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Chapter 2 Structures of Solids
Chapter 2 Structures of Solids
Structures of Solids
Chapter 2
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Chapter 2
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Chapter 2
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Chapter 2
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2.
3.
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Chapter 2
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Structure of a Buckyball
Carbon Nano-tube
A nanotube (also known as a buckytube) is a member of the fullerene structural
family, which also includes buckyballs. Whereas buckyballs are spherical in shape,
a nanotube is cylindrical, with at least one end typically capped with a hemisphere
of the buckyball structure. Their name is derived from their size, since the
diameter of a nanotube is on the order of a few nanometers , while they can be up
to several centimeters in length. There are two main types of nanotubes: singlewalled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs).
Chapter 2
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Experimental Determination
of Crystal Structures
Braggs Law
2 d sin = n
Chapter 2
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Chapter 2
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Single crystal
Powder
Chapter 2
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Crystal Lattices
To describe crystals, three-dimensional views must be used.
The repeating unit of the lattice is called the unit cell.
The simple cubic cell (primitive cubic) is the simplest unit
cell and has structural particles centered only at its corners.
The body-centered cubic (bcc) structure has an additional
structural particle at the center of the cube.
The face-centered cubic (fcc) structure has an additional
structural particle at the center of each face.
Chapter 2
Slide 13 of 85
Unit Cells In
Cubic Crystal Structures
simple cubic
(primitive cubic)
bcc
Chapter 2
fcc
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Primitive cubic
Body-centered cubic
Chapter 2
Face-centered cubic
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Closest packed
a
ab
abc
aba
unoccupied holes
Chapter 2
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abab
Hexagonal close-packed structure
polytypes
abcabc
Cubic close-packed structure
= Face-centered cubic
Chapter 2
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Chapter 2
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Na+:
Cl-:
Coord. #:
6;
atom/ unit cell
Na: Cl= 4: 4 = 1: 1
Cl- at fcc
Na+ at Oh holes
NaCl
Chapter 2
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Zn2+:
Coord. #:
4;
atom/ unit cell
Zn: S = 4: 4 = 1: 1
S2-:
S2- at fcc
Zn2+ at Td holes
ZnS
Chapter 2
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NaCl(s)
Na+(g) + Cl-(g)
f 0(NaCl)
IE(Na)
-EA(Cl)
sublimation (Na)
Na(s) + 1/2Cl2(g)
Na(g) + Cl(g)
1/2D(Cl-Cl)
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H = - U 0 < 0
Chapter 2
~1%
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A Z + Z e2
Ec =
4 0 r
A : Madelung Constant
Chapter 2
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Chapter 2
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Born equation
electrostatic energy
B: constant
n: Born exponent
Ion configuration
He
Ne
Ar, Cu+
Kr, Ag+
10
Xe, Au+
12
Chapter 2
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Slide 29 of 85
For NaCl
A = 1.74756
Z1 = 1, Z2 = -1
d0 = rNa+ + rCl- = 2.81 x10-10 m
n = (nNa+ + nCl-) /2 = (7+9)/2 = 8
Chapter 2
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NAZ + Z e 2
0.345
U0 =
(1
)
4 0 d 0
d0
Unit in ? , 10-10 m
2. Kapustinskii equation
nZ + Z
0.345
U0 =
(1
)
d0
d0
= 1.21 MJ. ? mol-1
Chapter 2
MCO3(s ) MO(s ) + CO 2 (g )
Data at 298K
Mg
Ca
Sr
Ba
G0 (kJ/mol)
+48.3
+130.4
+183.8
+218.1
H0 (kJ/mol)
+100.6
+178.3
+234.6
+269.3
S0 (J/K mol)
+175.0
+160.6
+171.0
+172.1
T (?C)
300
840
1100
1300
G 0 = H 0 - TS 0
H 0
decomposition T =
S 0
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Enthalpy of solution
Hydration enthalpy
<0
>0
G 0 = H 0 - T S 0 = L - T S 0
Chapter 2
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Hydration enthalpy
H hyd
U 0
Z2 1
=
1
2r
1
r+ + r
H hydration = H M + + H X =
1 1
+
r+ r
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Chapter 2
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Fajan's rules
Fajan's Rule: the degree of covalent character of ionic
bond
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m.p. (?C)
Crys str
HgF2
645 (dec)
cubic
HgCl2
276
HgBr2
HgI2
m.p. (?C)
Crys str
CaF2
1418
cubic
orthorhombic
CaCl2
775
cubic
236
rhombohedral
CaBr2
742
rhom.
