Intermolecular

Forces
Relevant Vocabulary
 Phase - A homogeneous part of a system in contact with other parts
of the system, but separated from t h e s e other parts by well-
defined boundaries.
 Condensed phases - Liquids and solids
 Intramolecular forces and intermolecular forces -
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a molecule.
Kinetic Molecular Theory

1. All matter is made of tiny particles.

2. These particles are in constant motion
3. The speed of particles is proportional to temperature. Increased
temperature means greater speed.
4. Solids, liquids, and gases differ in distances between particles, in the
freedom of motion of particles, and in the extent to which the
particles interact.
5. For an animation showing the motion of particles in a solid, liquid or
gas, the lesson below may be viewed.
CHECK LINK: http://preparatorychemistry.com/KMT_flash.htm
Kinetic Molecular Theory of Liquids
and Solids
Molecular level comparison of
gases, liquids and solids.
Intermolecular Forces
 They are attractive forces that act between molecules or particles in
the solid or liquid states. Generally, these attractive forces are much
weaker than bonding forces.
 Common indicators of strength of intermolecular forces are melting
points and boiling points of substances.
 When a solid melts, or a liquid boils, the particles move away
from each other. As they do, intermolecular forces of attraction
are broken. The stronger the intermolecular forces to be
broken, the larger the amount of energy needed to break
them, hence, the higher the melting point for solid to liquid
transformation, and boiling point for liquid to gas
transformation.
Different Types of Intermolecular
Forces
Dispersion forces – these forces of attraction result from temporary
dipole moments induced in ordinarily nonpolar molecules. These
forces are present between all types of molecules due to the
movement of electrons. As electrons move around the nucleus, an
uneven distribution causes momentary charge separations. Slightly
positive sides of a molecule are attracted to the slightly negative
sides of the adjacent molecule.
 The extent to which a dipole moment can be induced in a molecule is
called its polarisability.
London Dispersion Forces between
Helium Atoms
 An Illustration of London Dispersion Forces using Helium atoms (2 electrons) •
Consider atoms of helium. The average distribution of electrons around each nucleus
is spherically symmetrical. The atoms are nonpolar and possess no dipole moment.
 • At a given instant in time, the distribution of electrons around an individual atom,
may not be perfectly symmetrical. Both electrons may be on one side of the nucleus,
as shown on the leftmost atom in the figure below.
 • The atom would have an apparent dipole moment at that instant in time (i.e.
a transient dipole).
 • A close neighboring atom, shown on the right, would be influenced by this apparent
dipole. The electrons of the neighboring atom would move away from the negative
region of the dipole. Due to electron repulsion, a temporary dipole on one atom can
induce a similar dipole on a neighboring atom
 • This will cause the neighboring atoms to be attracted to one another. This is called
the London dispersion force (or just dispersion force). It is significant only when the
atoms are close together.
London Dispersion Forces between
Helium Atoms
Dipole-dipole Forces
 Attractive forces between polar molecules (molecules that possess
dipole moments). In polar molecules the electrons are unevenly
distributed because some elements are more electronegative than
others. The partial negative side of one molecule is attracted to the
partial positive side of another molecule.
 This type of force is stronger than the dispersion forces because
polar molecules have a permanent uneven distribution of electrons.
The nature of attraction is electrostatic and can be understood in
terms of Coulomb’s law: The larger the dipole moment, the stronger
the attraction.
Hydrogen Bond
 A special type of dipole-dipole interaction between the hydrogen
atom in a polar bond, such as N‒H, O‒H, or F‒H, and an
electronegative O, N, or F atom. Hydrogen bonds between water
molecules are particularly strong.
 The interaction is written as

A ‒ H ••• B or A‒
H ••• A

 A and B represent O, N, or F; A ‒ H is one molecule or part of a

molecule and A or B is a part of another molecule; the dotted line
represents the hydrogen bond.
Examples of hydrogen bonding in water (H2O),
ammonia (NH3) and hydrogen fluoride (HF):
Schematic diagram for determining
intermolecular forces in a
substance:
Alternative Schematic Diagram for determining
Intermolecular Forces in a Substance
Notes on Molecular Polarity:
 To determine the polarity of a molecule, both the bonds present and the
overall shape of the molecule should be considered. Two or more polar
bonds may cancel each other out leading to a nonpolar molecule.
 A molecule will be nonpolar if: • All of the terminal atoms (or groups) are
the same • All of the terminal atoms (or groups) are symmetrically
arranged around the central atom • The terminal atoms (or groups) have
the same charges • Example: CO2

 A molecule will be polar if: • One or more terminal atoms differ from
each other. • At least one polar bond is present. • The terminal atoms
are not symmetrically arranged • The molecule has one slightly positive
end and one slightly negative end. • Example: H2O
Properties of Liquids and Intermolecular Forces –
The properties of liquids that were observed are consequences of the interactions of
particles that make up the liquid.

