Solid state chemistry

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Solid state chemistry

  1. 1. SOLID STATE CHEMISTRY
  2. 2. COnTEnTS• Introduction• Types of solids• Crystal Structures• Elements of Symmetry• Bragg’s equation• Allotropes of carbon: Diamond, graphite & Fullerene
  3. 3. InTRODUCTIOnThree phases of matter: Gas Liquid Solid
  4. 4. Gasmolecules 4
  5. 5. Liquidmolecules 5
  6. 6. Solidmolecules 6
  7. 7. WHAT IS SOLID? • Definite shape. • Definite volume. • Highly incompressible. • Rigid. • Constituent particles held closely by strong intermolecular forces. • Fixed position of constituents.
  8. 8. TYPES OF SOLIDS Two types (based upon atomic arrangement, binding energy, physical & chemical properties):1.Crystalline2. Amorphous
  9. 9. CRYSTALLInE SOLIDS• The building constituents arrange themselves in regular manner throughout the entire three dimensional network.• Existence of crystalline lattice.• A crystalline lattice is a solid figure which has a definite geometrical shape, with flat faces and sharp edges.• Incompressible orderly arranged units.• Definite sharp melting point.• Anisotropy.• Definite geometry.• Give x-ray diffraction bands.• Examples: NaCl, CsCl, etc.
  10. 10. AMORPHOUS SOLIDS• Derived from Greek word ‘Omorphe’ meaning shapeless.• No regular but haphazard arrangement of atoms or molecules.• Also considered as non-crystalline solids or super- cooled liquids.• No sharp m.p.• Isotropic.• No definite geometrical shape.• Do not give x-ray diffraction bands.• Examples: glass, rubber, plastics.
  11. 11. TYPES OF CRYSTAL STRUCTURES • Ionic crystals • Covalent crystals • Molecular crystals • Metallic crystals
  12. 12. IOnIC CRYSTALS• Lattice points are occupied by positive and negative ions.• Hard and brittle solids.• High m.p. due to very strong electrostatic forces of attraction.• Poor conductors of electricity in solid state but good in molten state.• Packing of spheres depends upon:  presence of charged species present.  difference in the size of anions and cations. • Two types:  AB types.  AB2 types.
  13. 13. COvALEnT CRYSTALS• Lattice points are occupied by neutral atoms.• Atoms are held together by covalent bonds• Hard solids.• High m.p.• Poor conductors of electricity.• Two common examples: diamond & graphite.
  14. 14. MOLECULAR CRYSTALS• Lattice points are occupied by neutral molecules.• The molecules are held together by vander Waal’s forces.• Very soft solids.• Low m.p.• Poor conductors of electricity.
  15. 15. METALLIC CRYSTALS• Lattice points are occupied by positive metal ions surrounded by a sea of mobile e-.• Soft to very hard.• Metals have high tensile strength.• Good conductors of electricity.• Malleable and ductile.• Bonding electrons in metals remain delocalized over the entire crystal.• High density.
  16. 16. LAWS OF SYMMETRY• Plane of symmetry• Centre of symmetry• Axis of symmetry.