259
tetragonal
CaI2
783
hexagonal
Chapter 2
Halides
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Examples:
For ions with noble gas (ns2 np6 ) structure, the only factor that
have to be considered are size and charge factor.
a) Charge factor
i) Cations
Na+ Mg2+ Al3+
Increasing charge : increase in polarizing power
ii) Anions
N3-
O2-
F-
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Chlorides
Conductance in
molten state
NaCl
MgCl2
AlCl3
800
715
sublimation
1440
1410
183
133
29
1.5 x 10-5
SiCl4
-70
57
covalency
Chapter 2
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b) Size factor
i)
Cations
Be2+ Mg2+ Ca2+ Sr2+ Ba2+
melting point /
C
Conductance in
molten state
BeCl2
MgCl2
404
715
0.056
29
CaCl2
774
52
SrCl2
870
56
BaCl2
covalency
955
Chapter 2
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ii) Anions
F-
Cl-
Br-
I-
Chapter 2
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MCO3(s ) MO(s ) + CO 2 (g )
Carbonates Decomp. Temp. (?C)
BeCO3
250
MgCO3
540
CaCO3
SrCO3
900
1289
BaCO3
1360
Some covalent
character
Oxides
wurtzite
structure
NaCl
structure
m.p. (?C)
BeO
2530
MgO
2826
CaO
SrO
2613
2430
BaO
1923
covalency
Ionic compounds
Chapter 2
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Close-packing of Spheres
in Three Dimensions
Chapter 2
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Tetrahedral holes
Octahedral holes
Cubic holes
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rh/r = 0.414
rh/r = 0.225
rh/r = 0.156
Chapter 2
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Chapter 2
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Chapter 2
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Considering
anion-anion
repulsion
Chapter 2
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Na+:
Cl-:
Coord. #:
6;
atom/ unit cell
Na: Cl= 4: 4 = 1: 1
Cl- at fcc
Na+ at Oh holes
NaCl
Chapter 2
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Rock-salt structure
Chapter 2
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As3- at hcp
Polariable cation
& anion
Ni3+ at Oh holes
Chapter 2
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Zn2+:
Coord. #:
4;
atom/ unit cell
Zn: S = 4: 4 = 1: 1
S2-:
S2- at fcc
Zn2+ at Td holes
ZnS
Chapter 2
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S2- at hcp
Polymorph of ZnS
Zn2+ at Td holes
Chapter 2
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PtS
Pt2+ at fcc
S2- at Td holes
Ca2+ at fcc
F- at Td holes
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Chapter 2
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O2- at hcp
Ti4+ at Oh holes
Coord. #: Ti: 6; O: 3
atom/ unit cell
Ti: O= 2: 4 = 1: 2
Chapter 2
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Chapter 2
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Chapter 2
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Increasing covalency
Chapter 2
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Chapter 2
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Chapter 2
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Chapter 2
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Chapter 2
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Increasing covalency
Chapter 2
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Chapter 2
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CdCl2
Cl- at ccp
Cd 2+ at Oh sites
(alternate O layers)
Chapter 2
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CdI2
I- at hcp
Cd 2+ at Oh sites
(alternate O layer)
Chapter 2
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298pm
366pm
MoS2
Mo4+ at hcp
S2- at Td sites
Chapter 2
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Chapter 2
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YBa2Cu3O7
Chapter 2
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Quartz SiO2
Chapter 2
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Chapter 2
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Chapter 2
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Chapter 2
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Chapter 2
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Mineral
Pyrophyllite
Montmorillonite
Beidellite
Nontronite
Ideal formulab
Dioctahedral minerals
Al2 (Si4 O10)(OH)2
Nax (Al2-xMgx )(Si4 O10)
(OH)2 .zH2 O
Mx (Al2 )(AlxSi4-xO10 )
(OH)2 .zH2 O
Mx (Fe3+,Al)2 (AlxSi4-xO10 )
CEC c
(meq/100 g)
0
60 - 120
60 - 120
60 - 120
(OH)2 .zH2 O
Trioctahedral minerals
Talc
Mg 3(Si4O10 )(OH)2
0
Hectorite
(Na2 Ca)x/2 (LixMg3-x)
60 - 120
(Si4 O10)(OH)2.zH2O
Saponite
Cax/2 Mg 3(AlxSi4-xO10)
60 - 120
.zH2 O
Sauconite
Mx (Zn,Mg)3(AlxSi4-xO10 )
.zH2 O
a: Only major cations are shown.
b: x depends on the origin of the mineral; montmorillonites can
show a degree of substitution x in the octahedral sheet in the range
0.05- 0.52. Natural samples generally show substitutions in both
octahedral and tetrahedral sheets, which renders the real situations
more complex.
c: Cation-exchange capacity.
Chapter 2
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Chapter 2
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Chapter 2
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Chapter 2
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