI . Ag Br. Frenkel defect A point defect which arises due to displacement of a smaller ion from its lattice site to interstitial hole. KCl. CsCl and Ag Br Examples Exeption Ag Br shows both type of defects Ionic crystals with high coordination number and having comparable ionic radii. Point defects are of three types : (i) (ii) Stoichiometric defect Non stoichiometric defect and (iii) Impurity defects.
13 Non stoichiometric defects : A defect in a crystal due to which stoichiometry (ie ratio of cation to anion) of the compound is changed. anions diffuse in to the surface of the crystal and combine with alkali metal atoms to give NaCl. it loses oxygen and Zn2+ ions when an alkali metal halide (NaCl. These defects arise in two ways :(i) (ii) * By metal excess Metal deficiency Metal Excess defect can arise in a crytal by anion vacancy or by extra cation occupying Interstitial hole. the electrical neutrality. Some of the to maintain electrical neutrality. are trapped is interstitial holes along KCl) is heated in an atmosphere of with electrons in the neighboring sites alkali metal vapours. The electron released vacancy are trapped in anionic *These defects are found in the crystals which is likely to possesses frenkel defect. . Metal excess defect due to anion Metal excess defect due to interstitial vacancy cations * A compound may have excess If an extra cation is present in an metal ion if an anion is absent from interstitial site and electrical neutrality its lattice site leaving a hole which is is maintained by the presence of occupied by the electron to maintain electron in the nearby interstitial sites. when it is * This defect is generally developed heated. This defect arises in ZnO.
g. The formula of nonstoichiometric FeO is fe0. addition of SrCl2 to NaCl or CdCl2 to .0 white.95 O1. FeS and NiO. FeO. * Metal deficiency defect : There are many solids which are difficult to prepare in stoichiometric composition and contain less amount of metal as compared to the stoichiometric proportion. Incase of FeO some of Fe2+ ions are missing and loss of +ve charge is balanced by the presence of required number of Fe3+ ions. NaCl becomes yellow. E. For example.g. For the loss three Fe2+ ions in a crystal there will be two Fe3+ ions in the cation vacancies and one cation vacancy will be unoccupied. an anion vacancy is called F-centre. This defect generally found in compounds in which metal exhibits variable valency e. KCl – Violet and LiCl— pink. F-centre in a crystal make it coloured & para-magnetic. Impurity defects : These defects in the Ionic solids may be introduced by adding impurity ions having different valence state than that of the host ions and creating cation vacancy. The formula of Zinc oxide * F-Centre : An electron trapped in becomes Zn(1+x) O.14 * These types of defects are found is the crystal which is likely to possess * Zn O becomes yellow other wise it is schottky defect.
Insulators : These are the solids with very low conductivities ranging from 10-20 to 10-10 ohm-1 m-1 Size of energy gap in conductors.g. E. In case of Insulators. (ii) (iii) Semiconductors : These are the solids with conductivities ranging between 10-6 to 104 ohm-1 m-1. .15 AgCl yields solid solutions in which there will be one cation vacancy for every impurity ion added. semiconductoss and Insulators:In metal (conductors) there in no energy gap due to overlapping between valence band and conduction band and it decreases with increase in temperature. Sn (Tin) Eg = 8 kg/mol . It is an Insulator. Diamond (Eg=511 kg/mol has large energy gap. the energy gap is very small and conductivity increase with increase in temperature eg. (Na+) (Cl-) (Na+) (Cl-) (Na+) Cation vacancy (Cl) (Na+) (Cl-) (Cl-) (Sr2+) (Cl-) (Cl-) (Na+) (Na+) (Cl-) (Cl-) (Na+) (Na+) (Cl-) 12. (i) Conductors : The solids with conductivities ranging between 104 to 107 ohm-1 m-1 are called conductors. Properties of Solids : (a) Electrical properties of Solids Solids can be classified into three types on the basis of their conductivities. Si and Ge (Eg = 111 kj/mol). the energy gap is very large and therefore the vacant conduction bond is not available to the electrons of the completely filled valence band. In case of semi conductors like germanium and silicon. Metals have conductivities in the order of 107 ohm-1 m-1 are good conductors.
sincemore electons can jump to the conduction bond. Fig. (b). This process is called doping. (a) Electron-rich impurities : Si/Ge (Group -14) doped with electron-rich impurity P/As (Group -15) is called n-type semi conductor. Such impurities introduce electronic defects in them. (b) Electron-deficient impurities : Si/Ge (Group-14) doped with electrondeficient impurity B/Al (Group-13) is called p-type semi conductor. Si and Ge show this type of behavior and are called intrinsic semi conductors. The conductivity of Semi conductors can be increased by adding an appropriate amount of suitable impurity.16 Diagrammatical representation of energy gap (Eg) : Electrical conductivity of semiconductors increase with rise in temperature. . Doping can be done with an imparity which is electron rich or electron deficient as compared to the intrinsic semi conductor Si or Ge. Fig.
(i) (ii) Orbital motion of electron around the nucleus Spin motion of electron around its own axis. Each electron therefore behave like a tiny magnet. The origion of these properties lies in the motion of an electron in a atom. (b) Magnetic properties : Every substance has some magnetic property associated with it. The magnetic moments which originate from two types of motions. Creation of n-type and p-type semi conductors by doping groups 13 and 15 elements. Magnetic moment Magnetic moment .17 (c).