  17. 17. ELEMEnTS OF SYMMETRY In CUbIC CRYSTAL• Rectangular planes of symmetry: 3• Diagonal planes of symmetry: 6• Axes of four-fold symmetry: 3• Axes of three-fold symmetry: 4• Axes of two-fold symmetry: 6• Centre of symmetry: 1 Total symmetry elements: 23
  18. 18. Planes of symmetryRectangular plane of Diagonal plane ofsymmetry: 3 symmetry: 6
  19. 19. axis of symmetryFour-fold axis of Three-fold axis ofsymmetry: 3 symmetry: 4
  20. 20. axis & centre of symmetryTwo-fold axis of Centre of symmetry: 1symmetry: 6
  21. 21. tyPes of cubic crystals Four types: 1.Simple or primitive type 2. Body-centered 3. Face-centered 4. End face-centered
  22. 22. Simple or primitive type (sc) Body-centered cell (bcc)
  23. 23. Face-centered cell (fcc) End face-centered cell
  24. 24. number of atoms Per unit cell in a cubic lattice • Simple cubic cell: 1atom/unit cell of sc • Body-centered cell: 2 atoms/unit cell of bcc • Face-centered cell: 4 atoms/unit cell of fcc • End face-centered cell: 2 atoms/unit cell
  25. 25. No of atoms per unit cell= 8 x 1/8 = 1
  26. 26. No of atoms per unit cell= 8 x 1/8 = 1
  27. 27. e.g.Polonium52% of the space is occupied by the atoms
  28. 28. No of atoms present per unit cell = (8 x 1/8 ) + (1 x 1) = 2
  29. 29. No of atoms per unit cell= (8 x 1/8) +1 = 2
  30. 30. e.g. CsCl, CsBr68% of the space is occupied by the atoms
  31. 31. No of atoms present per unit cell = (8 x 1/8 ) + (6 x 1/2) = 4
  32. 32. e.g. NaCl, NaF, KBr, MgO74% of the space is occupied by the atoms
  33. 33. of atoms present per unit cell = (8 x 1/8 ) + (2 x 1/2) = 2
  34. 34. atomic radius of a cubic lattice • Simple cubic cell: r = a/2 • Face-centered cubic cell: r = a/√8 • Body-centered cubic cell: r = √3a/4 (where a → length of cube)
  35. 35. Radius Ratio Rule• Relation between the radius, co-ordination number and the structural arrangement of the molecule. Radius ratio =• Greater the radius ratio, larger the size of the cation and hence the co-ordination number.• density = (z*Ma)/Na*a^3 Ma=mass no.,Na=avogadro, a= side length, z=no. of atoms
  36. 36. stRuctuRal analysis by Radius Ratio RuleS.NO. RADIUS CO-ORDINATION SHAPE EXAMPLE RATIO NUMBER 1. 0.0 – 0.155 2 Linear HF- 2. 0.155–0.225 3 Triangular B2O3, BN planar 3. 0.225– 0.414 4 Tetrahedral ZnS, SiO4-4 4. 0.414– 0.732 6 Octahedral NaCl 5. 0.732 – 1.0 8 Body-centered CsCl cubic
  37. 37. bRaVais lattices• Unit cell parameters: Lengths a, b & c. Angles α, β & γ.• Total crystal lattices: 7• Total Bravais lattices: 14
  38. 38. cRystal systems with unit cell paRameteRsS.No. System Cell Crystal Bravais Min. Sym. Dimensions Angles Lattices Elements1. Cubic a=b=c α=β=γ=90ْ sc, fcc, 3-fold axes: 4 bcc = 3 4-fold axes: 32. Orthorhombic a≠b≠c α=β=γ=90ْ sc, fcc, 2-fold axes: 3 bcc, efcc =43. Tetragonal a=b≠c α=β=γ=90ْ sc, bcc= 2 4-fold axis: 1
  39. 39. S.No. System Cell Crystal Bravais Min. Sym. Dimensions Angles Lattices Elements 4. Monoclinic a≠b≠c α = γ = 90ْ sc, efcc = 2 2-fold axis: 1 β ≠ 90ْ 5. Triclinic a≠b≠c α≠β≠γ≠ 90ْ sc = 1 1-fold axis: 1 6. Hexagonal a=b≠c α = β = 90ْ sc = 1 6-fold axis: 1 γ = 120ْ 7. Rhombohedral a=b=c α=β=γ≠ 90ْ sc = 1 3-fold axis: 1 or Trigonal
