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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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เนื้อหา Inorganic Solid 1. Classification of Bonds and Crystals

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Inorganic solid 1 classification of bonds and crystals

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


Inorganic solid 1 classification of bonds and crystals

Acid-base Chemistry

1. Acid-Base concepts

2. Measures of Acid-Base Strength

3. Hard and Soft Acid and Bases


Classification of bonds and crystals

Classification of Bonds and Crystals


Ionic bond

Ionic bond

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.


Covalent bond

Covalent bond


Inorganic solid 1 classification of bonds and crystals

Metallic bond

  • Metallic bonds fall into two categories.

  • simple metal valence electron sp-shell electron crystal conduction electron crystal

  • 2. the case in which the valence electrons are from the sp-

  • shells of the metal ions; this bonding is quite weak.

  • the valence electrons are from partially filled d-shells, and this bonding is quite strong. The d-bonds dominate when both types of bonding are present.


Type of crystals

Type of crystals ()

  • Solid () (atom) (molecule) (ion) rigid crystal lattice

  • (interaction) (ionic bond) (metallic bond) (covalent bond) (hydrogen bond) - (dipole-dipole forces) (van der Waals forces)


Ionic crystals

Ionic crystals ()

NaCl


Metallic crystals

Metallic crystals ()

  • metallic crystal (lattice of cation)

electrical conductivity metallic lattice

electrical conductivity


Covalent crystals

Covalent crystals ()

  • crystal lattice

diamond

lattice


Inorganic solid 1 classification of bonds and crystals

  • diamond (SiO2) (Si) (BN)

sp3 hybridization

CCC 109.5o


Atomic molecular crystals

Atomic-molecular crystals

  • (Londondispersion forces) - (dipole-dipole forces) (Atomic-molecular crystals) 2 (directional) (nondirectional) Atomic-molecular crystals dry ice (CO2) (CH4) (HCl) (P4)


Inorganic solid 1 classification of bonds and crystals

H-O---H 109.5

London dispersion

intermolecular forces


A type crystal lattices

A-type crystal lattices

  • Space lattice and unit cells

    Space lattice

    Unit cell space lattice

    (1) space lattice

    (2)


Inorganic solid 1 classification of bonds and crystals

haxagonal space lattice 2 dimension 4 a) Lattice b) (rhombic) c) rectangle lattice d) hexagon unit cell


A type lattices

A-type lattices

  • A-type lattices simple cubic lattice

A-type lattice cubic lattice hard

sphere


Inorganic solid 1 classification of bonds and crystals

simple cubic lattice (a) unit cell lattice

6

(b) 1/8 (c) space lattice highlight unit cell 8 ()


Inorganic solid 1 classification of bonds and crystals

  • b l (cell edge) d (diameter of sphere) l = d 1 cubic unit cell l3( d3)

    [(4/3)(d/2)3] x 1

Fraction of space

occupied by sphere

= 0.52

=

d3


Inorganic solid 1 classification of bonds and crystals

A-type lattice


Inorganic solid 1 classification of bonds and crystals

Unit cell (a) simple (b) body-centered (c) face-centered

cubic lettices


Inorganic solid 1 classification of bonds and crystals

  • (density) mass (Avogadros number)

    (g/cm3) = 1 atom (AW/6.02 x 1023)(g/atom)

d3 cm3

simple cubic lattice


Inorganic solid 1 classification of bonds and crystals

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


Inorganic solid 1 classification of bonds and crystals

  • Body-centered cubic (bcc)

    simple cubic lattice cubic cell b) 8 cubic 1/8 8 2[=1+8(1/8)] l d cell edge sphere diameter


Inorganic solid 1 classification of bonds and crystals

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)


Inorganic solid 1 classification of bonds and crystals

(a)

  • 7.10cubic and hexagonal

  • Close-packed structures

  • Layer A of both structures

  • Layer A and B of both structures showing two types of depression

  • (c) ABCABC layer of cpp structure

  • (d) ABABAB layer of hcc structures


Inorganic solid 1 classification of bonds and crystals

7.11 cpp structure fcc unit cell ABCABC layer

(b) fcc unit cell ABCABC layer

(c) space lattice fcc unit cell ABCABC layer


Inorganic solid 1 classification of bonds and crystals

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


Inorganic solid 1 classification of bonds and crystals

  • Hexagonal

  • closed packed unit cell

  • ABABAB layer

(b)

12


Inorganic solid 1 classification of bonds and crystals

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


Inorganic solid 1 classification of bonds and crystals

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


Ab n type crystal lattices

ABn-type crystal lattices

  • ABn-type lattices (ionic crystral) A-type lattice (hole)

