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7Condensed

phases:
liquids and
solids
7.1 Liquids
• In a liquid, intermolecular forces are
strong enough to confine the
molecules to a specific volume
• Molecules are able to move freely
within a liquid
• Liquids are fluid
• Liquids cannot expand or contract
significantly
7.1 Liquids
• Properties of liquids
– Surface tension
• Measure of the resistance of a liquid to an
increase in its surface area
• There is a net attractive force on molecules
at the surface that pulls them towards the
interior of the liquid
• Cohesive forces attract molecules in the
liquid to one another
• Adhesive forces attract molecules in the
liquid to the walls of the container
7.1 Liquids
7.1 Liquids
– Capillary action
• The upward movement of water against the
downward force of gravity
7.1 Liquids
– Viscosity
• A liquid’s resistance to flow
• The greater the viscosity, the more slowly the
liquid pours
• A measure of how easily molecules slide by
one another
• This is affected by a combination of molecular
shape and the strength of the intermolecular
forces
• Viscosity is affected by temperature
7.1 Liquids
• Vapour pressure
– The distribution of molecular energies
guarantees that some of the molecules
in any liquid have enough kinetic energy
to overcome the intermolecular forces
that confine the liquid
– Whenever a liquid has an exposed
surface, some of its molecules will
escape into the vapour phase
7.1 Liquids
– The number of molecules of a liquid that have
enough energy to escape into the vapour
phase depends on:
• The strength of intermolecular forces
• The temperature
7.1 Liquids
– Vapour pressure is the pressure at which
dynamic equilibrium is achieved in a
closed container
7.2 Solids
• Magnitudes of forces
– Forces in solids range from very small to
extremely large
– Ions, atoms or molecules in solids can
be bound together by various attractive
forces:
• Intermolecular forces
• Metallic bonding
• Covalent bonds
• Ionic interactions
7.2 Solids
7.2 Solids
• Molecular solids
– Aggregates of molecules bound together
by intermolecular forces
– The forces can be dispersion, dipolar,
hydrogen bonding or a combination
– Many larger molecules have sufficient
dispersion forces to exist as solids at
room temperature
– Eg naphthalene
7.2 Solids
7.2 Solids
– Dimethyl oxalate is an example of a molecular
solid with dipolar interactions

