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Chapter 1 Eng
Chapter 1 Eng
Chapter 1 Eng
• General comments
• 4 major states of matter:
– Plasma
– Gas
– Liquid
– Solid crystalline structure
• Three metastable states: (self reading)
– Amorphous
– Supercooling liquid
– Superheating liquid
– Liquid crystal (self reading)
1. Plasma:
– Plasma has neither a definite volume nor a definite shape.
Plasma often is seen in ionized gases, but it is distinct from a
gas because it possesses unique properties. Free electrical
charges (not bound to atoms or ions) cause the plasma to be
electrically conductive. The plasma may be formed by heating
and ionizing a gas. Examples of plasma include stars,
lightning, fluorescent lights, and neon signs.
2. Gas
– In a gas, the particles have a great deal of space between them
and have high kinetic energy. A gas has no definite shape or
volume. If unconfined, the particles of a gas will spread out
indefinitely; if confined, the gas will expand to fill its
container. When a gas is put under pressure by reducing the
volume of the container, the space between particles is
reduced and the gas is compressed.
• At low pressure, high temperature, the
distance between gas molecules are far. Thus,
the size and intermolecular forces are
negligible. The gas is considered as ideal and
followed ideal gas law:
PV = nRT
• In which:
– P is the gas pressure (affecting the container wall).
– V is the volume of the container.
– n is number of moles of gas.
– R is the universal gas constant
– T is the absolute temperature
• At high pressure, low temperature, the distance
between gas molecules becomes closer so that the
size and intermolecular force are important. The
gas is real gas and followed:
a
(P + 2 )(V − b) = RT
V
a
• In which 2
reflects the intermolecular forces
V
– b is the specific volume of the gas molecules
• Liquefaction of gas
• At normal pressure, gas becomes liquid at a
certain temperature. The temperature is called
condensation point of the gas. At that
temperature, the liquid also becomes vapor.
Therefore, the temperature is also called
boiling point of the liquid.
• The gas becomes liquid because the energy is
removed by increasing the pressure or
reducing the temperature. Therefore, the
condensation point can be lowered by
decreasing the pressure.
• However, increasing pressure to liquefy the
gas has a limit. At high temperature, the
liquid can not exist under any pressure.
• The highest temperature at which the liquid
can exist is critical temperature (Tc) and the
required pressure to liquefy the gas at that
temperature is called critical pressure (Pc).
Volume of 1 mole of gas at Tc and Pc is
critical volume. At critical point, the volume
of gas and solid are equal, thus the densities
of them are identical.
3. Liquid:
• is an intermediate phase existing between
solid and gaseous phases. At room
temperature, structure of liquid near the
structure of solid crystalline.
• Different from solid crystalline, there are
empty spaces in liquid, the particles in liquid
can move easily. Liquids conform to the shape
of the container and isotropic in magnetic, light
and mechanical properties. Liquid is almost
incompressible.
Comparison between structure of solids (a)
and liquid (b)
4. Crystalline and amorphous solid state
• Crystalline
• Atoms are arranged in strictly regular 3
dimension
• Therefore:
– Defined structure and shape.
– Long range order.
– Anisotropic.
– Sharp melting point.
Examples
SiO2 crystal
(Cristobalite)
• Amorphous:
• Structure is similar to liquid, has an irregular
arrangement of solid particles
• Therefore:
– Undefined structure and shape.
– Short range order
– Isotrophic
– No particular melting point.
2. Structure of crystals
• Center of Symmetry
- If an imaginary straight
line can be passed
through a crystal from
any point on the surface
of crystal such that the
point of entry is similar
to the point of exit, then
the crystal has a center
of symmetry.
• Plane of Symmetry
– When an imaginary
plane is passed through
a crystal such that the
portion of the crystal on
one side of the plane is
a reflection, or mirror
image, of the portion
on the other side of the
plane, the plane is
a plane of
symmetry (often called
a mirror plane).
• Axis of Symmetry
– When an imaginary line
can be passed through a
crystal such that the
crystal can be rotated
360o about the line to
fill the same space n
(two, three, four, or six)
times, it has an axis of
symmetry.
– n is the order of the axis
(L4 in this example)
2. Internal structure of crystals
CsCl Ar CO2
3. Crystal systems and unit cells
• A crystal can be classified according to its
elements of symmetry. For example, it may
belong to one of 230 space groups, 32 point
groups, 14 Bravais lattices, and 7 crystal systems:
1. Island-like structure
2. Chain-like structure
3. Layer-like structure
4. Coordination structure
1. Island-like structure
• Each species form an isolated island located at the
lattice nodes.
