SOLID STATE

1. Introduction :

CHEMISTRY

SOLID STATE

Matter can exists in three physical states namely ; solid, liquid and gas. Matter consists of tiny particals (atoms, ions or molecules). If the particles are very far off from one another, they behave like gases ; nearer, they behave like liquids, and nearest, like solids. The fundamental difference between the three states of aggregation lies essentially in the difference of the relative amounts of energy possessed by the particles in the three states. The relative energies in the different states of matter are governed by two universal opposing tendencies associated with the particles: (i) (ii) They have tendency of mutual attraction. They have tendency of escape from one another which is known as escaping tendency. Whether a given system would exist as a solid, liquid or gas depends upon the relative strength of these opposing tendencies. If the escaping tendency is greater than the attraction between them, the molecules will be carried far from each other to distances which are large as compared with their diameters, the system will exists in gaseous state. But in the liquid state the molecular attraction exceeds the escaping tendency and in the solid state the forces of attraction are so much greater than those of escaping tendency that each particles is bound into a definite place in a rigid position by the mutual attraction of molecules.

2.

Solids :
Solids are characterised by the state of matter in which particles are closely packed and held together by strong inter molecular attractive force. Properties of Solids :

(a) (b) (c) (d) (e) (f)

In solid state the particles are not able to move randomly. They have definite shape and volume. Solids have high density. Solids have high and sharp melting point which is depend on the strength or value of binding energy. They are very low compressible. They show very slow diffusion. Types of Solids :

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SOLID STATE
Crystalline solids : (a) (b) (c)

CHEMISTRY

In this type of solids the atoms or molecule are arranged in a regular pattern in the three dimensional network. They have well defined geometrical pattern, sharp melting point, definite heat of fusion and anisotropic nature. Anisotropic means they exhibit different physical properties in all directions. e.g. The electrical and thermal conductivities are different directions.

(d) (e)

They are generally incompressible. The general examples of crystalline solids are as Quartz, diamond etc. Amorphous Solids :

(a) (b) (c) (d) (e)

In this type of solids, the arrangement of building constituents is not regular. They are regarded as super cooled liquids with high viscosity in which the force of attraction holding the molecules together are so great, that the material becomes rigid but there is no regularity in structure. They do not have sharp melting points. They are isotropic as they exhibit same physical properties in all the directions. The general examples of this solids are as glass, Rubber, plastics etc.

Defference between crystalline and amorphous solids : Property
1. Shape
2. Melting point 3. Heat of fusion 4. Compressibility

Crystalline solids
They have definite and regular geometrical form. They have definite melting point They have a definite heat of fusion They are rigid and incompressible.

Amorphous solids
They do not have definite and regular geometrical form. They do not have definite melting point They do not have definite heat of fusion These may be compressed to any appreciable extent.

5. Cutting with a Sharp edged tool

They are given cleavage i.e. they break into two pieces with plane surfaces.

They are given irregular cleavage i.e. they break into two pieces with irregular surface.

6. Isotropy and Anisotropy

They are anisotropic.

They are isotropic.

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study of crystals : Crystal : A crystal is a homogeneous portion of a solid substance made by regular pattern of structural units bonded by plane surface making definite angles with each other. ions and molecules in different sites in three dimensional space is called space lattice.E. Interfacial angles : The angle between the perpendiculars two intersecting faces called interfacial angles. (4) Maximum P. Edge : An edge is formed by the intersection of two adjacent faces. the atoms are located at the position of (1) Zero P.E. To which of the following categories does it belong (1) Ionic solid Q.E.4 Amorphous solids (1) Possess sharp melting points (2) Undergo clean cleavage when cut with knife (3) Do not undergo clean cleavage when cut with knife (4) Possess orderly arrangement over long distances Answers : (1) 4 (2) 3 (3) 2 (4) 3 3. (3) Minimum P. (2) Infinite P. (a) (b) Law of constancy of symmetry : According to this law. results in a crystal of the given substance called unit cell. 4.3 Graphite is an example of (1) Ionic solid tal (2) Covalent solid (3) Vander waal’s crystal (4) Metallic crys- Q. A crystal possess following three types of symmetry. Space lattice : The arrangement of constituents like atom.E. all crystals of a substance have the same elements of symmetry. Face : The plane surface of the crystal are called faces.SOLID STATE Q.2 (2) Covalent solid (3) Metallic (4) Molecular In a crystal. Q. Unit cell : The smallest repeating unit in space lattice which when repeats over and over again. # [60] 60 .1 CHEMISTRY Questions based on types of solids : A solid X melts slightly above 273K and is a poor conductor of heat and electricity.

four and six fold respectively. (ii) Axis of three fold symmetry. (e) (i) Axis of two fold symmetry. (iii) Axis of four fold symmetry. l efer h d k r y Axis of symmetry : (a) (b) (c) (d) It is an imaginary line about which the crystal may be rotated so that it presents the same appearance more than once in a complete rotation through 360º. # [61] 61 . (iv) Axis of six fold symmetry.SOLID STATE Plane of symmetry : CHEMISTRY It is an imaginary plane which passes through the centre of a crystal can divide it into two equal portions which are exactly the mirror images to each other. four times (90º) and six times (60º) in one rotation. tetrad and hexad respectively. The axes of symmetry are called diad. It is the original appearance and is repeated twice (180º). triad. Five fold symmetry is not found in crystals. These axes of symmetry are also called as two fold. thrice (120º).