Fluid - A gas or a liquid; a substance that can flow.

Surface tension - The measure of the elastic force in the surface of a liquid. It is the
amount of energy required to stretch or increase the surface of a liquid by a unit area.
Capillary action The tendency of a liquid to rise in narrow tubes or to be drawn into small
openings.
Viscosity - A measure of a fluid’s resistance to flow.
Vapor - A gaseous substance that exist naturally as a liquid or solid at normal temperature
Vaporization - The change of phase from liquid to vapor (gaseous phase).
Vapor pressure of a liquid - The equilibrium pressure of a vapor above its liquid; that is,
the pressure exerted by the vapor above the surface of the liquid in a closed container.
Boiling point - The temperature at which a liquid boils. The boiling point of a liquid when
the external pressure is 1 atm is called the normal boiling point.
Molar heat of vaporization (ΔHvap) - The energy (usually in kilojoules) required to
vaporize 1 mole of a liquid at a given temperature.
SURFACE TENSION
 Surface tension is the measure of the elastic force in the surface of a
liquid. It is the amount of energy required to stretch or increase the
surface of a liquid by a unit area.
 It is manifested as some sort of skin on the surface of a liquid or in a
drop of liquid. Use the illustrations given below to show
manifestations of surface tension.
 Molecules within a liquid are pulled in all directions by intermolecular
forces. Molecules at the surface are pulled downward and sideways by
other molecules, not upward away from the surface.
 These intermolecular forces tend to pull the molecules into the liquid
and cause the surface to tighten like an elastic film or “skin”.
CAPILLARY ACTION
 Capillary action is the tendency of a liquid to rise in narrow tubes or
be drawn into small openings such as those between grains of a rock.
Capillary action, also known as capillarity, is a result of intermolecular
attraction between the liquid and solid materials.
Two types of forces are involved in
capillary action:
 Cohesion is the intermolecular attraction between like molecules (the liquid
molecules).
 Adhesion is an attraction between unlike molecules (such as those in water and
in the particles that make up the glass tube).
 These forces also define the shape of the surface of a liquid in a cylindrical
container (the meniscus!)
 When the cohesive forces between the liquid molecules are greater than the
adhesive forces between the liquid and the walls of the container, the surface
of the liquid is convex. Example: mercury in a container
 When the cohesive forces between the liquid molecules are lesser than the
adhesive forces between the liquid and the walls of the container, the surface of
the liquid is concave. Example: water in a glass container
 When both adhesive and cohesive forces are equal, the surface is horizontal.
Example: distilled water in a silver vessel
Viscosity - is a measure of a fluid’s resistance to flow. The
greater the viscosity, the slower the liquid flows.

 Viscosity is expressed in units of centipoise. The table below gives

viscosities of liquids of some pure substances. Water has viscosity of
1 centipoise or 0.001 Pa/s at 20oC. Substances with lower viscosities
include carbon tetrachloride and benzene. Glycerol has a resistance
to flow of more than a thousand times greater than water.
VAPOR PRESSURE OF A LIQUID
 Gas molecules move in random directions, collide with other gas
particles and the walls of the container. Some will strike the liquid
surface and condense back into it. In the closed flask, none of the
gas particles are able to get out of the container, and eventually,
the number of molecules that go into the gaseous state would equal
the number of molecules that condense back.
 When the rate of condensation of the gas becomes equal to the rate
of evaporation of the liquid, the gas in the container is said to be
in equilibrium with the liquid.

liquid ⇋ vapor (gas)

 In this condition, the amount of gas and liquid no longer changes.