• Interaction between lattice nodes/species: Van de
Waals force, Hydrogen bond, electrostatic force
(complex ions) → Ulattice is small → Tfusion Tboiling is
low → gas or liquid at room temperature
• Covalent bond: only within the nodes.
• Lattice nodes: finite molecules, complex ions, noble
gas atoms.
• Molecular lattice and ionic lattice with complex ions
are island-like structure
Example: H2, O2, N2, Ar, CO2, X2, HCHC, H2O, K2[TiCl6]
2. Chain-like structure
BeCl2
AB2
• Chain has unit structure of square AB4
with stoichiometric formula of AB2
(example PdCl2)
PdCl2
AB2
• Chain has unit structure of octahedral AB6 with
stoichiometric formula of AB4 (example MgCl2.2H2O)
MgCl2.2H2O
AB4
• Chain has unit structure of octahedral AB6 with
stoichiometric formula of AB5 (example CrF5- in
CaCrF6 compound)
CaCrF6
AB5
3. Layer-like structure
Al(OH)3 AB3
• Layer like structure has unit structure of
octahedral (AB6) with a stoichiometric
formula of AB3example: CdI2
AB2
4. Coordination structure
• In a coordination structure, each species
(lattice node) is surrounded by a definite
number of species (atoms, simple ion),
locating at an equal distance and connected by
the same strong bond (ionic, covalent or
metallic bond)
• Coordination structure includes atomic lattice,
ionic lattice (simple ion) and metallic lattice.
– Ionic bond and metallic bond are unsaturated and
non-directional → crystals of coordination structure
of ionic and metallic lattice have high value of
coordination number. They have been arranged in
most tightly packed.
– Crystals of coordination of covalent lattice
determined by the hybridization of atoms (directional
properties) → low value of coordination number (= 4)
• Coordination structures of stoichiometric
formula of A and different unit cells
Diamond AA4
W AA8
• Coordination structure of stoichiometric
formula of AB and different unit cells :
TiO2 (AB6)
SiO2 (AB4)
• Coordination
structure of
stoichiometric
formula AB3
and
octahedral
unit cell
ReO3 (AB6)
IV. Relation between bonding types, crystal
lattice structure and physico-chemical properties
of compounds
1. Metallic bond and metallic lattice
2. Ionic bond and ionic lattice
3. Covalent bond and atomic lattice,
molecular lattice
4. General comments on physical properties
of compounds
1. Compounds with metallic bond and
metallic lattice
a. Crystalline structure
b. Lattice energy
c. Physical properties
a. Crystalline structure
• In metallic crystal, nodes/points are metallic cation
Mn+ connected with each other by metallic bond and
arranged in most tightly packed structure. Valence e
move freely in entire crystal to form delocalized
bonding. Metallic lattice is a giant molecule. Whole
metallic system is a giant molecule.
W Cu Mg
(SPT = 8) (SPT = 12) (SPT = 12)
b. Lattice energy
Compounds Li Na K Rb
b. Lattice energy
c. Physical properties
a. Crystalline structure
Theoretical consideration
Experiment Born-Mayer Equation
Born-Haber Cycle Born-Lande Equation
Kapustinskii Equation
∆hsub,Na ½ Ediss
∆Hf
Na(s) + ½ Cl2(g) NaCl(s)
In which
∆Hsub,NaCl: heat of sublimation of Na = 108 kJ/mol
INa: ionization energy = 496 kJ/mol
Ediss: heat of dissociation of Cl2(k) = 224 kJ/mol
∆Hf: heat of formation of NaCl (r) = – 411 kJ/mol
ECl: electron affinity of Cl = – 349 kJ/mol
e 2 z+ z−
E = −K
r
COULOMB FORCE –BORN EQUATION
MN A e 2 z + z −
E ml = −
4πε0 r
Madelung constant
• The principle of calculating the Madelung constant can be explained, using
sodium chloride as an example.