  40. 40. examples of diffeRent cRystal systemsS.No. System Example1. Cubic NaCl, KCl, CaF2, Cu, ZnS, CsCl, Cu2O2. Orthorhombic BaSO4, KNO3, MgSiO3, K2SO4, CdSO4, AgBr3. Tetragonal SnO2, TiO2, ZrSiO44. Monoclinic CaSO4.2H2O, monoclinic S5. Triclinic CuSO4.5H2O, NaHSO4, H3PO36. Hexagonal PbI2, Mg, Cd, Zn, ZnO, BN, SiO2, HgS, CdS7. Rhombohedral or Trigonal Graphite, ICl, Al2O3, calcite (CaCO3), As, Sb, Bi
  41. 41. Cubic lattice
  42. 42. Orthorhombic lattice
  43. 43. Tetragonal lattices
  44. 44. Monoclinic lattice
  45. 45. Triclinic lattice
  46. 46. Hexagonal lattice
  47. 47. Rhombohedral (Trigonal) lattice
  48. 48. stRuctuRes of impoRtant ionic compounds 1. AB type: NaCl (rock salt) CsCl ZnS (zinc blende / sphalerite) 2. AB2 type: CaF2 (fluorite) TiO2 (rutile) SiO2
  49. 49. Structure of NaCl (Rock salt)• FCC type.• Co-ordination number 6:6.• Calculation of no. of atoms of NaCl/unit cell:Cl at corners: (8 × 1/8) =1Cl at face centres (6 × 1/2) =3Na at edge centres (12 × 1/4) = 3Na at body centre =1Unit cell contents are 4(Na+Cl-)i.e. per each unit cell, 4 NaCl units will be present.
  50. 50. stRuctuRe of sodium choRideCubic unit cell:smallest repeatable unit
  51. 51. Structure of CsCl• bcc type.• Co-ordination number 8:8.• Number of atoms/unit cell:1
  52. 52. Structure of ZnS• fcc type.• Co-ordination number 4:4.• Calculation of no. of atoms/unit cell: Total S = 8x1/8 + 6x1/2 = 4 Total Zn = 4 Hence, total ZnS = 4
  53. 53. Structure of CaF2 Ca+ F-• fcc type.• Co-ordination number: 8:4 (8 for cation, 4 for anion)*Note: All the compounds of AB2 type follow the same pattern.
  54. 54. Structure of K2O O -2 Na+• fcc type.• Co-ordination number: 4:8 4 for cation 8 for anion
  55. 55. Structure of important covalent compoundS 1.Diamond 2. Graphite
  56. 56. Diamond
  57. 57. Structure of diamond• fcc type.• Tetrahedral• C-C bond length = 1.34A• Refractive index = 2.4• High dispersive power of light• Non-conductor of electricity• 3d network• Hardest substance ever known.• Used as abrasive.
  58. 58. 3d- structure of diamond
  59. 59. Graphite
  60. 60. Structure of Graphite• One of the softest substances ever known.• 2-d hexagonal layer structure• C-C bond length = 1.45A• Inter layer distance = 3.54A• Sliding nature• sp2 hybridisation with one electron left over.• Specific gravity 2.2• Electrical conductor• Metallic lustre• Used as good lubricant.
  61. 61. 2d- structure of graphite
  62. 62. fullureneS
  63. 63. Important points about Fullurenes • Discovered in 1985 as C60. • Consists of spherical, ellipsoid or cylindrical arrangement of dozens of C-atoms. • 3 types:  Spherical: Also called ‘bucky balls’. Molecule of the year 1991 by Science magazine.  Cylindrical: C nanotubes or buckytubes.  Planar.
  64. 64. Structure of fullurenes• 60 C-atoms arranged in pentagons and hexagons.• 7Å in diameter.• Soccer-ball shaped molecule with 20 six-membered & 12 five-membered rings.• Each pentagon is surrounded by five hexagons.• No two pentagons are adjecent.• Each carbon is sp2-hybridized.• Used: as photoresistant. in the preparation of super-conductors. in optical devices. in batteries as charge carriers.
  65. 65. BraGG’S eQuationX-rayTube Detector Incident radiation “Reflected” radiation 1 2 θ θ X Z Y d Transmitted radiation Beam 2 lags beam 1 by XYZ = 2d sin θ so 2d sin θ = nλ Bragg’s Law

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