Vapor Pressure
 Like any gas sample, the molecules in the gaseous state over its
liquid create a pressure. The greater the number of gaseous
particles, the greater the pressure exerted by the gas. The pressure
exerted by the gas in equilibrium with a liquid in a closed container
at a given temperature is called the equilibrium vapor pressure or
simply vapor pressure of the liquid.
 The equilibrium vapor pressure is the maximum vapor pressure of a
liquid at a given temperature and that it is constant at a constant
temperature. It increases with temperature.
 Vapor pressure is independent of the amount of liquid as well as the
surface area of the liquid in contact with the gas.
Vapor Pressure of Water vs.
Temperature

Observation:
As the temperature increases, the vapor
pressure of water also increases.
When temperature is high, more molecules
have enough energy to escape from the liquid. At
a lower temperature, fewer molecules have
sufficient energy to escape from the liquid.
Given in the graph below are the vapor pressures for four common liquids: diethyl
ether, ethyl alcohol, water and ethylene glycol, as a function of temperature. For all
four liquids, the vapor pressure increases as temperature increases.
Vapor Pressure to Strength of
Intermolecular Forces - The stronger the intermolecular
forces of attraction, the lower the vapor pressure of a liquid.
 Consider the vapor pressures of the following substances. Relate
vapor pressure to strength of intermolecular forces.

Observation: Ethyl alcohol and water have very low vapor pressures. Both liquids have the
strong dipole-dipole interaction called hydrogen bonding. Acetone is polar but does not have
H-bonding. Its vapor pressure is of intermediate value. Pentane is a nonpolar substance, and its
vapor pressure is high compared to those of water and ethyl alcohol.
When liquids evaporate, the molecules have to have sufficient energy to break the attractive
forces that hold them in the liquid state. The stronger these intermolecular forces are, the
greater the amount of energy needed to break them.
For some substances with weak intermolecular forces, the energy requirement is easy obtained
from collisions with other molecules and absorption of energy from the surroundings. Many
molecules can vaporize, resulting in a high vapor pressure. For molecules with strong
intermolecular forces, gathering enough energy may not be as easy, and register low vapor
pressures.
MOLAR HEAT OF VAPORIZATION
AND BOILING POINT
 The relationship between vapor pressure and strength of
intermolecular forces is consistent with the trends in two other
properties of liquids, the enthalpy or molar heat of vaporization, and
the boiling point of the liquid.
 Molar Heat of Vaporization - The molar heat of vaporization (ΔHvap) is
the energy required to vaporize 1 mole of a liquid at a given
temperature. H is the symbol for enthalpy, which means heat
content at a given standard condition.
Boiling Point
 The boiling point of a liquid is the temperature at which the liquid converts into a gas. A
more complete definition includes the vapor pressure, and this is given below.
 A liquid boils when its vapor pressure equals the pressure acting on the surface of the
liquid. The boiling point is the temperature at which the vapor pressure of a liquid is
equal to the external pressure.
 The normal boiling point is the temperature at which the liquid converts to a gas when
the external pressure is 1 atm. The normal boiling point of water is 100oC.
 The boiling point of a liquid depends on the external pressure. For example, at 1 atm,
water boils at 100OC, but if the pressure is reduced to 0.5 atm, water boils at only 82
OC.
The boiling points of substances often reflect the strength of the intermolecular forces
operating among the molecules. At the BP, enough energy must be supplied to overcome
the attractive forces among molecules before they can enter the vapor phase.
WATER: A VERY UNUSUAL LIQUID
 Water is an essential substance to life. It is the most abundant compound on earth, and
comprises about more than 60% of the human body. But it is also one of the most
unusual substances on earth.