– Crystals of benzoic acid contain pairs of


molecules held together head to head by
hydrogen bonds. These pairs then stack in
planes which are held together by dispersion
forces
7.2 Solids
7.2 Solids
• Network solids
– Have very high melting points
– Held together by covalent bonds which
are much harder to break than
intermolecular forces
– Bonding patterns determine the
properties of network solids
– Covalent bonds make network solids
extremely durable
7.2 Solids
7.2 Solids
• Metallic solids
– Derives primarily from electrons in highly
delocalised valence orbitals
– Consists of a regular array of metal atoms
embedded in a ‘sea’ of mobile valence
electrons
7.2 Solids
– Wide range of melting points
– Strength of metallic bonding is variable
– Metals are ductile and malleable
7.2 Solids
7.2 Solids
• Ionic solids
– Contain cations and anions strongly
attracted to each other by electrostatic
forces
– Their stoichiometries are determined by
the charges carried by the positive and
negative ions
– Many ionic solids contain metal cations
and polyatomic anions
7.3 Phase changes
• There are three different phases of
matter: gas, liquid and solid
• A phase change is the transition of a
substance from one phase to another
• Phase changes depend on
temperature, pressure, and the
magnitudes of intermolecular and
bonding forces
7.3 Phase changes
7.3 Phase changes
• As a phase change occurs, temperature
remains constant
• A substance must completely change phase
before the temperature of the system can
increase (or decrease)
• Phase changes require that energy (usually
in the form of heat) be either supplied to or
removed from the substance undergoing
the phase change
7.3 Phase changes
• Molar enthalpy of vaporisation, ∆ Hvap : the heat
needed to vaporise one mole of a substance at
its normal boiling point.
• Molar enthalpy of fusion, ∆ Hfus : the heat needed
to melt one mole of a substance at its normal
melting point.
• Molar enthalpy of sublimation, ∆ Hsub : the heat
needed to vaporise one mole of a substance from
the solid phase (skips the liquid phase)
7.3 Phase changes
7.3 Phase changes
• The effect of pressure is mainly seen
for phase transitions involving gases
• A gas at constant temperature can be
liquefied by increasing the pressure
• The pressure at which a gas liquefies
at a specific temperature is known as
the condensation point
7.3 Phase changes
– Supercritical fluids
• A supercritical fluid is a fluid that has certain
properties of both liquids and gases
• The critical temperature is the temperature at
which the densities in the gas phase and
liquid phase become equal and we can no
longer distinguish between phases or
observe a phase boundary
• The associated pressure is called the critical
pressure
• The combination of these is the critical point
7.3 Phase changes
7.3 Phase changes
• Phase diagrams
– A way of showing the phase behaviour of a
substance as a function of temperature and
pressure
7.3 Phase changes
– Characteristic features of phase diagrams:
• Boundary lines between phases separate the
regions where each phase is
thermodynamically stable
• Movement across a boundary line corresponds
to a phase change
• At any point along a boundary line, the two
phases on either side of the line coexist in a
state of dynamic equilibrium
7.3 Phase changes
• Three boundary lines meet at a single point
called a triple point
• Above the temperature specified by the
critical point, the gas cannot be liquefied
under any pressure
• What happens as temperature changes at
constant pressure can be determined by
drawing a horizontal line at the appropriate
pressure on the phase diagram
• The temperature for conversion between the
gas phase and a condensed phase depends
strongly on pressure
7.3 Phase changes
• The melting temperature is almost independent of
pressure, and making the boundary line between
solid and liquid nearly vertical
• The solid-gas boundary line extrapolates to
p = 0 Pa and T = 0 K
7.3 Phase changes
– All phase diagrams of pure substances share
the 10 common features listed previously
– The detailed appearance of a phase diagram is
different for each substance, as determined by
the strength of the interactions between its
constituents
– Phase diagrams are constructed by measuring
the temperatures and pressures and which
phase changes occur
7.3 Phase changes
7.3 Phase changes
– Many
substances
have more
than one solid
phase
7.4 Order in solids
• Molecules in gases and liquids can
move relatively freely
• The atoms, molecules or ions in a
solid are in fixed positions
• Their motions are restricted to
vibrations about these fixed positions
7.4 Order in solids
• Close-packed structures
– Assume we can approximate a metal
atom with a sphere
– A hexagonal arrangement is able to fit
more spheres into the same area
– This hexagonal arrangement of identical
spheres is the most dense packing you
can achieve in one layer of spheres
7.4 Order in solids
7.4 Order in solids
– When a second layer is added, to achieve the
most compact arrangement, each sphere in
layer B sits in one of the ‘dimples’ between a
trio of spheres in layer A
7.4 Order in solids
– As additional layers of spheres are added, the
layer B eventually looks identical to the layer A,
except offset slightly to allow the spheres to
nestle in the dimples formed by the layer below
7.4 Order in solids
– If spheres in the third layer lie directly
above the first, the structure is called
hexagonal close-packed (hcp)
– If spheres in the third layer are offset
from both of the layers, the structure is
called cubic close-packed (ccp)
– The two structure types are called close-
packed structures because they achieve
maximum space filling for identical
spheres
7.4 Order in solids
7.4 Order in solids
7.4 Order in solids
• The crystal lattice and the unit cell
– A lattice is a pattern of points
– Every individual point is a lattice point

– The unit cell is the smallest unique repeating unit of a


lattice
7.4 Order in solids
– The same lattice can be used to describe
many different designs or structures
7.4 Order in solids
• Cubic structures
– In a simple cubic crystal, layers of atoms
stack one directly above another, so that all
atoms lie along straight lines at right angles
7.4 Order in solids
– Primitive cubic structure: layers of
atoms stacked one directly above
another, so that all atoms lie along
straight lines at right angles
– Body-centred cubic lattice (bcc): simple
cube with one entire atom in the center
of the cube (in the body)
– Face-centred cubic (fcc): simple cube
with atoms in the center of each face of
the cube
7.4 Order in solids
• Ionic solids
– The packing in ionic crystals requires
that ions of opposite charge alternate
with one another to maximise attractions
and minimise repulsions
– The cations and anions are usually
different sizes
– Adopt a variety of structures that depend
on the stoichiometry and relative sizes of
the ions
7.4 Order in solids