(a) Elements of symmetry : The total number of planes. axes and centre of symmetries possessed by a crystal is termed as elements of symmetry. (i) (ii) (iii) Plane of symmetry Axes of symmetry Centre of symmetry (3 + (3 + 6) 4 + (1) 6) = = = 9 13 1 ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ Total symmetry = 23 6. (b) But on the other hand Bravais showed that there are only seven types of crystal system.SOLID STATE Centre of symmetry : (a) CHEMISTRY It is a point in the crystal that any line drawn through it intersects the surface of the crystal at equal distance on either side. Y Centre of symmetry X Z Note : Only simple cubic system have one centre of symmetry. (a) crystal system : On the basis of geometrical consideration theoritically there can be 32 different combinations of elements of symmetry of crystal. (b) A cubic crystal possesses total 23 elements of symmetry. Other system do not have centre of symmetry. These are : – (i) Cubic (iii) Orthorhombic (v) Hexagonal (vii) Triclinic (ii) Tetragonal (iv) Trigonal or Rhombohedral (vi) Monoclinic (c) There are 14 Bravais lattices under seven crystal systems as follows : # [62] 62 . 5.

Cubic Axial distance a=b=c CHEMISTRY The Bravais Lattices Axial angles α = β = γ = 90º Space lattice a. Orthorhombic a ≠ b ≠ c α = β = γ = 90º f.SOLID STATE Crystal system 1. 3. Tetragonal a=b≠c α = β = γ = 90º d. Body centered : Points at the eight corners and at the body centre # [63] 63 . Simple : Lattice points at the eight corners of the unit cells. Simple : Points at the eight corners of the unit cell g. Simple : Points at the eight corners of the unit cell e. Face centered : Points at the eight corners and at the six face centeres Unit cell 2. Body centered : Points at the eight corners and at the body centered c. Body centered : Po int s at the eight corners and at the body centre. b. End centered : Also called side centered or base centered points at the eight corners and at two face centres opposite to each other h.

Simple : Po int s at the eight corners of the unit cell. # [64] 64 . End centered : Po int s at the eight corners and at two face centres opposite to the each other. Face centered : Points at the eight corners and at the six face centres α = β = γ ≠ 90º 4.SOLID STATE CHEMISTRY h. 5. Simple : i. Hexagonal a=b≠c α = β = 90º γ = 120º k. Monoclinic a≠b≠c α = β = 90º ≠ γ I. 6. Simple : Points at the eight corners of the unit cell. or ii. m. Po int s at the twelve corners of the hexagonal prism and at the centres of the two hexagonal faces. Po int s at the twelve corners of the unit cell out lined by thick line. Rhombohedral or Trigonal a=b=c j. Body centered : Points at the eight corners and at the body centre i.

H3BO3. Sb. CdS. TiO2. ZnS. NiSO4. NaNO3. ZnO. Ice. Graphite. Cu2O. Cd. Crystal system Cubic Space lattice Simple Examples Pb. Rhombic sulphur. 5H2O. Triclinic Simple # [65] 65 .SOLID STATE 7. Cu. Mg. K2SO4. Au. 1. Monoclinic Simple 7. KCl. Quartz. KNO3. Orthorhombic Simple 4. Simple : Po int s at the eight corners of the unit cell. K2Cr2O7. 3. BaSO4. 2. CaSO4. 2H2O. Calcite. Na2B4O7. Zn. Na2SO4. CaSO4. Hg. PbWO4. Diamond. PbCO3. As. Beryl. S. ZnO2. HgS. 5. CHEMISTRY a≠b≠c α ≠ β ≠ γ 90º Triclinic y c α b z γ β a x n. 10H2O. CaF2 and Alums. ICl. Bi. 7H2O. Monoclinic sulphur CaSO4 . Trigonal or Rhombohedral Hexagonal Simple Simple 6.No. White Sn. NaCl. ZrSiO4. 10 H2O. MgSO4. Ag. Pbl2. Tetragonal Simple SnO2.

(a) (b) (c) CHEMISTRY mathematical analysis of cubic system (types and analysis) : Simplest crystal is to be studied in cubic system. Atomic radius : It is defined as the half of the distance between nearest neighbouring atoms in a crystal. It is expressed in terms of length of the edge (a) of the unit cell of the crystal. Three types of cubic systems are following. Simple Cubic (SC) : Atoms are arranged at the corners of the cube. Body Centered Cubic (BCC) : Atoms are arranged at the corners and at the centre of the cube. 8 Each of six face centered atoms is shared by two adjacent unit cells and therefore one face centred atom contribute half of its share. (a) Simple cubic structure [S.SOLID STATE 7.C. total Z = 3 + 1 = 4 atoms per unit cell. Means 6× 1 = 3 atom per unit cell. 2 (iii) So.] a 2 Radius of atom ‘r’ = (b) Face centered cubic structure (FCC) ‘r’ = a 2 2 (c) Body centered cubic structure (BCC) ‘r’ = 3a 4 a=b=c α = β = γ = 90º Number of atoms per unit cell / unit cell contents : The total number of atoms contained with in the unit cell for a simple cubic called the unit cell content. (a) Simple cubic structure (sc) : Q Each corner atom is shared by eight surrounding cubes. 8 ∴ (b) (i) (ii) z=8× 1 8 Face centered cubic structure (fcc) : The eight corners atoms contribute for 1 of an atom and thus one atom per unit cell. it contributes for 1 of an atom. # [66] 66 . Therefore. Face Centered Cubic (FCC) : Atoms are arranged at the corners and at centered of the each faces.