MnO. V2O3. (c) Ferromagnetic solids : These are strongly attracted by the external magnetic field and show permanent magnetism even if external magnetic field is removed e. NaCl. They lose magnetism in the absence of external magnetic field e.g. TiO2. 02. (b) Paramagnetic solids : These are weakly attracted by external magnetic field and have unpaired electrons.In these type of solids the domain (A group of metal ions in a small region) orient in anti parallel direction in equal number so that the net magnetic moment is zero eg. Co. substances can be classified into five categories :(a) Diamagnetic solids : These are weakly repelled by external magnetic field and do not have unpaired electron e.g. (e) Ferromagnetic solids :.18 On the basis of magnetic properties.g. Ni. (d) Anti ferromagnetism :.In these type of solids the magnetic moment of domains are oriented in anti parallel direction in unequal number so that the net magnetic moment is very small e. CrO2. Fe3+.g. (a) (b) (c) Schematic alignment of magnetic moments in (a) Ferromagnetic (b) anti ferromagnetic and (c) Ferromagnetic substances . Fe. TiO. Cu0. C6H6. Fe3O4 (Magnetite) and all ferrites like MgFe2O4 and Zn Fe2O4.
Cite one example each of following : (i) Solid which exhibit schottky defect and (ii) Frenkel defect.g. If NaCl is doped with 10-2 mol% of SrCl2. the coordination number decreases e. Analysis shows that Nickel oxide has formula Ni0. when NaCl (6 : 6 coordination) crystal is subjected to high pressure it changes to CsCl-type structure (8:8coordinations) If temperature is increased. What happens when Zn O is heated strongly ? Point out the Kind of defect developed in ZnO as a result of heating. What is F-centre ? What are its effect on the properties of solid. Define the terms “ Valence band. What happens when Fe3o4 is heated to 850 K and why ? 7. 2. forbiddon zone.19 Important questions (Un solved) 1. 9. 5. 3. Give at least two important application of n and p-type semi-conductors. 4. Radius ratio r+/rStructure Coordination No.g. What is the concentration of cation vacancy and actual number of cation vacancies ? For Bright Students (Add to your Knwolwedge) 1..98 O1. 10. Relation between radius ratio and coordination number for Ionic crystals : Radius ratio : It is the ratio of radius of cation to radius of anion in an ionic crystal. Which of these two CdCl2 and NaCl will produce schottky defect ? 6.0 What fraction of Nickel exists as Ni2+ and Ni3+ ions ? 8. Examples . Effect of temperature and pressure on crystal structure : with the increase in pressure the corrdination number increases resulting is change in the crystal structure e. ferrimagnetic solids and ferro magnetic solids. conduction band. State difference between schottky and frenkel defects. (iii) Schottky and frenkel defects both. When CsCl (8:8-coordination) crystal is heated to 760 K it changes to NaCl type structure (6:6 – coordination) 2.
225 0. NH4Cl Na+=6 Cl. Te Br.C.C. Na. Calculation of no. Rb2O. Cu Br. Cs Br. BaCl2.C. SrF2. K2O. TlCN CuCl.414-0.C. BN SiO44-. K and Rb Mgo. No.155 0. Na+= 12x1/4+Body centre = edge centre+Body centre = 3+1 = 4 Cl = 8x1/8+6x1/2 corners + face centres =1+3=4 + Cs = Body centre =1 Cl. ZnS MgO.No . Cs Br. TlCl. Cs+=8 Cl-=8 1 Zn2+=4 S2-=4 4 F.732 0.c.= 6 4 (ii) CsCl B. Cs I.C.C. Li2O.c. of formula units per U. 3. Halides of Li.= Corners = 8x1/8=1 Zn2+=4 (50% of Tetra hedral vids) 2S =4 (at corners and face cntre) 2+ Ca =4(one at corner + three At face centres) F = 8 (at 100% Tetra hedral voids) + Na =8 (one at each Tetra hedral void) O2-=4 (One at (i) AB Rock Salttype (NaCl) F. TlI.C.155-0. of cations and onions per unit cell. BaF2. (iii) Zn S (Zinc blende) AB2Type CaF2 (Fluorit e type) A2BType Na2O F.20 0-0.732-1.414 0. AgF.) 2 3 4 6 8 HF2 B2O3.C. NaCl CsCl.00 Linear Triangular Tetra hedral O ctahedral Cubic (b.225-0. BeS. CuI AgI. AB2.C. PbF2 Ca2+=8 F-=4 4 F. Structure of simple cubic Ionic compounds (AB.C.C. SrCl2 CdF2. A2B-Types) Type Structure Example Co. Rb2S Na+=4 O2-=8 4 .
5. What is the coordination no.0222x1023 mol-1.022 x 1023] . how large a cation can fit in each of the Tetra hedral void ? Lead II sulphide crystal has NaCl structure. If the radius of Bromide ion is 0. [Molar Mass of CsCl = 168.5. at masses : Pb = 207. Mgo has NaCl-type structure. (NA=6. Also distance between cesium and chloride ions. Calculate the edge length of unit cell. of Cation and anions in CaF2 and K2O. of oxide ion? The ionic radii of Mg2+ and O2 ions are 66 pm and 140 pm respectively.) Important Question (Un solved) 1. What are the coordination no.0 g/cc. S = 32) 6.21 (Anti fluo rite) corner three at Face centres.182 nm. Caesium chloride crystallizes as a body centred cubic lattice and has a density 4. 2. What is its density ? The edge length of the uniti cell of PbS crystal is 500 pm. NA=6. 3. What type of interstial void Mg2+ is likely to occupy ? What is the probable coordination number of Mg2+ ion ? 4.