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Classification of solids

:

Crystalline and Amorphous solids:

S.No. Crystalline Solids Amorphous solids
1 Regular internal arrangement of particles irregular internal arrangement of particles
2 Sharp melting point Melt over a rage of temperature
3 Regarded as true solids Regarded as super cooled liquids or pseudo solids
4 Undergo regular cut Undergo irregular cut.

5 Anisotropic in nature Isotropic in nature

Based on binding forces

Crystal Classification
Unit Particles Binding Forces Properties Examples
Atomic Atoms London dispersion forces
Soft, very low melting, poor thermal
Noble gases
and
electrical conductors
Molecular Polar or Vander Waal’s forces Fairly
(Londonsoft, low to moderately Dry
highice
melting
(solid, methane
non – polar molecules
dispersion, dipole – dipole
points,
forces
poor thermal and electrical conductors
hydrogen bonds)
Ionic Positive and negative
Ionic bonds
ions Hard and brittle, high melting NaCl,
points,ZnS
high
heats of fusion, poor thermal and electrical
conductors
Covalent Atoms that are connected
Covalent bonds
in Very hard, very high melting points,
Diamond,
poorquartz, silicon
covalent bond network thermal and electrical conductors

Metallic Solids
Cations in electron
Metallic
cloudbonds Soft to very hard, low to very All
highmetallic
meltingelements, for
points, excellent thermal and electrical
example, Cu, Fe, Zn
conductors, malleable and ductile

Bragg Equation:

nλ = 2dsinθ,

Where d= distance between the plane

n = order of refraction

θ= angel of refraction

λ = wavelength

Face Centered.SnO2 Monoclinic Primitive. Bi. b≠ 90o As. Body Centered a=b≠c a = b = g = 90o TiO2. CaCO3 Number of atoms in unit cells. Bodya Centered. Primitive cubic unit cell: Number of atoms at corners = 8×1/8 =1 Number of atoms in faces = 0 Number of atoms at body-centre: =0 Total number of atoms = 1 Body-centred cubic unit cell: Number of atoms at corners = 8×1/8 =1 Number of atoms in faces = 0 Number of atoms at body-centre: =1 Total number of atoms = 2 Face-centred cubic or cubic-close packed unit cell: Number of atoms at corners = 8×1/8 =1 Number of atoms in faces = 6×1/2 = 3 Number of atoms at body-centre: = 0 Total number of atoms = 4 Packing Efficiency Volume occupied by all the atoms present in unit cell / Total volume of unit cell)×100 . ZnS Orthorhombic ≠ b ≠ c Enda = b = g = 90o Primitive. Zn. Face Centered.2H2O o o Triclinic Primitive a≠b≠c a≠b≠g≠900 K2Cr2O7. End Centered a≠b≠c a = g = 90 . NaCl. Cd RhombohedraPrimitive a=b=c a = g = 90o. b≠ 90 CaSO4. Crystal Systems: Total number of crystal systems: 7 Total number of Bravais Lattices: 14 Crystal Systems Bravais Lattices Intercepts Crystal angle Example Cubic Primitive.Au Diamond. Bodya Centered =b=c a = b = g = 90o Pb. K2SO4 Centered Tetragonal Primitive.Hg.Ag. SiO2. g = 120Mg. Sb. CaSO45H2O Hexagonal Primitive a=b≠c 0 o a = b = 90 . KNO2.

414 ≤ x < 0. Number of tetrahedral voids = 2× Number of octahedral voids.225 AlCl3 Planar Triangle 4 0.414 ≤ x < 0. Relation between edge length ‘a’ and Close structure Number of atoms per unit cell ‘z’. Coordination numbers and radius ratio: Coordination numbers Geometry Radius ratio (x) Example 2 Linear x < 0.732 NaCl .225 ≤ x < 0.732 PtCl42- Square planar 6 0.414 ZnS Tetrahedron 4 0.155 BeF2 3 0.4% Density of crystal lattice: r =(Number of atoms per unit cell × Mass number)/(Volume of unit cell × NA) or Octahedral and Tetrahedral Voids: Number of octahedral voids = Number of effective atoms present in unit cell Number of tetrahedral voids = 2×Number of effective atoms present in unit cell So. Packing Efficiency radius of atom ‘r’ hcp and ccp or fcc 4 r = a/(2√2) 74% bcc 2 r = (√3/4)a 68% Simple cubic lattice 1 r = a/2 52.155 ≤ x < 0.