) : It is defined as ratio of the volume of the unit cell that is occupied by spheres of the unit cell to the total volume of the unit cell. For bcc CN = 8. wt. For fcc CN = 12. Centre atom contribute one atom per unit cell.N. # [67] 67 . Packing fraction (P.SOLID STATE (c) (i) (ii) (iii) CHEMISTRY Body centered cubic structure (bcc) : Eight Corner atoms contribute one atom per unit cell. Body centered cubic 8 3. So. For simple cubic system CN = 6. Density of lattice matter = volume of unit cell = N × volume of unit cell Where Z is the number of atoms per unit cell and N is the Avogadro number.F. total 1 + 1 = 2 atoms per unit cell. Z = 8 × 1 + 1=2 8 Number of Atoms in Unit Cell It can be determined by the simplest relation where = nc nf ni + + 8 2 1 nc = number of atoms at the corners of the cube = 8 nf = number of atoms at six faces of the cube = 6 ni = number of atoms inside the cube = 1 Cubic unit cell nc nf ni Total atom in per unit cell 1. Density of lattice matter : (a) It is defined as the ratio of mass per unit cell to the total volume of unit cell. Face centered cubic 8 Co-ordination number (C. (b) mass per unit cell Z × At. It depends upon structure of the crystal. Simple cubic 8 0 0 6 0 1 0 1 2 4 2.) : (a) (b) (c) (d) (e) It is defined as the number of nearest neighbours or touching particles with other particle present in a crystal is called its co-ordination number.

SOLID STATE (a) Simple cubic unit cell : CHEMISTRY Let the radius of atom in packing = r Atoms are present at the corner of the cube. = 52% % of void = 100 – 52 = 48% (b) Body centered cubic unit cell : Number of atoms per unit cell = 8 × 1 +1=2 8 r= 3a 4 2× 4 3 πr 3 3 4r ⎞ = 0. = ⎛ ⎜ ⎜ ⎝ 4 3 πr 3 3 4r ⎞ = 0.F.F. = ⎛ ⎜ ⎜ ⎝ % P.F. = 68% % of void = 100 – 68 = 32% (c) Face centered cubic unit cell : Number of atoms per unit cell = 4 r= 2a 4 4× P.74 ⎟ ⎟ 2⎠ % P.F.F. % P.52 ( 2r )3 therefore. = 74% % of void = 100 – 74 = 26% # [68] 68 .68 ⎟ ⎟ 3⎠ P. each of the eight atom present at the eight corners shared amongst eight unit cells.F. P. Hence number of atoms per unit cell = 8 × 1 =1 8 again r= a 2 4 3 πr 3 = = 0.

CuBr.. of formula per Unit cell 1. CuI. CsCl . AgBr.C.SOLID STATE CHEMISTRY Crystal Structure of Some Cubic lonic Solids Crystal Structure Units Brief description and Examples – + Co-ordination Number + No. Zinc. K and Rb. Na ions occupy all the octahedral voids. AgI etc. From the dimensions of the unit cell. Then : rc + ra = a/2 Where rc and ra are radius of cation and anion.) structure Cs ions in the cubic void Example : CsCl. it is possible to calculate ionic radii. SrF2. Antifluorite Structure (Li2O – type) Negative ions means O + –2 in CCP Na – 4 O –8 –2 + 4 and Positive Li ions in all the tetrahedral voids. cube of edge length ‘a’ having cations and anions say NaCl structure. BaCl2 etc. NH4Cl etc. Example : Na2O 8. Rock Salt (NaCl-type) Cl ions in C.type Cl ions at the corner of cube and (B. Let. Example : CaF2. Zn ions occupy alter tetrahedral voids i.C. Example : Halides of Li. CsI etc.C. –2 +2 + Cs – 8 – + 1 Cl – 8 +2 3. only half of the total number of tetrahedral voids are occupied Examples : ZnS.P. CuCl. – Na – 6 Cl – 6 – 4 2. Na.C.C.P. CsBr. ionic radii : X-ray diffraction or electron diffraction techniques provides the necessary information regarding unit cell. Fluorite Structure (CaF2 – type) Ca ions (+ve ions) in C.P. and F Ca – +2 –8 4 ions(-ve ions) in all the tetrahedral voids. BaF2.e. # [69] 69 . F –4 5. AgCl. +2 – Zn –4 4 S –4 –2 4. Blende (ZnS) S ions in C.

