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เนื้อหา Inorganic Solid 1. Classification of Bonds and Crystals 2. The effect of radius ratio and change in structure 3. Lattice energy 4. Defect structures 5. Structure of Silicates 6. Metallic bonding 7. Alloys Symmetry and Group theory
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Inorganic Solid
1. Classification of Bonds and Crystals
2. The effect of radius ratio and change in structure
3. Lattice energy
4. Defect structures
5. Structure of Silicates
6. Metallic bonding
7. Alloys
Symmetry and Group theory
1. Symmetry elements and operations
2. Point group
3. Properties and representations of groups
4. Examples and applications of symmetry
Acid-base Chemistry
1. Acid-Base concepts
2. Measures of Acid-Base Strength
3. Hard and Soft Acid and Bases
An atom of sodium (Na) donates one of its electrons to an atom of chlorine (Cl) in a chemical reaction. The resulting positive ion (Na+) and negative ion (Cl) form a stable molecule (sodium chloride, or common table salt) based on this ionic bond.
Metallic bond
NaCl
electrical conductivity metallic lattice
electrical conductivity
diamond
lattice
sp3 hybridization
CCC 109.5o
H-O---H 109.5
London dispersion
intermolecular forces
Space lattice
Unit cell space lattice
(1) space lattice
(2)
haxagonal space lattice 2 dimension 4 a) Lattice b) (rhombic) c) rectangle lattice d) hexagon unit cell
A-type lattice cubic lattice hard
sphere
simple cubic lattice (a) unit cell lattice
6
(b) 1/8 (c) space lattice highlight unit cell 8 ()
[(4/3)(d/2)3] x 1
Fraction of space
occupied by sphere
= 0.52
=
d3
A-type lattice
Unit cell (a) simple (b) body-centered (c) face-centered
cubic lettices
(g/cm3) = 1 atom (AW/6.02 x 1023)(g/atom)
d3 cm3
simple cubic lattice
ccp 1.28
=4 atom(63.54 g/mol/6.02 x1023 atom/mol)
[2(1.28 x 10-8)2]3
= 8.90 g/cm3
simple cubic lattice cubic cell b) 8 cubic 1/8 8 2[=1+8(1/8)] l d cell edge sphere diameter
x sphere diameter cell edge
body-centered unit (a) body diagonal
face diagonal cell edge (b) cell edge
l face diagonal l2
Body diagonal = 2d = l3 ; l = 2d/3
from (b)
from (a)
(a)
7.11 cpp structure fcc unit cell ABCABC layer
(b) fcc unit cell ABCABC layer
(c) space lattice fcc unit cell ABCABC layer
cpp structure fcc unit cell
cpp = ABCABC = fcc
7.12 fcc unit cell ABCABC layer (center of hexagon) 12
fcc unit cell
= 8(1/8) + 6(1/2) = 4
Face diagonal = l2 = 2d
l = 2d = d2
2
(b)
12
This point is
In both unit
Cell 1 and 4
7.14c
Total points per = 2(1/2) + 3 + 12(1/6) = 6
hcp unit cell
at corners of
hexagons
in hexagonal
faces
Wholly within
cell
7.15 14 Bravais lattices
7 unit cell
cubic, tetragonal, orthorhombic,
rhobohedral, hexagonal, monoclinic triclinic P = primitive simple I = body-centered, F = face-centered C = base-centered
7.17
simple cubic unit cell
cubic hole 7.17 space-filling model
(radius) cubic hole
7.18 tetrahedral octahedral hole a) tetrahedral
(b) triangle (c) triangle
octahedral hole (d) (square)
(e) triangle
60
7.19 face-centered cubic unit cell Octahedral
tetrahedral holes octahedral hole 12
tetrahedral hole
4 octahedral hole tetrahedral hole
()
center
at cell edges
= [1+12(1/4)] octahedral holes/unit cell
4 spheres/unit cell
= 1 octahedral hole/ sphere
= 8 tetrahedral holes/unit cell
4 spheres/unit cell
= 2 tetrahedral holes/sphere
7.20 (a) three dimension (b) cross-section
A-type lattice
1/10
Size of holes cubic > octahedral > tetrahedral
Coord. No. 8 6 4
7.20
r +/r
trigonal 0.155
tetrahedral 0.225
octahedral 0.414
cubic 0.732
7.3
r +/r - 0.155 to 0.225 to 0.414 to 0.732 to higher values
C.N. 3 4 6 8
trigonal tetrahedral octahedral cubic
7.21 x-ray
diffection map electron
density contour NaCl
(electron/3 contour Line boundary
C.N Na+ radius,
(b)CsCl Cs+ cubic holes Cl-
(d)Zinc blend Zn2+ tetrahedral holes fcc S2-
Wurtzite unit cell
(e) Wurtzite Zn2+ tetrahedral holes hcp S2-
ABCABC layer structure fcc unit cell
172 173 174 Figure 7.22
(C.N. of A) x (no. of A in formula) = (C.N. of B) x (no. of B in formula)
A B AB
Fluorite, CaF2, F-
fcc Ca2+
Ca2+ cubic hole simple cubic F-
Rutile, TiO2
Rutile, TiO2 Ti4+ non-close-packed array
Structures involving polyatomic molecular and ions
(a)
(b)
(b) Potassium hexachloroplatinate (IV)
K2PtCl6 antifluorite
K+ tetrahedral holes
fcc PtCl62-
C) Calcium carbide, CaC2 C22-
fcc Ca2+
D) Calcium carbonate, CaCO3
Ca2+
face-centered rhombohe
dral CO32-
Frenkel defect (ionic lattice) interstitial sites
Fe2+ Fe2+ Fe3+
(oxigen-iron ratio)
stoichiometry Fe0.95O
(impurity) rubies
Emeralds lattice defect edge dislocation
cubic close-packed (face centered-cubic) normal spinel A(II) 1/8 B(III) stoichiometry A 1 4 B 2 4 normal spinel 100 inverse
spinel B(III) A(II)
7.26 a portion of the space lattice of the spinel structure (AIIB2IIIO4)
showing the A(II) cations (occupying 2 of possible 16 tetrahedral sites
(or one-eighth of the tetrahedral holes) and the B(III) cations occupying
Four of possible eighth octahedral sites (or one-half of the octahedral
holes)
7.27
Crystal field stabilization
Energy (CFSE)
NiFe2O4 (a) Ni2+
(d8) (b) Fe3+ (d5)
Weak-field tetrahedral
octahedral holes