M3+ is generally Al. and ThO2 voids Z= 4 Coordination number of anion = 4 Coordination number of cation = 8 Anti. The tetravalent cation is in the center of the unit cell occupying octahedral void. CaTiO3. Fe. Z=2 Coordination number of = 8 Pervoskite Structure One of the cation is bivalent and the other is tetravalent. LiCl. Fe. Ni. center of the unit cell.Fluorite Structures Na2O. Octahedron 8 Body centered cubic 0. 3+ tetrahedral voids in a FCC lattice of oxide ions and M ions are Structure present in half of the octahedral voids. Z=4 Coordination number =6 Zinc Blende Structure Anion (S2-) forms fcc units and cation (Zn2+) occupy ZnSalternate . where M2+ is present in one-eighthMgAl2of O4 . Spinel and Inverse Spinel Spinel :M2+M23+O4. RbCl voids.999 CsCl Classification of Ionic Structures: Structures Descriptions Examples . Zn and Mn.732 ≤ x < 0. M2+ is usually Mg. Fe3O4.FeCr2O4 etc. Co. Cesium Halide Structure Halide ions are primitive cubic while the metal ion Alloccupies Halides the of Cesium. Cr and Rh. BeO tetrahedral voids Z=4 Coordination number =4 Fluorite Structures Cation (Ca2+) forms fcc units and anions (F-) occupy CaFtetrahedral 2. . K2O and Rb2O.octahedral KCl.The BaTiO3 bivalent ions are present in primitive cubic lattice with oxide ions on the centers of all the six square faces. UO2. ZnAl2O4. Mn. + Rock Salt Structure Anion(Cl ) forms fcc units and cation(Na ) occupyNaCl. Oxide ions are face centered and metal ions occupy all the tetrahedral voids.

ZnS Important points  Schottky defect appears more often than frenkel defect because wnergy needed to form a schottky defect is much less than that needed to form a frenkel defect. Schottky Defects Some of the lattice points in a crystal are unoccupied. Defects in crystal: •Any departure from perfectly ordered arrangement of the constituent particles in the crystal called imperfection or defect. cation and anion should have similer in size and coordination number should be high.Strong should have strong ionic characters. Does not affect density of the crystal. which is called lattice vacancy or holes Appears in ionic compounds in which anions and cations are of nearly same size. Non stoichiometric defects 3.AgBr shows both schottkey and frankel defect.CsCl AgBr 2. Stoichiometry of substance do not disturbed defect is called stoichiometric defect these defects are of the following types. . Examples: NaCl and KCl. Impurity defects 1. Stoichiometric defects 2. Conditions. Conditions.Defects If imperfection in the crystal are such that the ratio between cation and onions remains same. Stoichiometric.  Due to defects or holes lowers the lattice energy and stability of the crystal  Due to closeness of similar charge di electric constant increase Non stoichiometric defects:- If a result of the imperfactions in the crystal the ratio.electrical conductance increases more than schottky Examples: AgBr. •The defects in the crystal are arises when crystallization takes place at the fast or moderate rates because the constituent particles does not get sufficient time to arrange in perfect order. Entropy increases. low coordination number. 1. of the cations and anions becomes difference from that indicated by ideal chemical formula. Decreases the density of lattice Electrical neutrality is same Electrical conductance slightly increases. Types of the point defects:- 1. The defects are called non-stoichiometric defects. Frenkel Defects Ion dislocate from its position and occupies an interstitial position between the lattice points Appears in crystals in which the negative ions are much larger than the positive ion.should have difference in size.

