1

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.

Glass,

plastics,

Rubber,

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

Physical Nature

Electrical Conductivity

Melting point

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

Metallic bonding.

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

Covalent bonding

3. *

*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.

Lattice Site : The position occupied by a constituent particle in a space lattice is called lattice site. Eg. Corner, Body centre, Face centre etc.

Unit Cell : The smallest part of the crystal lattice which when repeated over and over again produces the complete crystal is called unit cell.

4.

Calculation of number of atoms (z) per unit cell/rank of Unit Cell of a Cubic crystal system :

Unit Cell

No. atoms

of

No. of atoms

No.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.C. Body centered 8x1/8=1 Cubic U.C. Face Centred Cubic U.C. 8x1/8=1

1 2 4

5. Seven Primitive unit cells and their possible variations as centred unit cells: Crystal System Possible Variations Axial distances or Edge * Cubic Primitive, Body Lengths a=b=c ===900 NaCl, ZnS, Cu Axial angles Examples

centred, face * Tetragonal centred Primitive, Body centred *Orthorhom -bic Primitive, Body Centred, Face * Hexagonal 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, Na2SO4.10 H2O K2Cr207, CuSO4.5 H2O, H3BO3 6. Close Packing in Crystals : Two dimensional close packing in metallic crystals. Square close Packing Hexagonal Close Packing Clinic ==r=900 a=b=c =r=900 = 1200 Calcite (CaCO3), HgS == r=900 Graphite, ZnO, CdS ==900 r=1200 a=b = c = =r=900 RhombicSulphur, KNO3, BaSO4 a=b=c ==r=900 White Tin, SnO2, TiO2, CaSO4

* The particles of adjacent rows show vertical as well as horizontal alignment. * Coordination number of each particle is four. * 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. Packing fraction or packing efficiency is about 60.4%

The shape of void is triangular. * The shape of void is tetraangular As the packing efficiency of hexagonal close packing is more than square close packing. Hence H.C.P. 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.

The lattice thus generated is the simple cubic lattice, and its unit cell is the primitive cubic unit cell.

(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.Packing ABC ABC.Packing ABAB.or H.C.P. packing is generated by ABC ABC or C.C.P. is stacking H.C.P.-layers one over the other generated by stacking such that spheres in each alternate layer are H.C.P. layers one over vertically aligned the layer aligned other are such that spheres in every fourth vertically

Hexagonal close packing, e.g. Mo, Mg, Be etc. Packing efficiency is 74%

Cubic close packing, e.g. Cu, Ag, Au, Fe, Ni, Al, etc. Packing efficiency is 74%

7. VOIDS : The hollow or vacant spaces among the constituent particles in close packed structures are called voids or interstitials. 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. particle is one.

hadral void is 4. per particle is 2.

* The number of tetra hedral voids The number of octahedral voids per Radius ratio in tetrahedral void is Radius ratio in octahedral void is 0.414. 0.225. 8. Relation ship between density and edge length of a unit Cell of a crystal. Donsity d of unit cell = Mass of Unit cell Volume of unit cell No. of atoms x Mass of each atom = Volume of Unit cell d = Z x M /a3 x NA Z No. of atom/U.C., M Molar mass of element aedge length of U.C. and NAAvogadros No.

9. Packing efficiency in case of metal crystals with the assumption that atoms are touching each other. Packing efficiency = Volume occupied by all the spheres in the unit cell x 100 / volume of U.C. For simple cubic system :a=2r No. of spheres/U.C. = one Packing fraction = 1 x 4/3 kk r3x100 ---------------------(2r)3 = 52.4% For body centered Cubic system :BC = 2 a CD = 4 r = 3 a or a = 4r/3 No. of spheres per U.C. = 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. of spheres per U.C. = 4 Packing efficiency = 4x4/3 kk r3 x 100 ------------------(2 2 r)3 = 74% 10. Important Questions (Sold) 1. Some glass objects from ancient civilizations are found to become milky in appearance, why ?

