Some important terms and defination Anisotropy- the property due to which crystals shows different physical properties

(eg.opticals properties, magnetic properties) in different planes of crystal, is called anisotropy. Isotropy- the property due to which crystals shows some physical properties in all directions is called isotropic. Eg. All amorphous solids are isotropic. ``

Lattice- a three dimensional regular arrangement of atoms molecules or ions are called lattice. Unit cell- the smallest unit which repeats to form a lattice is unit cell. Three types of unit cells with properties

Types of unit cell

definations

No. of atoms/unit cell=z

Relation between r&a r =a/2

Packing efficiency

Simple cubic/Primitive

B.C.C

FCC

Lattice point are present at corners of cube Lattice point are present at corners& body of cube Lattice point are present at corners &faces of cube

1/88=1 that is Z=1

52.5%

1/88=1 01 in body Z=1+1=2 1/88=1 1/26(faces)=3 Z=1+3=4

r= 3 a/4

68%

R= 2a/4

74%

Voids
Two types of voids.
Tetrahedral In this types of voides the centre of atoms/ions lies at the corners of regular tetra hedron. Octahedral In these types of voids the centre of atoms/ ions (spheres) lies at corners of regular octahedron. Co-ordination number of void is 6. No. of octaldnal void

Cordinator number of void is 4. No. of tetraledial void is twice the no. of atoms/ions(spheres) lattice i.e if v is the no. of close packed spheres. 2n is the of octahedial void. Radius ratio for ionic crystalls. r/r =0.414 to 0.225 Density =d d= ZM/ aNa Z = no. of atoms per unit cell M = atomic/ molecular mass a = edge length Na= Avogadros no.

=No. of atom/ions(spheres) in Lattice i.e. N is the no.of closed packed spheres then n no. of void =N Radius ratio for ionic crystall r+/r- = 0.414-0.732

Z = no. of lattice point per unit cell a = Edge length of lube r = radius of lattice point (atom or ion) Packing efficiency = volume occupied by atoms/ ions in unit cell/total volume of unit cell 100 in two dimension - 1) Square close packing - 2) Hexagonal close packing

Hexagonel close packing Square close packing

Hexagonal square

Central atom is surrounded by 4 athoms Marked as (1,2,3,4) ie. 1,2,3,4 are is in intimate contact with central atom has coordination number 4

Central atom is surrounded by 6 athoms Marked as (1,2,3,4,5,6) all these spheres are in intimate contact with central atom central atom has coordination number6

Square close packing:Central atom is surrounded by four other atoms marked as (1,2,3,4) i.e 1,2,3,4 are in intimate contact with central atom. Coordination number = 4. Hexagonal close packing:Central atom is surrounded by six other atoms marked as (I,II,3,4,5,6) all these spheres are in intimate contact with central atom. Coordination number = 6

Packing in three dimention

Simple cubic packing A Hexagonal close packing A Cubic close packing A

Defects

Point Defect

Line Defect

Stoichiometric 1a) Frankel defect 1b) Schottky defect 1c) Vacancy defect 1d) Interstitial defect

Non- Stoichiometric - Metal excess defects (due to anionic vacancies) - Metal excess defect (due to presence of extra cations)

Impurity Defect

Stoichiometric defect:- The point defect in which stoiciometriy of solids are not disturbed. Non stoichoimetric defect:- The point defect in which the stoichiometry of solids are essential disturbed. Impurity Defect:- The defects which arises due to mixing impurity into solid crystall. Eg: When Srcl 2 / Cacl 2 is mixed in molten Nacl then some of the sites of Na+ are occupied by Sr +2. Since Sr +2 is bivalent it replaces 2Na + ions out of 2 sites. One is occupied by Sr+ other remains vacant creating impurity defect. 1a) Schottky defect :- the defect in which pairs of cations and anion are missing from its original crystall site is called schottky defect . Note This defect can be seen when cations and anions are of comparable size. Eg is Nacl,AgBr, kcl etc

1b) Frankel defect :- the defect in which cations (smaller size) laeves its original site and slips into interstitial void such defect is known as frankel defect. 1c) Vacancy defect :- when some of the sites are vacant the crystall is said to be develop vacancy defect aslo called thermodynamic defect - Schottky defect belong to this category - This defect leads to decrease in density 1d) Interstitial defect:- when interstitial site are occupied by some constituent particle the crystals is said to develop interstitial defect - This defect leads to increase in density F centre A point defect shown by alkali metal halide if heated in presence of alkali. Electron loosed by alkali metal gets trapped in the crystal which then exhibits colour in the visible region due to excitation of electron NaCl heated in presence of Na ------- yellow colour KCl heated in presence of K ------- violet colour LiCl heated in presence of Li ------- pink colour (ii) Metal excess defect :- generally shown by zinc oxide on heating acquires colour due to loss of oxygen. Zinc ions goes to interstitial void an electrons to neighboring void exhibiting colour . (iii) Metal deficiency defect :- Insuch type of defect metal is deficient and charge neutrality is maintained by acquiring higher oxidation state by some of the metal presnt in crystal . This defect is shown by oxide of transition elements because they have the ability to exist in variable oxidation state. egFe0.93O, Ni0.98O. Electrical properties of solids Conduction of electricity in solids.