414 – 0.155 – 0.82 × 10 Fraction of total volume occupied by atoms in a simple cube is - (1) π 2 (2) 3π 8 (3) 2π 6 (4) π 6 Ans (4) Sol.20 cm 3 = 13. Each edge of the unit cell is 2.9 cm .88 Å.414 – 0.82 × 23 5 6 10 (3) 4.732 – 0.155 0.732 0.225 0. The density of the metal –3 2 is 7.9 × 10 The volume of 100 g of the metal= m 100 = ρ 7. In a simple cubic system.1 A metallic element exists as cubic lattice.414 0.999 C.(1) 6.12 × 10 Ans (2) The volume of the unit cell = (2.9 × 10 −24 cm3 23 3 Number of unit cells in this volume = Ex.85 × 10 (2) 5.2 = 5.N.732 0.225 – 0.88 Å) 3 –24 Sol.20 g cm . number of atoms a = 2r ∴ Packing fraction = Volume occupied by one atom Volume of unit cell # [70] 70 .37 × 10 (4) 2. = 23. rc + ra = 3a 2 Limiting Radius Ratio and Structure Limiting radius ratio (r+) / (r–) < 0. 13. Shape 2 3 4 4 6 8 Linear Planar triangle Tetrahedral Square planar Octahedral Body-centred cubic Examples based on characteristics of cubic system : Ex.9 cm3 23. How many unit cell will be present in 100 g of the metal .SOLID STATE Radius of Cl = – CHEMISTRY a ( a / 2)2 + ( a / 2)2 = 4 2 a/2 90º Na+ a/2 Cl¯ Cl¯ For body centered lattice say CsCl.

SOLID STATE CHEMISTRY 4 3 4 3 πr πr = 3 = 3 3 = ( 2r ) a3 π 6 Questions based on characteristics of cubic system : Q.2 TiO2 is well known example of (1) Triclinic system (3) Monoclinic system Q.. Radius of metal atom = 3a 4 a 2 2 (3) For fcc lattice.4 A binary solid (A B ) has a rock salt structure. # [71] 71 . then which one is correct relationship (1) For simple cubic lattice.6 The number of atoms present in a simple cubic unit cell are (1) 4 (2) 3 (3) 2 (4) 1 Q... classification of crystals : According to attractive force which hold crystal together are generally of five types and thus crystal can be classified into five types.1 A crystal may have one or more planes and one or more axes of symmetry but it possesses(1) Two centres of symmetry (3) No centre of symmetry Q. Radius of metal atom = (4) All Q.. Radius of metal atom = a 2 (2) For bcc lattice. If the edge length is 400 pm and radius of cation is 75 pm the radius of anion is (1) 100 pm (2) 125 pm (3) 250 pm (4) 325 pm + – Q.3 (2) Tetragonal system (4) None (2) One centre of symmetry (4) None The arrangement ABC ABC .7 The number of atoms/molecules contained in one face centred cubic unit cell of a monoatomic substance is (1) 4 Answer : (1) 2 (2) 2 (2) 6 (3) 4 (4) 2 (5) 4 (3) 8 (6) 4 (4) 12 (7) 1 9. is referred to as (1) Octahedral close packing (3) Tetrahedral close packing (2) Hexagonal close packing (4) Cubic close packing Q..5 If a is the length of unit cell...

e. Ice Crystal etc. Example based on types of crystals : Ex. Molecular bonds are formed for those elements or compounds whose electronic configuration is such that there is little transfer of electrons between their atoms. Such crystal are normally found in ionic compound.2 # [72] 72 . (b) Molecular Crystals : (a) In molecular crystals. (b) The molecules having H-atom attached on N.g.g. the lattice consists of assemblage of positive ions immersed in a sea of mobile electrons.SOLID STATE Ionic Crystals : (a) CHEMISTRY The lattices in ionic crystal consists of alternative positive and negative ions in equivalent amount arranged in an order so that the potential energy of the ions in the lattice is minimum. atoms at their lattice point are held together by shared pairs of electrons between them.g. Diamond.1 Iodine crystal are Ans (3) (1) Metallic Solid Sol. the repeating unit is chemically identifiable atoms or molecules which do not carry a net charge. The mutual repulsion of free electrons. The mutual repulsion of ion cores. Graphite. The covalent bonding extends through out the crystals in spatial direction and has no small molecules in the conventional sense. e. The binding force is due to (a) (b) (c) Attraction between positive ions or ion cores of the metal and electron cloud. (2) Ionic solid (3) Molecular solid (4) Covalent solid Molecular solids are the substances having molecules as constituent units having interparticle forces such as Vander Waal’s forces or hydrogen bonds. NaCl → Na + Cl + – (b) Covalent Crystals : (a) In covalent crystals. O or F give hydrogen bonding crystals. (c) Noble gases. The existence of H-bonding in the crystal lattice is beyond doubt. e. Which of the following is molecular crystal (1) Noble gas (2) Ice (3) 1 and 2 both (4) None Ans (3) Ex. e.g. Mettallic Crystals : In metallic crystals.