Ans. At some temperature they under go crystallization, which make them milky in appearance. 2. Glass panes fixed to windows or doors of old buildings are found to be thicker at bottom than at the top. Why ? Ans. Glass is an amorphous solid, which has property of fluidity. 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. What is the formula of the compound ? Ans. No. of x atoms = 8 x 1/8 = 1 No. of y atoms = 1 No. of o atoms = 12 x = 3 Formula of compound = XYO3 4. Potassium crystallizes in a body centred cubic lattice. What is the approximate number of unit cells in 11.7 g of potassium ? [ At. Mass of k = 39 U ] Ans. No. of moles of k = 11.7/39 = 0.3 No. of atoms of k = 0.3 x 6.022 x 1023 No. of atoms of k per B.C.C. Unit Cell = 2 No. of Unit cells = 0.3 x 6.022x1023 = 9.03 x 1022 5. 2 A compound is formed by two elements M and N. The element N forms CCP and atoms of M occupy 1/3rd of tetrahedral voids, What is the formula of the compound ? Ans. No. of N atoms = 8 x 1/8 + 6 x = 4 No. of M atoms = 8 x 1/3 = 8/3 Formula of compound = M8/3 N4 = M2N3 6. Niobium Crystallizes in body centered cubic structure of density 8.55 g cm-3. Calculate atomic radius of niobium. [Atomic mass of Nb = 92.91 U ] Ans. d = Z x M / a3 x NA or a3 = 2 x 92.91 6.0222 x 1023x8.55

10

= 3.609 x 10-23 = 36.09 x 10-24 a = 3.305 x 10-8 cm = 330.5 pm 4r = 3 a or r= 1.732 x 330.5 ---------------4 = 143 pm. 7. An element crystallizes in a structure having a FCC unit cell of an edge 200 pm. Calculate the density, if 200 g of this element contains 2.4 x 1024 atoms. Ans. d= a3 x NA Here we can take d = (200) x (10 ) x 2.4 x 10 8.
3 -10 3 24

ZxM

M/NA = 200/2.4 x 1024 4 x 200 = 41.67 g/cc

The density of chromium metal is 7.2 g/cc. If the unit cell is cubic with an edge length of 289 pm, determine the type of the unit cell present in its crystals. [Atomic mass of Cr = 52 U ; NA = 6.02 x 1023 ]

Ans. d=

ZxM a3 x NA

or Z=

d x a3 x NA M

7.2 x (289)3 x (10-10)3 x 6.02 x 1023 or Z = 52 = 2.011 = 2 Unit Cell is B.C.C.

11

Important Questions (Un sold)

1. 2. 3. 4. What is unit cell ? calculate the number of atoms in a f.c.c. unit cell of an element. Two elements P and Q have B.C.C. and F.C.C. structures. What will be the number of tetrahendral and octahedral voids per unit cell ? Give the coordination number of tetrahedral and octahedral voids. An element exists as hexagonal close packed structures as well as cubic close packed structure. In which case the element would have higher density ? 5. In a compound, oxide ions have CCP arrangement. Cations A are present in one eighth of the tetrahedral voids and cations B occupy half the octahedral voids. What is the simplest formula of the compound? 6. 7. 8. If the radius of bromide ion is 0.182 pm, how large a cation can fit in each of the letrahedral void ? Iron has body centred cubic structure. The edge length of the unit cell is found to be 286 pm. What is the radius of an iron atom ? Calculate the density of silver which crystallizes in the F.C.C. structure. The distance between the nearest silver atoms is 287 pm. (Molar mass of silver = 107.87 g/mol).

Imperfections in Crystals
11. Any deviation from perfectly ordered arrangement of constituent particles in a crystal is called imperfection or defect. 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. Defects in crystals modify the existing properties or even introduce new properties in a crystal. Broadly, we can classify the defects into two categories : (i) Point defects or atomic defects (ii) Line defects.

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. Point defects are of three types : (i) (ii) Stoichiometric defect Non stoichiometric defect and (iii) Impurity defects.

Stolchiometric defects : A defect in a crystal due to which the stoichiometry of the crystal remains unaltered. These defects are of two types. Property Definition Schott Ky defect A point defect which arises due to complete missing of ion pairs. Frenkel defect A point defect which arises due to displacement of a smaller ion from its lattice site to interstitial hole.