– Many ionic solids have the same unit cell


structure as the sodium chloride lattice
7.4 Order in solids
– Many ionic
compounds have
stoichiometries that
differ from 1:1
7.5 X-ray diffraction
• Can be used to determine the
arrangement of atoms, ions or
molecules in a crystalline structure
• When the crystal is exposed to
X-rays, intense beams, diffracted
because of constructive interference,
appear only in specific directions
• In other directions, no X-rays appear
because of destructive interference
7.5 X-ray diffraction
• The X-rays coming from the crystal are
recorded and form a diffraction pattern
7.5 X-ray diffraction
• The Bragg equation relates λ, θ and the
distance between the planes of atoms,
d: nλ = 2dsinθ
7.6 Amorphous solids
• When a liquid is cooled slowly, it often
solidifies as a crystalline solid
• When solids form rapidly, their atoms,
ions or molecules may become
locked into positions other than those
of a regular crystal
• These materials are said to be
amorphous, meaning ‘without form’
7.6 Amorphous solids
• Do not diffract
X-rays
• Glass is an entire
family of
amorphous solids
based on silica
7.7 Crystal imperfections
• Many solid materials are crystalline but
contain defects
• Crystalline defects can profoundly alter
the properties of a solid material
• Doped semiconductors are solids into
which impurity ‘defects’ are introduced
• Some gemstones are crystals containing
impurities giving them colour
7.7 Crystal
imperfections
– Substitutional
impurities replace one
atom with another

– Interstitial impurities
occupy the spaces
between regular
atoms
7.8 Modern ceramics
• Ceramics are materials composed of
inorganic components that have been
heat-treated
• Many manufactured ceramics are
made from inorganic minerals such as
clay, silica (sand) and other silicates
• In recent times, advanced ceramics
have been prepared by chemists
7.8 Modern ceramics
• Properties of ceramics
– Almost all ceramics are very hard
– They have very high melting points
– Are often used as refractories
– Most ceramics do not conduct electricity
– Generally contain metals with high
positive oxidation states, combined with
small nonmetals with high negative
oxidation states
7.8 Modern ceramics
7.8 Modern ceramics
• Applications of advanced ceramics
– Thin ceramic films are used as
antireflective coatings on optical surfaces
– Partially stabilised zirconia is used to
make portions of hip-joint replacements
– Boron nitride powder is used in cosmetics
– Silicon nitride is used to make engine
components for diesel engines
7.8 Modern ceramics
• High-temperature superconductors
– A superconductor is a material which
offers no resistance to the flow of
electricity
– They can be levigated by a magnetic field
Summary
• Liquids are fluids, but cannot expand
or contract significantly
• Viscosity, surface tension and
capillary action depend mostly on the
strengths of intermolecular attractions
within the liquid
• Vapour pressure is the pressure at
which the number of molecules
escaping the liquid exactly matches
the number being captured
Summary
• Solids are rigid
• Solids may be classified as molecular,
metallic, network or ionic solids
• A phase change occurs when a
substance undergoes a transition
from one phase to another
• Temperatures and pressures at which
equilibria can exist between phases
are shown in a phase diagram
Summary
• Approximating atoms as spheres allows
us to determine their possible close-
packed arrangements
• The overall structure of any crystalline
solid can be described in terms of a
repeating three-dimensional array of
lattice points, which is called a lattice
• X-ray diffraction can be used to
determine the structure of crystalline
solids
Summary
• Amorphous solids do not have a
regular arrangement of atoms, ions or
molecules
• The most important example is glass
• Crystalline defects can significantly
alter the properties of a solid
• Ceramics are composed of inorganic
components that have been heat-
treated