Band Theory The atomic orbitals of metals atoms forms molecules orbital which is very close to each other and forms a band. If the band is filled (occupied) it is called Valence band. If the bond is unoccupied it is called conduction band. Energy band between two bands are called forbidden zone. In conductors there is no low energy gap between valence band and conductor band. So electron can easily jump from valence band to conduction band and that is why metal shows conductivity. In insulator energy gap between valance band and conduction band is high. So electrons can not flow easily so it behaves as insulator. In semiconductor energy gap between valance band and conduction band is intermediate as in conductors and insulators. So some electrons can jump from V.B. to C.B. and it behaves as semiconductors.

Magnetic Properties

*Ferromagnetic substance- Those substance in which magnetic domains are aligned in parallel direction. Eg:- Iron, Cobalt , Nickel. These substances can be permanently Magnetized . They are strongly attracted by Magnets.

*Ant ferromagnetic substance- Those substance in which Magnetic domains are alligned in antiparallel direction and they are in equal number. Eg:- MnO *Ferrimagnetic substances- Those substances in which Magnetic domains are alligned in parallel and antiparallel direction in unequal number. *Paramagnetic substance- Those substance in which is weakly attracted by Magnetic field. These substances have unpaired electron in their orbital. Eg:- O2 ,CO+2, Fe+3, Cr+3 -They are magnetised in magnetic field. *Diamagnetic substances- that substance which is weekly repelled by magnetic field. Those substances have paired electron in their orbital. Eg:- H2O, Nacl, C6H6 -They are weakly magnetised by magnetic field. Pyroelectricity :- It is a phenomena of producing electricity when any pyroelectric substance is heated Piezoelectricity;- It is a phenomena of producing electricity when any piezoelectric substance is subjected to any mechanical stress or vice versa eg:-quartz Questions 1. Li heated with Licl gave pink colour. Why? Ans:- Due to formation of F center. 2. Which point defect does not involve change in density? Ans:- Frankel Defect. 3. Why F.C.C is also called C.C.P? Ans:- Because in FCC the packing efficiency is highest i.e. 74% in which spheres are packed very close to each other. 4. What will be coordination number of an atom in a)hcp b) BCC Ans:- a) 12 b) 8 5. Nacl doped with Mgcl2. Name the defect that will arise? Ans:- Impurity defect 6. Nacl doped with 10/1000 mol % of Alcl3. Calculate the conc. of cation vacancies.

Ans:- 10/1000 mol %= 10/100000 mol 1 Al+3 will produce= 2cation vacancy One mark questions:Q1.What is the effect of Schottky and Frankel defects on the density of crystalline solids? Q.2 Name an element with which germanium can be doped to produce an n-type semiconductor. Q.3 Why is potassium chloride sometimes violet instead of pure white? Q.4 Define the term amorphous. Q.4 What is coordination number of a metal atom in ccp structure ? Q.5 How can a ferromagnetic substance be changed to a paramagnetic one? Q.6 What is the Frenkel defect ? Q.7 What is the difference between glass and quartz, though both contain Silicate units? Q.8 Which solid is likely to be the best material for converting sunlight into electricity? Q.9 How is ferromagnetism different from Para magnetism? Q.10 Solid solution of group 13 or 15 impurities with group 14 elements is to found to exhibit unusual electrical properties. Why? Two mark questions:Q.1 Lithium metal crystal has body centered cubic structure. Its density is 0.53 g cm/3 and its molar mass is 6.94 g mol/1. Calculate the cation vacancies per mole. [NA = 6.0231023] Ans. 434810-23cm3 Q.2 What is meant by (i) 12-16 compound and (ii) 13 15 compound ? Give examples. Q.3 Gold (atomic radius = 0.144 nm) crystallizes in a face centered unit cell. What is the length of a side of the cell ? Q.4 Silver forms ccp lattice and X-ray studies of its crystals show that the edge length of its unit cell its 408.6pm. Calculate the density of silver (A Atomic mass = 107.9u) Q.5 An element with molar mass 2.710-2 kg mol -1 forms a cubic unit cell with edge length 405pm. If its density is 2.7103 kg m-3, what is the nature of the cubic unit cell ? Three mark questions:Q.1 Assign reason of the following: (i) Phosphorus doped slicon is a semiconductor. (ii) Schottky defect lowers the density of a solid. Q.2 (a) Determine the type of cubic lattice to which a given crystal belongs if it has edge length of 290 pm and density is 7.80 g /cm/3 (Molecular mass = 56 g/ mol) (b) Why does zinc oxide exhibit enhanced electrical conductivity on heating ? Q.3 Explain the following terms with suitable example :(i) Ferri magnetism (ii) n type semi conductor (iii) Forbidden zone. Q.4 Calculate the distance between Na+ and Cl in NaCl crystal if its density is 2.165gm/cm3. [molar mass of NaCl is 58.5gm/mol] Q.5 Schottky defect generate an equal number of cation and anion vacancy while doping produces only cation vacancy.

HOTS
Q.1 Refractive index of a solid is observed to have the same value alon all direction. Comment on the nature of solid. Would it show cleavage property? Q.2 Some of the very old glass objects appear slightly milky instead of being transparent. Explain why? Q.3 Explain the deference between conductivity of sodium and magnesium.

Q.4 List out the defects with following property . (i) Defects causing change in conductivity. (ii) Defect causing change in density. Q.5 The following to graph represent conductivity as a function of temperature. Giving reason explain the type of substances.

Conductivity Conductivity

Temp

Temp