Density

It decreases

Conductivity Increases Mechanical Decreases Stress Type of Crystal in which the defect arises NaCl, 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.

It remains the same. Increases Decreases

Ionic crystals with low coordination number and having large difference in ionic radii Zn S, Agcl, Ag Br, AgI

13

Non stoichiometric defects : A defect in a crystal due to which stoichiometry (ie ratio of cation to anion) of the compound is changed. 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. 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. the electrical neutrality. This defect arises in ZnO, when it is * This defect is generally developed heated, it loses oxygen and Zn2+ ions when an alkali metal halide (NaCl, are trapped is interstitial holes along KCl) is heated in an atmosphere of with electrons in the neighboring sites alkali metal vapours. Some of the to maintain electrical neutrality. anions diffuse in to the surface of the crystal and combine with alkali metal atoms to give NaCl. The electron released vacancy are trapped in anionic

*These defects are found in the crystals which is likely to possesses frenkel defect.

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. an anion vacancy is called F-centre. F-centre in a crystal make it coloured & para-magnetic. E.g. NaCl becomes yellow, KCl Violet and LiCl pink. * 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. This defect generally found in compounds in which metal exhibits variable valency e.g. FeO, FeS and NiO. 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. 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. The formula of nonstoichiometric FeO is fe0.95 O1.0 white. The formula of Zinc oxide * F-Centre : An electron trapped in becomes Zn(1+x) O.

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. For example, addition of SrCl2 to NaCl or CdCl2 to

15

AgCl yields solid solutions in which there will be one cation vacancy for every impurity ion added. (Na+) (Cl-) (Na+) (Cl-) (Na+) Cation vacancy (Cl) (Na+) (Cl-) (Cl-) (Sr2+) (Cl-) (Cl-) (Na+) (Na+) (Cl-) (Cl-) (Na+) (Na+) (Cl-)

12. Properties of Solids : (a) Electrical properties of Solids Solids can be classified into three types on the basis of their conductivities. (i) Conductors : The solids with conductivities ranging between 104 to 107 ohm-1 m-1 are called conductors. Metals have conductivities in the order of 107 ohm-1 m-1 are good conductors. (ii) (iii) Semiconductors : These are the solids with conductivities ranging between 10-6 to 104 ohm-1 m-1. 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, 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 . In case of semi conductors like germanium and silicon, the energy gap is very small and conductivity increase with increase in temperature eg. Si and Ge (Eg = 111 kj/mol). In case of Insulators, the energy gap is very large and therefore the vacant conduction bond is not available to the electrons of the completely filled valence band. E.g. Diamond (Eg=511 kg/mol has large energy gap. It is an Insulator.

16

Diagrammatical representation of energy gap (Eg) :

Electrical conductivity of semiconductors increase with rise in temperature, sincemore electons can jump to the conduction bond. 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. This process is called doping. Doping can be done with an imparity which is electron rich or electron deficient as compared to the intrinsic semi conductor Si or Ge. Such impurities introduce electronic defects in them. (a) Electron-rich impurities : Si/Ge (Group -14) doped with electron-rich impurity P/As (Group -15) is called n-type semi conductor. Fig. (b). (b) Electron-deficient impurities : Si/Ge (Group-14) doped with electrondeficient impurity B/Al (Group-13) is called p-type semi conductor. Fig.

17

(c).

Creation of n-type and p-type semi conductors by doping groups 13 and 15 elements. (b) Magnetic properties : Every substance has some magnetic property associated with it. The origion of these properties lies in the motion of an electron in a atom. Each electron therefore behave like a tiny magnet. The magnetic moments which originate from two types of motions. (i) (ii) Orbital motion of electron around the nucleus Spin motion of electron around its own axis. Magnetic moment Magnetic moment

18

On the basis of magnetic properties, 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. TiO2, V2O3, NaCl, C6H6. (b) Paramagnetic solids : These are weakly attracted by external magnetic field and have unpaired electrons. They lose magnetism in the absence of external magnetic field e.g. Cu0, 02, Fe3+, TiO. (c) Ferromagnetic solids : These are strongly attracted by the external magnetic field and show permanent magnetism even if external magnetic field is removed e.g. Fe, Co, Ni, CrO2. (d) Anti ferromagnetism :- 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. MnO. (e) Ferromagnetic solids :- 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.g. Fe3O4 (Magnetite) and all ferrites like MgFe2O4 and Zn Fe2O4.