This type of packing is called close packing. The packing of these spheres takes place in such a way that they occupy the maximum available space and hence the crystal has maximum density.4 Certain crystals produce electric signals on application of pressure. The total number of atoms of the element in these cell will be (1) 24.3 (2) Diamond (3) Graphite (4) All 23 23 23 23 (4) 12.18 × 10 (3) 6. This phenomenon is called(1) Pyro electricity (2) Ferroelectricity (2) 4 (3) 3 (3) Piezoelectricity (4) 3 (4) Ferrielectricity Answer : (1) 1 10.04 × 10 Q. packing of constituents in crystals : In order to understand the packing of the constituent particles in a crystal. while metal atoms occupy the body centres of half the cubes. X X X X X X X X Fig.SOLID STATE Q. One and two surfaces of square lattice.08 × 10 A certain metal fluoride crystallises in such a way that F atoms occupy simple cubic lattice sites. It is of two types : Close packing in two dimensions : The two possible arrangements of close packing in two dimensions.16 × 10 (2) 36. Square close packing : In which the spheres in the adjacent row lie just one over the other and show a horizontal as well as vertical alignment and form square. # [73] 73 . it is assumed that these particles are hard spheres of identical size.08 × 10 unit cells.2 Which is covalent solid (1) Fe2O3 Q. The formula of metal fluoride is (1) M2F (2) MF (3) MF2 (4) MF8 Q.1 CHEMISTRY 23 Questions based on types of crystals : An element occurring in the BCC structure has 12. Each sphere in this arrangement is in contact with four other spheres.

. The similar pattern is noticed throughout the crystal structure.. Close packing in three dimensions : There are also two different ways to arrange spheres in three dimensional close packing. In hexagonal close packing about 60. The arrangement is found to represent hexagonal close packing (hcp) symmetry which means that whole structure possesses one six fold of symmetry. Hexagonal close packing (HCP) structure. square close packing occupies only 52.4% of the space by spheres. whose centres lie at the corners of an equiliateral triangle are called triangular voids.4% of available space is occupied by spheres. whose centres lie at the corners of a square are called square voids. Fig. Comparison between Hexagonal Close Packing and Square Close Packing : 1. A A B B A A Fig...... Hexagonal close packing : To arrange the spheres vertically above those in the first layer so that each sphere of the third layer lies strictly above a sphere of the first layer... One and two surfaces of hexagonal lattice. The spheres in the third row are vertically aligned with sphere in first row.SOLID STATE Hexagonal close packing : CHEMISTRY In which the spheres in every second row are seated in the depression between the spheres of first row. 3... # [74] 74 .. 2... This arrangement if continued indefinitely in the same sequence is represented as AB AB AB . Hexagonal close packing is more dense than square close packing. In square close packing the vacent spaces (voids) are between four touching spheres. While in hexagonal close packing the vacent spaces (voids) are between three touching spheres... Whereas.

. Imperfection not only modify the properties of solids but also give rise to new properties. For example.SOLID STATE Cubic close packing : CHEMISTRY To arrange the spheres on the other set of hollow marked B. e. 11. NaCl (1 : 1) These solids show following types of defects : # [75] 75 . Cubic close packing (CCP) structure Body centred cubic arrangement : This structure will be obtained if the spheres in first layer (marked A) of cubic closed pakcing are slightly opened up and thus none of these is in contact with each other. IMPERFECTIONS IN SOLID : Any deviation from the perfectly ordered arrangement constitutes a defect or imperfection. is represented as ABC ABC ABC . This type of conduction is known as intrinsic conduction... In this way the spheres in fourth layer will correspond with those in the first layer.. These electrons are free to move in the crystal and are responsible for electrical conductivity.. Electronic imperfection : Generally. This arrangement possesses cubic close packing (CCP).. The electron deficient bond formed by the release of an electron is called a hole.. A A B B C C Fig. 1... Atomic imperfection : The defect which arise due to irregularity in the arrangement of atoms or ions are called atomic imperfection. In the presence of electric field the positive holes move in a direction opposite to that of the electrons and conduct electricity. If continued indefinitely in the same sequence. in the crystals of pure Si or Ge some electrons are released thermally from the covalent bonds at temperature above 0 K. This arrangement. Stoichiometric defect : The compounds in which the number of positive and negative ions are exactly in the ratio indicated by their chemical formula are called stoichiometric compound. Point defect is caused by missing as misplaced atoms or ions. But at high temperatures. some of the electrons may occupy higher energy state depending upon the temperature.g. Crystals may also possess additional defect due to the presence of impurities. electrons are present in fully occupied lowest energy state. These defects sometimes called thermodynamic defects because the number of these defects depends on the temperature.. One can put the second layer of the spheres (marked B) on the top of the first layer in such a way that each sphere of the second layer is in contact with four spheres of the layer below it..

2. Schottky defect is more common in ionic compounds which high co-ordination number and where the size of positive and negative ions are almost equal. The holes occupied by electrons are called F-centres and are responsible for the colour of the compound.SOLID STATE (a) Schottky defect : CHEMISTRY This type of defect is created when same number of positive ion and negative ion are missing from their respective positions leaving behind a pair of holes. AgBr.g. KBr etc. VOx (Where x can very between 0. CsCl. Frenkel defects are common in ionic compounds which have low co-ordination number and in which there is large difference in size between positive and negative ions. leaving a hole which is occupied by electron to maintain electrical neutrality.6 to 1. (b) Interstitial Defect : This type of defect is caused due to the presence of ions in the normally vacant interstitial sites in the crystal. these defects are of following types : (a) Metal excess defects due to anion vacancies : A compound may have excess metal ion if a negative ion is absent from its lattice site. Eg.3) In these compounds balance of positive and negative charges is maintained by having extra electrons or extra positive charge. M X + X — M X + X — — M X M + + — M X + — M X + — X — M + — M + Frenkel Defect Eg. Such compounds are called Non-stoichiometric compounds. Non Stoichiometric Defect : There are many compound in which the ratio of positive and negative ions present in the compound differs from that required by ideal formula of the compound. (c) Frenkel Defect : This type of defect is created when an ion leaves its correct lattice site and occupies an interstitial site. # [76] 76 . The presence of large number of schottky defects in crystal results in significant decrease in its density. ZnS. AgI etc. AgCl. e. So. NaCl. KCl.