They are of two types:- i. For example when ZnO is heated it loses oxygen and turns yellow due to following ZnO → Zn+2 + (1/2)O2 + 2e- The excess interstitial sites and the electrons in neighbouring interstitial sites.When NaCl is heated in an atmosphere of Na vapours. Example:. For example it is difficult to prepare ferrous oxide with ideal composition because ferum exists as both Fe+2 and Fe+3 ions thus we obtain Fe0.ions then diffuse to the surface where the combine with Na+ ions which becomes due to losing electrons. By presence of extra cation in interstitial sites:- • Metal excess may also be caused by an extra cation occupying the interstial site. Impotant points- Such crystal can conduct electricity to some extant and can be used as semiconductors Appeared coloured due to presence of free electrons.Farbe-which means colour}They are responsible for imparting colour to the crystals. potassium in KCl makes it violet. •These electrons loses by Na atom are diffuse back into the crystal and occupy the vacant site created by Cl- ions and imparts Yellow colour to NaCl crystal ii. Due to metal deficiency the compounds obtained are non stoichiometric.93 to 0.The interstitial sites containing the electron thus trapped in the anion vacancies are called the F – centers. Metal excess due to anion.95O or FexO with x = 0.Li excess in LiCl makes it pink . leaving a hole which is occupied by an electron. The excess of Na atoms deposition the surface of NaCl crystal Cl. Metal excess defects:. there by maintain the electrical neutrality.96(due to variable oxidation states ) Second due to an extra anions occupying interstitial sites- . {F. Metal deficiency defect:-this defect can occur in two ways first defect occurs when the metal shows the variable valancy.A negative ion may be missing from its lattice site.

If an electron jump from neighbouring site to fill this hole a another hole is generated at that site and it continues. In case of ionic solids the impurities are introduced by adding impurity of ions. This increases conductivity of silicon. Or it is present at the vacant interstitial site example n – type semi conductor. If the impurity ions are in different valnce state from that of host ions.Impurity defects or extrinsic defects:- These defects are arises when foreign atoms are present at the lattice site in place of the host atom. The vacancies of Na+ ions are created and these are occupied by sr+2 ions. As conductivity is increases due to electrons thus the germanium crystal doped with e. the silicon or germanium atom at some lattice sites are substituted by P or As. Thus a hole is get created at the site of fourth electron is missing. ii. p – type semi conductor. Doping with electron rich impurities (formation of n – type semi conductor):- Group in elements like silicon or germanium has 4 electrons in valance Shell. Now doped atom have 5 valence electrons after forming four covalent bonds. Thus if electric field is applied the electrons move towards +vely charged plate and electron holes move towards negative charged plate as they carry +ve charge. The process of adding impurities to the crystalline is called as doping. This is called electron hole or electron vacancy.rich impurity are called n – type semi conductors. The fifth free electron is gets delocalized. . Due to three valance electron all atom forms 3 valance bond with 3 silicon atoms. Introducing Impurity in covalent solids:- i. Doping with electron deficit impurities:. Thus a semiconductor with increased conducting is formed and called P – type semiconductor. When it is doped by group 15 element like P or As. Vacancies are created if mole ten NaCl containing a little impurity of SrCl2 and is allowed to cool. Thus it form four covalent bonds with neighbouring atoms.(P – type semi conductor) If group 14 element like silicon are doped with 3 valance electron containing 13 group elements like Al or Ga.

electrical neutrality as well as Stoichiometry of the compound are maintained this type of defect is called frenkel defect. from its lattice site and is occupies the interstitial site. . Non stoichiometric defects 3.If an ion is missing. There are mainly two types of defects:- 1. 2. 2. Line defect:. Stoichiometry of substance do not disturbed defect is called stoichiometric defect these defects are of the following types.When the deviation from the ideal arrangement exists in the entire row of lattice points the defect is called as line defect. Impurity defects Stoichiometric defect:- If imperfection in the crystal are such that the ratio between cation and onions remains same.  The defects in the crystal are arises when crystallization takes place at the fast or moderate rates because the constituent particles does not get sufficient time to arrange in perfect order. Vacancy defect:- When is in a crystalline substance. Schottky defect:- o If in an ionic crystal of the type A+B. KCl o Which compounds have small difference in size of cation and anions show defect. Compounds exhibiting schottky defect are NaCl. 2. It is also called dislocation defect.Defect or Imperfection:-  Any departure from perfectly ordered arrangement of the constituent particles in the crystal called imperfection or defect. Interstitial defect:- o When some extra constituent particles are present in the interstitial site the crystal is said to be have interstitial defect. 3. 3. 1. So that electrical neutrality is remained is called schottky defect. o This defect increases density of the crystal o These above types of defects are shown only by non – ionic solids. Frenkel defect:. some of the lattice sites are vacant the crystal is said to have vacancy defect it results in decrease of density of substance. Types of the point defects:- 1. Point defect:-When the deviation or irregularities exists from ideal arrangement around a point or an atom in a crystalline substance the defect is called the point defect.equal number of cations and anions are missing from the lattice site. Stoichiometric defects 2. 1.

