Intermolecular Forces, Liquids

and Solids
AP Chapter 11
Molecular Comparison
 Intermolecular Forces
• In liquids, the intermolecular forces are
strong enough to keep the molecules in
close proximity, but the molecules have
enough kinetic energy to move past each
other.
• In solids, the forces are much stronger;
molecular motion is restrained and
particles occupy specific locations in a 3
dimensional geometric pattern.
Types of Intermolecular Forces
• Dipole-dipole forces – the forces that act
between polar molecules
• London dispersion forces – (Van der
Waals) the forces that act between non-
polar molecules, as well as all molecules
• Hydrogen bonding – occurs between
hydrogen and another element of high
electronegativity. (O-H, N-H, F-H)
Dipole-dipole
attraction
 Ion-Dipole Forces
• Ion-dipole forces occur between solutions
in which ionic compounds are dissolved in
polar solvents.
 Dipole-dipole Forces
• The strength of the bond increases with
the difference in electronegativity within
the molecule.
• The greater the electronegativity inside the
molecule, the stronger the dipole forces
between molecules.
Hydrogen Bonding in Ice
 London Dispersion Forces
• London Dispersion Forces increase in
strength with an increase in molecular
mass.
• This is the reason why the halogens go
from gas to solid as the atomic mass
increases.
Comparing Intermolecular Forces
 Viscosity
• The stronger the intermolecular forces, the
greater the viscosity, or resistance to
flow, of a liquid.
• Surface tension of liquids also increase
as intermolecular forces increase in
strength.
• Surface tension is defined as a measure of
the tendency of a liquid to maintain a high
surface area.
Surface Tension
 Capillary Action
• The adhesion of a liquid to the walls of a
narrow tube and the cohesion of a liquid
account for the capillary action and the
formation of a meniscus at the surface of a
liquid.
 Phase Changes
• Substances exist in more than one state
of matter.
• Phase changes are transformations from
one phase to another.
• Solid to liquid is melting (fusion), solid to
gas is sublimation, liquid to gas is
vaporization.
• Heats of fusion, vaporization and
sublimation are endothermic processes.
 Phase changes, continued.
• The reverse changes (freezing and
sublimation) are exothermic processes
(negative values.)
Heating and Cooling Curves
Formulas to Use in Calculations
• q = mCΔT
• q = mHfus
• q = mHvap
 Critical Temperature and
Pressure
• Critical temperature is the highest
temperature at which a liquid can exist.
• Above the critical temperature, the motional
energies of the molecule are greater than the
attractive forces that lead to the liquid state
regardless of how much pressure is applied.
• The critical pressure is the pressure required
to create a liquid at this critical temperature.
 Vapor Pressure
• Vapor pressure of a liquid indicates the
tendency of a liquid to evaporate.
• Molecules can escape the surface of a
liquid and into the gas phase by
evaporation.
• The pressure exerted back onto the
surface of the liquid by the vapor is called
the vapor pressure.
 Dynamic Equilibrium
• The condition in which two opposing processes
are occurring simultaneously at equal rates is
called dynamic equilibrium.
• When some molecules are escaping the
surface of a liquid and some molecules are
condensing at an equal rate, the system is in
dynamic equilibrium.
• This process happens only in a closed system!
 Volatility
• Substances with very high vapor pressure,
such as gasoline, evaporate more quickly
than substances with low vapor pressure,
such as motor oil.
• Liquids that evaporate readily are said to
be volatile.
 Boiling Point
• A liquid boils when its vapor pressure equals
the external pressure acting on the surface of
the liquid.
• This is the point where bubbles of vapor form
within the liquid.
• The normal boiling point of a liquid at 1 atm
pressure is the normal boiling point.
• The temp. at which a liquid boils increases with
increasing external pressure.
 Phase Diagrams
• A phase diagram is a graphic way to
summarize the conditions under which
equilibria exist between the different states
of matter.
• These diagrams allow for the prediction of
the phase of a substance that is stable at
any given temperature and pressure.
 Phase Diagram definitions
• The line T to C is the vapor pressure curve of the
liquid. It represents the equilibrium between the
liquid and the gas phases.
• The vapor pressure curve ends at C, the critical
point, which is the critical temperature and critical
pressure for that substance.
• Beyond that point, the liquid and gas phases
become indistinguishable and the state is a
supercritical fluid.
• The line that separates the solid phase
from the gas phase represents the change
in the vapor pressure of the solid as it
sublimes at different temperatures.
• An increase in pressure usually favors the
more compact solid phase, so higher
temperatures are required to melt the solid
at higher pressures.
• Point T, where the three curves intersect,
is known as the triple point. All three
phases are in equilibrium at this
temperature and pressure.
 Structures of Solids
• In a crystalline solid, the atoms, ions or
molecules are ordered in well-defined, 3-
dimensional arrangements.
• The solids have flat surfaces or faces that
make definite angles with one another.
• An amorphous solid is a solid in which
particles have no orderly structure.
 Unit Cells
• The repeating unit of a solid is called a unit
cell.
• While there are several ways to choose
the unit cell, it is generally the smallest unit
cell that shows the symmetry of the entire
pattern.
A 2-dimensional analog of a lattice and its unit cell.
This shows the repeating pattern of the lattice.
 Crystalline Solids
• A crystalline solid can be represented by a
3-D array of points called a crystal lattice.
• Each point in the lattice is called a lattice
point, and represents an identical
environment within the solid.
• It acts like a scaffolding for the whole
crystal.
Lattice points This unit cell has
There is a
are at the lattice points at
lattice point at
corners only. the center of each
the center of
face, as well as
the unit cell.
each corner.
This is a space-filling view of cubic unit cells. Only the
portion of each atom that belongs to the unit cell is shown.
In the crystal structure of NaCl, we can center either
the Na+ (purple) or the Cl- ions (green) on the lattice
points. In both cases, they are face-centered cubic.
 Close-Packing of Spheres
• Many solids have close-packed structures
in which spherical particles are arranged
in order to leave the minimum amount of
space.
• There are two forms of close-packing;
cubic close-packing and hexagonal
close-packing.
 Close-Packing of Spheres
• In both cases, each sphere has a
coordination number of 12, which
means the each sphere has 12 equidistant
neighbors.
• There are 6 neighbors in one plane, 3
below and 3 above.
Hexagonal Cubic close-
close- packing
packing
 Bonding in Solids
• The physical properties of solids, such as
melting point and hardness depend on
both the arrangement of the particles and
on the attractive forces between them.
Types of Crystalline Solids
 Covalent Network Solids
• Covalent network solids consist of atoms held
together by covalent bonds in large networks
or chains.
• Because covalent bonds are much stronger
than intermolecular forces, these solids are
much harder and have higher melting points
than regular molecular solids.
• Diamond and graphite are 2 allotropes that
are network solids.
 Ionic Solids
• Ionic solids consist of ions held together
by ionic bonds.
• The strength of the ionic bonds depends
on the charges of the ions.
• NaCl, with charges of +1 and -1, has a
melting point of 801°C. MgO, with
charges of +2 and -2, has a melting point
of 2852°C.
Unit cells of some common ionic solids.
 Metallic Solids
• Metallic solids consist of metal atoms.
• They usually have hexagonal close-packed,
cubic close-packed (face-centered) or body-
centered cubic structures.
• Each atom is typically surrounded by 8 or 12
adjacent atoms.
• Held together with delocalized valence
electrons – (sea of mobile electrons)
 Sea of
mobile
electrons
in
metallic
bonds