+ — + — M X M X X— M X + M X + X— M + + M+ X e — — — M X — M + — M + Metal excess defects due to interstitial cation This type of defects are exhibited by the crystals which are likely to exbit “Frenkel defects. The charge is balanced by an adjacent ion having higher positive charge. : * * * The excess sodium in NaCl makes the crystal appears yellow.Center X— M+ Metal excess defects due to anion vacancies Eg. # [77] 77 .SOLID STATE M+ X— M+ X— CHEMISTRY X— M+ X— M+ M+ e— M+ X— X— M+ F .” (c) Metal deficiency due to cation vacancies : M+ X— M+ M+ X — X— M+ X— X— M+ X— M+ X— M+ X — X— M + X — M + Metal deficiency due to cation vacancies The non-stoichiometric compound may have metal deficiency due to the absence of metal ion from its lattice site. Electrically neutrality is maintained by the presence of an electron in the interstitial site. Excess potassium in KCl makes it violet. This type of defects are found in crystal which are likely to possess schottky Defects. Excess lithium in LiCl makes it pink. This type of defects are generally shown by compounds of transition metals. Greater the number of F-centres greater is the intensity of colour. (b) Metal excess defects due to interstitial cations : It may occur if an extra positive ion is present in an interstitial site.

1 Transition metals. A crystal.1 CHEMISTRY Examples based on imperfections in solid : In a crystal both ions are missing from normal sites in equal number. the number of tetrahedral holes are (1) 4N (2) N/2 (3) 2N (4) N Q. density remains unchanged but dielectric constant increases. This is an example of (1) F .centres (3) Frenkel defect Ans(4) Sol. Thus X . Questions based on imperfections in solid : Q. Schottky defects are arised when one positive ion and one negative ion are missing from their respective positions leaving behind a pair of holes.SOLID STATE Ex. B. C.2 In a close pack array of N spheres.packed structure (2) Tetrahedral voids (3) Octahedral voids (4) All of these Q. N) are accomodated in (1) Voids or holes in cubic .ray diffraction results from the scattering of X .2 Frenkel defect is noticed in (1) AgBr Sol. when they form interstitial compounds. Ex. the non-metals (H. # [78] 78 . These are more common in ionic compounds with high coordination number and having almost similar size of cations and anions. the negative ions (1) Occupy tetrahedral voids (3) Are arranged in ccp (2) Occupy octahedral voids (4) Are arrange in hcp (2) 3 (3) 3 Answer : (1) 4 12. (2) ZnS (3) AgI (4) All Ans (4) (2) Interstitial defect (4) Schotty defect Frenkel defect is arised when the cations are missing from their lattice sites and occupy interstitial sites. Experimental Method of Determining Crystal Structure : Crystal structure has been obtained by studying on the diffraction of X-rays by solids.rays which have wavelenghts of the same order as the spacing in crystal. having constituents particles arranged in planes at very small distances in three dimension array.3 In antiflourite structure. acts as diffraction grating for X . As a result of Frenkel defect.rays by a regular arrangement of atoms or ions.

SOLID STATE CHEMISTRY Diffraction pattern Crystal Lead-box with slit + 10.1 nm. they cancel. Almost all the metals at ordinary temperature are crystalline.rays passes through a crystalline solid.rays.000 Volts – Spots form diffraction X-rays Spots form incident beam Photographic plate (Front view) Photographic plate When a beam of X . If waves are out of phase.000 – 40. # [79] 79 . Common salt is an example of a crystalline solid. These metals may act as a natural three-dimensional gratings for the diffraction of X .atoms are arranged in fairly regular pattern with interatomic gaps of the order of 0. This enhancement of intensity is called constructive interference. (Addition) (a) Constructive interference of waves (Cancellati on) (b) Destructive interference of waves Bragg’s Law : X-rays are electromagnetic waves of short wavelength and may be diffracted by suitable diffracting centres. If waves are on same phase means if their peak are through coincides they add together to give wave of greater amplitude. In solid crystals. each atom in the beam scatters some of the radiations. This cancellation is called destructive interference.

