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AP Notes Chapter 12 & 13Intermolecular Forces, Liquids and SolidsIntermolecular Forces, Liquids and Solids
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1. Ion - Ion
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Dissociation Energy of Alkali Halides
500600700800900
10001100
Li Na K Rb Cs
Hdi
ssoc
(kJ/
mol
)
F
Cl
Br
I
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Dissociation Energy
Opposite of Lattice Energy
MX (s) M+(g) + X-
(g)
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1. Ion - Ion2. Ion - Permanent Dipole
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Hydrated IonsA particle that is only weakly polar but is much larger than ion alone
The number of waters of hydration depends on size of ion and strength of charge to be stabilized (typically less than 5)
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1. Ion - Ion2. Ion - Permanent Dipole3. Dipole - Dipole
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Occurs between molecules with
permanent dipoles (SO2 , CHCl3 , etc)
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Hydrogen-Bonding
Relatively strong attraction between a hydrogen atom in one molecule and a highly electronegative atom (F, O, N) in a different molecule
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Hydrogen-Bonding
Strong enough to produce a phase
change in a compound that should be more
random at that temperature(about 1.5 kJ)
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Dimer ofAcetic Acid
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Hydrogen-Bonding
How and why of bonding is not clear - most likely due to strong attraction between e- cloud of the highly EN atom and the nucleus of the H atom
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QUESTIONIs the hydrogen bond
a “true” chemical bond or is it just a
very strong electrostatic attraction?
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1. Ion - Ion2. Ion - Dipole3. Dipole – Dipole4. Dipole-Induced Dipole
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1. Ion - Ion2. Ion - Dipole3. Dipole – Dipole4. Dipole-Induced Dipole5. Dispersion Forces
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Dispersion Forces
Process of distorting an electron cloud by
electrostatic forces of attraction and
repulsion.Weakest of the
intermolecular forces.
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Non-polarmolecules
Momentary attractions
& repulsions
Temporarydipoles
established
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Dispersion forces also called
van der Waal’s forces
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LIQUIDS & SOLIDS
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Cohesive Forcesvarious
intermolecular forces holding a liquid together
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Vaporization Process in which a Process in which a
substance in the liquid substance in the liquid state becomes a gas.state becomes a gas.
Vaporization requires Vaporization requires energy since it involves energy since it involves separation of particles separation of particles that are attracted to one that are attracted to one another. another.
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Standard Molar Enthalpy of
Vaporization, Hºvap Energy required to convert one Energy required to convert one
mole of liquid to one mole of the mole of liquid to one mole of the corresponding gas at the BP.corresponding gas at the BP.
Always endothermic, Always endothermic, HHvapvap is is positive.positive.
Liquids having greater attractive Liquids having greater attractive forces have higher forces have higher HHvapvap
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2mv2
1 KE
Opposite of Evaporation
Condensation -- Exothermic
Condensation
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Viscosity
a measure of the resistance to
flow of a liquidEthylene Glycol & EtOH
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Surface Tension
the force that causes the surface of a
liquid to contract
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Paper Clip
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Adhesive Forces
the forces of attraction between a
liquid and a surface
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Capillary Action Meniscus
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SOLIDS
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Amorphous Solids
Arrangement of particles lacks an ordered internal
structure. As temp is lowered, molecules
move slower and stop in somewhat random
positions.
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Crystalline SolidsAtoms or ions are held
in simple, regular geometric patterns
IonicMolecular
Atomic
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Atomic SolidsNoble Gases
NetworkMetallic
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X-ray Crystallography
How do you determine the spacing and
position of atoms in an organized
solid like a crystal?
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X-ray Crystallography
Bragg discovered that nuclei of atoms or
ions in a crystal will defract x-rays and form a pattern on
photofilm that can be analyzed using simple trig &
geometry
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X-ray CrystallographyUse the fact that x-rays
are part of the electromagnetic
spectrumNuclei in crystalline solids are in layers that can act as a diffraction grating to the x-ray wavelength
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Crystalline Solids Diffract X-rays
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Let = “extra” distance that i’ must travel so
that r’ is in-phase with r
= xy + yzor = 2xy
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Using trigonometry:
sin dxy
d
xysin
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sin d 2
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But for constructive interference
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But for constructive interference
= nn = 2d sin
BRAGG EQUATION
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1. X-rays from a copperx-ray tube ( = 154 pm)were diffracted at an angle of 14.220 by acrystal of Si. What isthe interplanar spacingin silicon?