  • anionic lattices (hole) A-type lattices


Cubic octahedral and tetrahedral holes

Cubic, Octahedral and Tetrahedral Holes

7.17

simple cubic unit cell

cubic hole 7.17 space-filling model

(radius) cubic hole


Inorganic solid 1 classification of bonds and crystals

7.18 tetrahedral octahedral hole a) tetrahedral

(b) triangle (c) triangle

octahedral hole (d) (square)

(e) triangle

60


Inorganic solid 1 classification of bonds and crystals

7.19 face-centered cubic unit cell Octahedral

tetrahedral holes octahedral hole 12

tetrahedral hole

4 octahedral hole tetrahedral hole

()


Inorganic solid 1 classification of bonds and crystals

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


Radius ratios

Radius ratios

7.20 (a) three dimension (b) cross-section

A-type lattice


Inorganic solid 1 classification of bonds and crystals

  • 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


Inorganic solid 1 classification of bonds and crystals

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


Ionic radii

Ionic radii

7.21 x-ray

diffection map electron

density contour NaCl

(electron/3 contour Line boundary


Inorganic solid 1 classification of bonds and crystals

  • Shannon-Prewitt ionic radii 7.4, 7.5 7.6 ionic radius

    C.N Na+ radius,

  • 1.13

  • 1.16

  • 8 1.32


Inorganic solid 1 classification of bonds and crystals

  • NaCl ABCABC layers

  • (b) NaCl view as fcc Cl- with

  • Na+ in octahedral holes


Inorganic solid 1 classification of bonds and crystals

(b)CsCl Cs+ cubic holes Cl-


Inorganic solid 1 classification of bonds and crystals

(d)Zinc blend Zn2+ tetrahedral holes fcc S2-


Inorganic solid 1 classification of bonds and crystals

Wurtzite unit cell

(e) Wurtzite Zn2+ tetrahedral holes hcp S2-


Inorganic solid 1 classification of bonds and crystals

  • NaCl rock salt AB structure radius ratio sodium cation cubic closed-packed lattice chloride anion 7.22a

    ABCABC layer structure fcc unit cell

    172 173 174 Figure 7.22


Ab 2 structures

AB2 structures

  • AB compound 7.6

    (C.N. of A) x (no. of A in formula) = (C.N. of B) x (no. of B in formula)

    A B AB


Inorganic solid 1 classification of bonds and crystals

Fluorite, CaF2, F-

fcc Ca2+

Ca2+ cubic hole simple cubic F-


Inorganic solid 1 classification of bonds and crystals

Rutile, TiO2

Rutile, TiO2 Ti4+ non-close-packed array


Inorganic solid 1 classification of bonds and crystals

Structures involving polyatomic molecular and ions

(a)

(b)

(b) Potassium hexachloroplatinate (IV)

K2PtCl6 antifluorite

K+ tetrahedral holes

fcc PtCl62-

  • Dry ice, CO2 CO2

  • fcc array


Inorganic solid 1 classification of bonds and crystals

C) Calcium carbide, CaC2 C22-

fcc Ca2+

D) Calcium carbonate, CaCO3

Ca2+

face-centered rhombohe

dral CO32-


Defect structures

(Defect structures)

  • Simple vacancies

  • Unexpected occupation of interstitial sites

  • incorporation of impurities, that is, atoms and ions other than those of parent crystal

  • Various lattice imperfection


Types of defect structure

(Types of defect structure)

  • Schottky defect


Inorganic solid 1 classification of bonds and crystals

Frenkel defect (ionic lattice) interstitial sites


Inorganic solid 1 classification of bonds and crystals

  • defect stiochiometry iron(II)oxide, FeO

Fe2+ Fe2+ Fe3+

(oxigen-iron ratio)

stoichiometry Fe0.95O


Inorganic solid 1 classification of bonds and crystals

(impurity) rubies

Emeralds lattice defect edge dislocation


Spinel structure connecting crystal field effects with solid state structure

Spinel structure: Connecting crystal field effects with solid state structure

  • Spinel structure AIIB2IIIO4 MgAl2O4

    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)


Inorganic solid 1 classification of bonds and crystals

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)


Inorganic solid 1 classification of bonds and crystals

7.27

Crystal field stabilization

Energy (CFSE)

NiFe2O4 (a) Ni2+

(d8) (b) Fe3+ (d5)

Weak-field tetrahedral

octahedral holes


Inorganic solid 1 classification of bonds and crystals


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