we get 2d sin θ = nλ This equation is called Bragg’s equation.. in the above equation. corresponding to n = 1. Distance JEK = nλ .g. Evidently.e. some rays like DE. 3. 4.. YY’.. then undergo interference with each other. ZZ’. On the other hand..e. (i) where n is an integer. On the other hand. For monochromatic X .... . BC and EF may be in phase.. λ is constant and there are some specific angles θ1.. GH etc.. a ray like DE has to travel a longer distance. 2 .. 2... 3.. i. EF.(ii) Putting this value in equation (i).. 1. θ2... If d is the distance between the successive atomic planes. A part of the beam e... θ3.. the intensity of the reflected beam is very low... etc.. etc. If these reflected rays are in phase.... the extra distance JEK traversed by the ray DEF should be an integral multiple of the wavelength λ of the X–rays. ZZ’ etc.(iii) # [80] 80 ..... which is equal to JEK where BJ and BK are perpendiculars drawn on the lines DE and EF respectively.. if the reflected rays are out of phase.... penetrate into the crystal and are reflected by the atoms present in the atomic planes YY’.. i...etc. etc..... It is obvious that in order that the reflected rays. if the X ..rays. Thus... etc.. as represented by the lines XX’.. as compared to the ray AB..SOLID STATE A B C CHEMISTRY D E F θ L O M θ θ N X-ray reflection from crystals This method is based upon the principle that a crystal may be considered to be made up of a number of parallel equidistant atomic planes.. Suppose a beam of X–rays is incident on the crystal at angle θ..rays are incident at one of these.. The reflected beams like BC. they reinforce into each other and the intensity of the reflected rays is maximum. it is obvious from fig that JE – EK = d sinθ so that JEK = 2d sinθ .. the ray AB is reflected at the point B along the path BC.

The conductivity of semiconductors and insulators increases with increase in temperature while that of metals decreases. the conductivity of semi-conductors and insulators is mainly due to the presence of interstitial electrons and positive holes in the solids due to imperfections. otherwise they are absorbed. The interplaner spacing d and several informations about the structure of the solid canbe obtained with the help of monochromatic X-ray beam. the presence of defects in the crystal structure increases their conductivity. 13. Electrical conductivity of solids may arise through the motion of electrons and positive holes (electronic conductivity) or through the motion of ions (ionic conductivity). the laws of reflection are obeyed i. The conduction through electrons is called n-type conduction and through positive holes is called p-type conduction. (a) the angle of incidence is equal to the angle of reflection and (b) the incident ray.SOLID STATE CHEMISTRY they are reflected . substances are classified into the following two types. The electrical behaviour of some oxides of transition metals (belonging to fourth period) is given in table. Pure ionic solids where conduction can take place only through motion of ions are insulators. Electrical Properties of Some Trasition Oxides TiO(M) Ti2O3(M-I) TiO2(I) VO(M) V2O3M(I) VO2(M-I) V2O5(I) M = Metal . M-I = shows a transition from metal to insulator behaviour at a certain temperature. Properties of solids : Electric Properties : On the basis of electrical conductivity the solids can be broadly classified into the three types: (a) (b) (c) Metals (conductors) Insulators Semi-conductors. MAGNETIC PROPERTIES : On the basis of magnetic properties. However. When they are reflected. MnO(I) Cr2O3(I) CrO2(M) FeO(I) Mn2O3(I) MnO2(I) CoO(I) NiO(I) CuO(I) Fe2O3(I) (i) (ii) (iii) Paramagnetic substances Diamagnetic substances Ferromagnetic substances # [81] 81 . It may be noted that these oxides show wide variation in their electrical behaviour. the reflected ray and the normal to the reflecting plane are coplanar.e. Unlike metals. I = Insulator .

which do not contain any unpaired d-electrons and hence these are diamagnetic. Ti . This arises due to randumisation of spins at higher temperature e. Examples are Ni. ferrite Fe2O3. MnO. These substances lose their magnetism on removing the magnetic field. 3+ 4+ 2+ + (iii) Ferromagnetic substances : The substances possessing unpaired electrons are further classified in three different groups based on the alignment of magnetic moments of unpaired electrons. Magnetic Properties of Some Transition Metal Oxides TiO(p) Ti2O3(p)V2O3 (af) Ti2O2(p)VO2(p) VO(p) Cr2O3(af) CrO2(f) V2O5(d) MnO(af) Mn2O3(af) MnO2(af) FeO(af) Fe2O3(af) Fe3O4(fe) CoO(af)NiO(af) CuO(p) # [82] 82 . a paramagnetic substances when placed in an applied magnetic field. (a) Ferromagnetic substances (b) Antiferromagnetic substances (c) Ferrimagnetic substances (a) Ferromagnetic substances : The substances which are strongly attracted by magnetic field are termed as ferromagnetic substances. they are paramagnetic in behaviour. As a result of permanent magnet. the net magnetic moment is not zero. Fe. Since most of the transition metal ions have unpaired d-electrons. For example. The presence of an unpaired electron in an element causes it to behave like a permanent magnet. (b) Antiferromagnetic substances : When equal number of unpaired electrons are aligned in opposite directions.e. Cu . Co and CrO2. Mn2O3 and MnO2. It is important to note that diamagnetic substances show a decrease in weight while paramagnetic substances show an increase in weight in presence of a magnetic field. Such substances are termed as ferrimagnetic substances e. It is the property of the completely filled electronic subshells. Such substances are termed as antiferromagnetic substances. takes up a parallel position to the field. they show paramagnetic behaviour. (c) Ferrimagnetic substances : When unequal number of unpaired electrons are aligned in opposite directions. Zn . ferrimagnetic and antiferromagnetic substances show paramagnetic nature at higher temperatures.g. Fe3O4 is ferrimagnetic at room temperature but becomes paramagnetic at 850 K.g. these substances show magnetism even in the absence of magnetic field. It has been observed that the ferro-magnetic. (ii) Diamagnetic substances : Substances which are repelled by magnetic field are called diamagnetic. This type of substance have alignment of all the unpaired electrons in the same direction (orientation) These substances are permanently magnetised i.SOLID STATE (i) CHEMISTRY Paramagnetic substances : Substances which are weakly attracted into the magnetic field are called paramagnetic. etc. their magnetic moment (electron spin) will compensate each other magnetic moment. Paramagnetism is caused by the presence of unpaired electrons and since most of the transition metal atoms have unpaired d-electrons. The exceptions are Sc .