(a) (b) (c)

Schematic alignment of magnetic moments in (a) Ferromagnetic (b) anti ferromagnetic and (c) Ferromagnetic substances

19

Important questions (Un solved)

1. State difference between schottky and frenkel defects. 2. Cite one example each of following : (i) Solid which exhibit schottky defect and (ii) Frenkel defect. (iii) Schottky and frenkel defects both. 3. What is F-centre ? What are its effect on the properties of solid. 4. What happens when Zn O is heated strongly ? Point out the Kind of defect developed in ZnO as a result of heating. 5. Which of these two CdCl2 and NaCl will produce schottky defect ? 6. What happens when Fe3o4 is heated to 850 K and why ? 7. Analysis shows that Nickel oxide has formula Ni0.98 O1.0 What fraction of Nickel exists as Ni2+ and Ni3+ ions ? 8. Give at least two important application of n and p-type semi-conductors. 9. Define the terms Valence band, conduction band, forbiddon zone, ferrimagnetic solids and ferro magnetic solids. 10. If NaCl is doped with 10-2 mol% of SrCl2. What is the concentration of cation vacancy and actual number of cation vacancies ?

For Bright Students (Add to your Knwolwedge)

1. 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.g. when NaCl (6 : 6 coordination) crystal is subjected to high pressure it changes to CsCl-type structure (8:8coordinations) If temperature is increased, the coordination number decreases e.g.. When CsCl (8:8-coordination) crystal is heated to 760 K it changes to NaCl type structure (6:6 coordination) 2. 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. Radius ratio r+/rStructure Coordination No. Examples

20

0-0.155 0.155-0.225 0.225-0.414 0.414-0.732 0.732-1.00

Linear Triangular Tetra hedral O ctahedral Cubic (b.c.c.)

2 3 4 6 8

HF2 B2O3, BN SiO44-; ZnS MgO, NaCl CsCl, Cs Br.

3. Structure of simple cubic Ionic compounds (AB, AB2, A2B-Types) Type Structure Example Co.No . No. of formula units per U.C. Calculation of no. of cations and onions per unit cell. 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- = 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.C.C.

Halides of Li, Na, K and Rb Mgo, AgF, NH4Cl

Na+=6 Cl- = 6 4

(ii) CsCl B.C.C.

(iii) Zn S (Zinc blende) AB2Type CaF2 (Fluorit e type) A2BType Na2O

F.C.C.

Cs Br, Cs I, TlCl, Te Br, TlI, TlCN CuCl, Cu Br, CuI AgI, BeS.

Cs+=8 Cl-=8

Zn2+=4 S2-=4 4

F.C.C.

BaF2, BaCl2, SrF2, SrCl2 CdF2, PbF2

Ca2+=8 F-=4 4

F.C.C.

K2O, Li2O, Rb2O, Rb2S

Na+=4 O2-=8

21

(Anti fluo rite)

corner three at Face centres.)

Important Question (Un solved)

1. 2. 3. What are the coordination no. of Cation and anions in CaF2 and K2O. Mgo has NaCl-type structure. What is the coordination no. of oxide ion? The ionic radii of Mg2+ and O2 ions are 66 pm and 140 pm respectively. What type of interstial void Mg2+ is likely to occupy ? What is the probable coordination number of Mg2+ ion ? 4. 5. If the radius of Bromide ion is 0.182 nm, how large a cation can fit in each of the Tetra hedral void ? Lead II sulphide crystal has NaCl structure. What is its density ? The edge length of the uniti cell of PbS crystal is 500 pm. (NA=6.0222x1023 mol-1, at masses : Pb = 207, S = 32) 6. Caesium chloride crystallizes as a body centred cubic lattice and has a density 4.0 g/cc. Calculate the edge length of unit cell. Also distance between cesium and chloride ions. [Molar Mass of CsCl = 168.5, NA=6.022 x 1023]