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Solids
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Types of Solids
1. Atomic (Metals)
2. Molecular (Ice) 3. Ionic (NaCl)
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Structures of Metals
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The unit cell is the smallest
representation of the building block of the
regular lattice
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Unit CellOnly 23 different unit
cells have been defined
Called Brave’ LatticesPatterns are determined by crystallography
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Coordination NumberCN is related to net
atoms found within the unit cell
CN is the number of atoms closest to any
given atom in a crystal
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There are three Cubic Unit Cell TypesThere are three Cubic Unit Cell Types
(pc) primitive cubic or simple cubic(pc) primitive cubic or simple cubic(8 corners of cube) x (1/8 each corner in cell) = 1 net atom in cell(8 corners of cube) x (1/8 each corner in cell) = 1 net atom in cell
CN = 6CN = 6
(bcc) body centered cubic(bcc) body centered cubic(1 atom in cube) + (1 atom in cube) +
[(8 corners of cube) x (1/8 each corner in cell)] = 2 net atoms in [(8 corners of cube) x (1/8 each corner in cell)] = 2 net atoms in cellcell
CN = 8CN = 8
(fcc) face centered cubic(fcc) face centered cubic[(6 faces of cube) x (1/2 of atom in cell)] + [(6 faces of cube) x (1/2 of atom in cell)] +
[(8 corners of cube) x (1/8 each corner in cell)] = 4 net atoms in [(8 corners of cube) x (1/8 each corner in cell)] = 4 net atoms in cellcell
oror CN = 12CN = 12 (1 atom in cube) +(1 atom in cube) + [(12 edges of cube) x (1/4 each edge in cell)] = 4 net atoms in cell[(12 edges of cube) x (1/4 each edge in cell)] = 4 net atoms in cell
CN = 12CN = 12
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1 Atom per Cell
CN = 6
l = 2r
l
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2 Atoms per Cell
CN = 8l
22 2 r42
3
r4
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4 Atoms per Cell
CN = 12
l
2 22 r4
2r2
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Summary
Unit Cell
Atoms
Per Cell
C.N.
LengthOf Side
Cubic 1 6 2rBCC 2 8
FCC 4 12
34r
22r
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Face-centered cubicPrimitive cubic
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Structures of Metals
Closest Packing
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Structures of Metals
Closest Packing 1. Hexagonal 2. Cubic
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A-B A-B-C
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(Primitive cubic)
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2. Al crystallizes as a face centered cube. The atomic radius of Al is 143 pm. What is
the density of Al in g/cm3?
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3. What is the percent of empty space in a body
centered unit cell?
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VAPORPRESSURE
Evaporationand equilibrium
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Vapor Pressure
pressure in space above a liquid in a CLOSED container
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PROPERTIES1. closed container2. temperature dependent
3. subject to all laws of partial pressures
4. dynamic system
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Vapor Pressure temperature dependent
P
T
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To plot in a linear fashion, must transform the
variables.
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ln P
1/T (K)
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y = mx + b
& R = 8.314 J/K mol
R
H m :where vap
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therefore:
bT
1
R
H- P ln vap
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ln P
1/T (K)
define 2 points
1
2
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bT
1
R
H- P ln
bT
1
R
H- P ln
2
vap2
1
vap1
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Subtract: ln P1 - ln P2
bT
1
R
H--
bT
1
R
H-
2
vap
1
vap
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Collect terms & factor:
Clausius-ClapeyronEquation
12
vap
2
1
T
1
T
1
R
H
P
Pln
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SUMMARY OF IDEAS TO BE CONSIDERED:1. vapor pressure - temperature dependent2. volume determines time needed to establish vapor pressure - NOT final pressure
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3. H (condensation) = -H (vaporization)
4. Critical Point - (T,P) above which vapor cannot be liquefied - regardless of pressure5. Boiling: temperature where vapor pressure of liquid is the same as atmospheric pressure
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4. The temperature inside a pressure
cooker is 1150C. What is the vapor pressure
of water inside the pressure cooker?
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PHASE DIAGRAMS
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PHASE DIAGRAMPHASE DIAGRAM
A representation of the A representation of the phases of a substance in phases of a substance in
a closed system as a a closed system as a function of temperature function of temperature
and pressureand pressure
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Normal Boiling PointNormal Boiling Point
Temperature at which Temperature at which the vapor pressure of the vapor pressure of the liquid is exactly 1 the liquid is exactly 1
atmosphereatmosphere
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Normal Melting Normal Melting PointPoint
Temperature at which Temperature at which the solid and liquid the solid and liquid
states have the same states have the same vapor pressure when vapor pressure when
the total P = 1 atmthe total P = 1 atm
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Triple PointTriple Point
The point on a phase The point on a phase diagram at which all diagram at which all
three states of a three states of a substance are presentsubstance are present
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Critical TemperatureCritical Temperature
Temperature above Temperature above which vapor cannot be which vapor cannot be liquified no matter what liquified no matter what
pressure is appliedpressure is applied
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Critical PressureCritical Pressure
Minimum pressure Minimum pressure required to produce required to produce
liquefaction of a liquefaction of a substance at the substance at the
critical temperaturecritical temperature
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Critical PointCritical Point
Ordered pair ofOrdered pair of
Critical TemperatureCritical Temperature
& Critical Pressure& Critical Pressure
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CO2
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H2O
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sulfur