in bcc it is 68%. under the effect of applied field displacement of charges takes place. 14. 6. Actually certain atoms or ions get displaced upon heating. Such a crystal is known as piezoelectric crystal and this property is called piezoelectricity. CuCl. 2. However. For example. (iii) Ferroelectricity : In certain piezoelectric crystals. if there are 14 Na ions. + – – + – + # [83] 83 . in simple cubic it is 52% and in diamond it is 34%. af = anti-ferromagnetic . resulting in the creation of dipoles. α ≠ β ≠ γ ≠ 90º). Pota ssium dihydrogen phosphate (KH 2 PO 4 ) Potassium tartarate or Rochelle’s salt (KOOCCH(OH)CH(OH)COOK) and barium titanate (BaTiO2). BeS have zinc blende (ZnS) structure. (ii) Pyroelectricity : Some polar crystals upon heating produce small electric current. f = ferromagnetic . 5. In NaCl crystal. CsI. CsBr. Then 12 Cl ions are on the edge centres and 1 Cl at the bodycentre. Halides of all alkali metals (except those of Cs) and those of NH4 . Thus only fcc and hcp are close packed structures. lead zirconate (PbZrO3) is an antiferroelectric solid. the direction of polarisation may change on applying current.SOLID STATE CHEMISTRY p = paramagnetic . This phenomenon is known as ferroelectricity and the effect involved is called ferroelectric effect. TIBr. CsCN. TlI and TlCN have CsCl structure. 4. the two dipoles cancel on another so that there is no resultant dipole moment. (iv) Anti-ferroelectricity : When the dipoles in alternate lattices point up and down. (i) Piezoelectricity : A dielectic crystal which has a resultant dipole moment can produce electricity or show electrical property when external pressure is applied. then there are 13 Cl ions. CuI. The mechanical stress caused by the applied pressure results in electric current because of the displacement of the ions in the crystals. However. DIELECTRIC PROPERTIES : A dielectric is a substance in which an electric field gives rise to no net flow of electric charge. the dipoles are permanently polarised even in the absence of applied electric field. fe = ferrimagnetic . The examples of some ferroelectric solids are. Out of 14 Na ions. It can be vice-versa also. CuBr. TlCl. 3. Such piezoelectric crystals find applications as pick-ups in record players since electric signals are produced on applying pressure. AgI. Out of the seven crystal system triclinic is the most unsymmetrical system (a ≠ b ≠ c. 8 are on the corners and 6 are on the face-centres. 1. oxides and sulphides of alkaline earths (except BeS) and halides of siver (except AgI) have rock-salt (NaCl) type structure. d = diamagnetic. This phenomenon is known as pyroelectricity. This is due to the reason that electrons in a dielectric are tightly held by individual atoms. Such crystals are known as antiferroelectric crystals and the phenomenon is called antiferroelectricity. SPECIAL POINTS : The space occupied by hard spheres in fcc and hcp is 74%.

4K 2K – 5K <5K Substance (oxides) Y Ba2 Cu3 O7 Bi2 Ca2 Sr2 Cu3 O10 Tl2 Ca2 Ba2 Cu3 O10 125 K Temp. BaCl2. K2O. 11. Co. 90 K 105 K 19. Fe. K2S have antifluorite (Li2O type) structure. HgF2 have fluorite (CaF2) structure. Al and Ni. V. Zn. Pt. 20. Na2O. All noble gases have ccp structure except. CCP is present in Fe. 17. Some super conductors and temperatures of their superconductivity. CHEMISTRY SrCl2. He which has hcp structure. Cr. ferrites are ferrimagnetic. 18. Substance Hg Most metals Some organic compounds Temp. CdF2. Mo. 10. pyroxenes and asbestos are chain silicates. Ag. HCP is present in Be. sodium potassium tartarate (Rochelle salt) and potassium dihydrogen phosphate (KH2PO4) are ferroelectric solids. CrO2 are ferromagnetic. BCC is present in all alkali metals. clay is a sheet silicate and quartz is a three dimensional silicate. # [84] 84 . 16. Ca. Na2S. Beryl (Be3Al2Si6O18) is a cyclic/ring silicate. –9 2 –1 –1 –22 ohm cm whereas conductivity of semiconduc- –1 –1 14. Au. SrF2. 12. 13. Ni. BaF2. 8. Lead zirconate (PbZrO3) is an example of anti-ferroelectric crystal. Piezoelectric crystals are used as pick ups in record players. Amorphous silica is used for making photovoltaic cell (used for converting sunlight into electricity). Mg. NaCl and benzene are diamagnetic. Cu. MnO is anti ferromagnetic. The conductivity of insulators is of the order of 10 tors lies in the range 10 to 10 ohm cm . TiO2.SOLID STATE 7. Barrium titanate (BaTiO3). 15. 9.