• Let us consider one of the sodium ions in the NaCl lattice. The nearest
neighbours of each sodium ion are 6 chloride ions at a distance r. The
Coulomb energy of interaction with these ions will be (other constants are
skipped)
6
U1 = −
r
• Next, 12 sodium ions are arranged around the chosen sodium ion
at a distance of r√2. Since these ions have the same sign as the ion
under consideration, the interaction energy is written
12
U2 = −
r 2
• The following neighbours of this particular ion are 8 chloride ions
at a distance of r√3, which gives the contribution to their interaction energy
8
U3 = −
r 3
M – Madelung constant, depends on the structure of
lattice
Formula Coordination Structural type Radius ratio Madelung
number x = r+/R- Constant M
8 CsCl x > 0.723 1.763
CdI2 2.191
CdCl2 2.244
http://www.chem.latech.edu/~upali/chem281/281test/crystal.html
https://daniloroccatano.blog/2017/10/27/calculation-of-the-madelung-constant/
COMPARISON OF RESULTS FROM BORN-HABER CYCLE
AND BORN EQUATION
BORN – MAYER EQUATION
N A Z + Z − e2 d
U lattice =
− 1 − M
4πε o d o d o
In which
do = r+ + r-
d : constant (is 34.5 pm if r measured by pm, 10-12m)
Substituted other constants, we have:
1390 Z + Z − d
E ml =−
1 − M (kJ / mol)
do do
BORN – LANDE EQUATION
MN A Z + Z − e 2 1
U lattice =
− (1 − )
4πε 0 r0 n
MN A Z + Z − e 2 1
E ml• = (1 − )
4πε0 r0 n
23 −19 2
1.75x 6.023x10 (+1)(−1)(1.602 x10 ) 1
= −12 −12
(1 − )
4 x 3.142 x8.854 x10 x 282 x10 9.1
= −766376 J / mol = −766.376 kJ / mol
KAPUSTINSKII EQUATION
(1071.5) n | z + || z − |
E ml = − kJ / mol
r+ + r−
r measured in Å (10-10m).
n: number of ions in the empirical formular
Example: with NaCl
E = -(1071.5x2x1x1)/(2.83) = -757.24 kJ.mol
• The equation is simple, high accuracy and widely used.
• The equation is also used to estimate the thermos
chemical radii of ions as follows.
c. Stability and physical properties of ionic
crystals
• Polarization in ionic bond will increase the covalent
character of bonding, reduce the effective ionic
charge and therefore, lower the decomposed
temperature, melting point… in ionic crystals.
• Example: CaF2 is very stable, does not decompose
at 1000oC, while CuI2 does not exist at room
temperature.
– Explain: r[Cu2+] = 0.72 Å < r[Ca2+] = 0.99Å.
– And r[I-] >> r[F-], therefore Cu2+ will pull the electron
toward it, reduce the ionic degree. Therefore, Cu2+ easily
changes to Cu+, and I- changes to I2.
– CaF2 almost no , ionic degree is very high
Polarization in ionic bonding:
• The electron cloud distortion of the ions.
• In the perfect ionic model, the ions would be perfectly
spherical and the positive and negative ions would attract
each other but not distort each other. Reality is a bit
different because the positive ion will pull some of the
electron cloud of the negative ion towards itself.
• If the electron cloud is distorted there will be electron
density between the two ions giving the bond some covalent
character.
Farjan rule
• If a cation is highly charged it will exert a
strong electrostatic attraction on the anion
and distort the electron cloud.
• If the anion has a large electron cloud it will
be easily distorted.
• Example:
• Consider two series.
• Hybridization of AO.
• VSEPR theory
sp2
Liquid state Al: sp2 → sp3, Coord. No.=4 sharing 1 edge
O
O
σ
O
Liquid and solid: sp2 → sp3 form chain structure including tetrahedral
with 2 sharing vertices
Which case sharing the vertices, which case
sharing the edge?
• Coordination species are small size atoms: C, N,
O, F sharing the vertices (single bridge)
O
O
Coord .A y
AxBy =
Coord .B x
B = large size B = C, N, O, F
→ Share edge → Share point
→ Double connection → Single connection
Coordination
Island structure Chain structure Layer structure Structure
MA
Hydrogen
bonding
H3BO3 molecules
H2O H3BO3
4. General comments on physical
properties of compounds
• Stronger bond higher melting point and
boiling point
• In compounds with Van de Waal interaction,
higher molecular mass higher melting point
and boiling point. In the case that have
additional hydrogen bond, melting point and
boiling point will increase significantly
• Stronger bond higher melting point and boiling
point.
Compounds B Al NaCl H2S H2O
Melting 2076 660 601 -85,6 0
point, 0C
Compounds Li Na K Rb
Ideal crystal