They are responsible for imparting colour to the crystals.Example:- (AgCl. The process of adding impurities to the crystalline is called as doping. Main points of difference between schottky and frankel defect Non stoichiometric defects:- If a result of the imperfactions in the crystal the ratio. Metal excess defects:-  A negative ion may be missing from its lattice site.93 to 0. Introducing Impurity in covalent solids:- i. The excess of Na atoms deposition the surface of NaCl crystal Cl. Due to metal deficiency the compounds obtained are non stoichiometric. leaving a hole which is occupied by an electron. Vacancies are created if mole ten NaCl containing a little impurity of SrCl2 and is allowed to cool. If the impurity ions are in different valnce state from that of host ions. ZnS) shows this defect which have a large difference in size of cations and anions. For example it is difficult to prepare ferrous oxide with ideal composition because ferum exists as both Fe+2 and Fe+3 ions thus we obtain Fe0. For example when ZnO is heated it loses oxygen and turns yellow due to following ZnO → Zn+2 + (1/2)O2 + 2e- The excess interstitial sites and the electrons in neighbouring interstitial sites. of the cations and anions becomes difference from that indicated by ideal chemical formula. In case of ionic solids the impurities are introduced by adding impurity of ions.When NaCl is heated in an atmosphere of Na vapours. Doping with electron rich impurities (formation of n – type semi conductor):- . AgBr.ions then diffuse to the surface where the combine with Na+ ions which becomes due to losing electrons. there by maintain the electrical neutrality. AgI. Example:. The defects are called non- stoichiometric defects. By presence of extra cation in interstitial sites:-  • Metal excess may also be caused by an extra cation occupying the interstial site. Or it is present at the vacant interstitial site example n – type semi conductor.  Metal deficiency defect:.This defect occurs when the metal shows the variable valancy. p – type semi conductor.  The interstitial sites containing the electron thus trapped in the anion vacancies are called the F – centers.95O or FexO with x = 0. The vacancies of Na+ ions are created and thses are occupied by sr+2 ions.  These electrons loses by Na atom are diffuse back into the crystal and occupy the vacant site created by Cl. They are of two types:- i.ions and imparts Yellow colour to NaCl crystal ii.96 Impurity defects:- These defects are arises when foreign atoms are present at the lattice site in place of the host atom.

Thus a hole is get created at the site of fourth electron is missing. This is called electron hole or electron vacancy. This increases conductivity of silicon. ii.rich impurity are called n – type semi conductors. The fifth free electron is gets delocalized. o As conductivity is increases due to electrons thus the germanium crystal doped with e. o Thus if electric field is applied the electrons move towards +vely charged plate and electron holes move towards negative charged plate as they carry +ve charge. Thus a semiconductor with increased conducting is formed and called P – type semiconductor.(P – type semi conductor) o If group 14 element like silicon are doped with 3 valance electron containing 13 group elements like Al or Ga. When it is doped by group 15 element like P or As. o If an electron jump from neighbouring site to fill this hole a another hole is generated at that site and it continues. o Now doped atom have 5 valence electrons after forming four covalent bonds. . o Group in elements like silicon or germanium has 4 electrons in valance Shell. Thus it form four covalent bonds with neighbouring atoms. o Due to three valance electron all atom forms 3 valance bond with 3 silicon atoms. Doping with electron deficit impurities:. the silicon or germanium atom at some lattice sites are substituted by P or As.