The Unique Properties of Water

 • Water is a good solvent. A unique property of water is its ability to dissolve a large
variety of chemical substances. It dissolves salts and other ionic compounds, as well as
polar covalent compounds such as alcohols and organic substances that are capable of
forming hydrogen bonds with water. Gases like oxygen and carbon dioxide will dissolve in
water meaning that some animals do not need to breathe air in order to respire but they
must still be able to absorb oxygen and excrete carbon dioxide. Water is sometimes
called the universal solvent because it can dissolve so many things.
 Relate this property to the role of water in plant nutrition: Plants are able to absorb
nutrient ions dissolved in water. Relate this property to issues of pollution: Issues can
be caused however by the ease of which pollutants from farming and industrial plants are
dissolved.
 • Water has a high specific heat. Specific heat is the amount of heat or energy needed to
raise the temperature of one gram of a substance by 1oC. The specific heat of water is 1
calorie/g-oC (4.18 J/g-oC), one of the highest for many liquids.
 Water can absorb a large amount of heat even if its temperature rises only slightly. To
raise the temperature of water, the intermolecular hydrogen bonds should break. The
converse is also true; water can give off much heat with only a slight decrease in its
temperature. This allows large bodies of water to help moderate the temperature on
 It takes about 4.5 times greater amount of energy to heat up water than
an equal amount of land. Hence, large bodies of water heat up and cool
down more slowly than adjacent land masses.
 • The boiling point of water unusually high. Many compounds similar in
mass to water have much lower boiling points. The strong
intermolecular forces in water allow it to be a liquid at a large range of
temperatures.
 In the plot below, the broken lines direct one to the estimated boiling
points of HF, H 2O and NH3 if H-bonding was not present in these three
substances. (Image Source: http:// www.reasons.org/Media/
Default/Article/articles/water- designed-for-life-part-2-of-7/part2-2.png)
Solid water is less dense, and in fact
floats on liquid water.
 Unlike all other liquids, the molecules in solid water are actually
farther apart than they are in liquid water. When solid water forms,
the hydrogen bonds result in a very open structure with unoccupied
spaces, causing the solid to occupy a larger volume than the liquid.
This makes ice less dense than liquid water, causing ice to float on
water.
Intermolecular Forces of Liquids
and Solids; Solids and their
Properties
Fluid - A gas or a liquid; a substance that can flow.
Crystal or crystalline solid - A solid material whose components, such as atoms, molecules or
ions, are arranged in a highly ordered microscopic structure.
Ion - An atom or group of atoms that has a net positive or negative charge.
Ionic crystal - A solid that consists of positively and negatively charged ions held together by
electrostatic forces.
Electrostatic bonding - The attraction between oppositely charged ions in a chemical compound.
Ionic bond - The electrostatic force that holds ions together in an ionic compound.
Network solid or covalent network crystal - A solid that may be a chemical compound (or
element) in which atoms are bonded by covalent bonds in a continuous
network extending throughout the material.
Molecular crystal - A solid composed of molecules held together by van der Waals forces
(dispersion force, dipole- dipole attraction, hydrogen bonding).
Covalent bond - A bond in which one or more pairs of electrons are shared by two atoms.
Dipole-dipole forces - Attractive forces between polar molecules (molecules that possess
permanent dipole moments).
 (2) Two General Types of Solids
Solids can be categorized into two groups: the crystalline solids and the amorphous solids.
The differences in properties of these two groups of solids arise from the presence or absence of long
range order of arrangements of the particles in the solid.

 Arrangement of particles
The components of a solid can be arranged in two general ways: they can
form a regular repeating three-dimensional structure called a crystal lattice, thus
producing a crystalline solid, or they can aggregate with no particular long range
order, and form an amorphous solid (from the Greek ámorphos, meaning
“shapeless”).
Crystalline solids are arranged in fixed geometric patterns or lattices. Examples
of crystalline solids are ice and sodium chloride (NaCl), copper sulfate (CuSO4),
diamond, graphite, and sugar (C12H22O11). The ordered arrangement of their
units maximizes the space they occupy and are essentially incompressible.
Amorphous solids have a random orientation of particles. Examples of amorphous
solids are glass, plastic, coal, and rubber. They are considered super-cooled liquids
where molecules are arranged in a random manner similar to the liquid state.
Amorphous solids (e.g. glass), like liquids, do
not have long range order, but may have a
limited, localized order in their structures.
Behavior when heated
 The presence or absence of long-range order in the structure of solids
results in a difference in the behavior of the solid when heated.
 The structures of crystalline solids are built from repeating units
called crystal lattices. The surroundings of particles in the structure
are uniform, and the attractive forces experienced by the particles
are of similar types and strength. These attractive forces are broken
by the same amount of energy, and thus, crystals become liquids at a
specific temperature (i.e. the melting point). At this temperature,
physical properties of the crystalline solids change sharply.
 Amorphous solids soften gradually when they are heated. They tend
to melt over a wide range of temperature. This behavior is a result of
the variation in the arrangement of particles in their structures, causing
some parts of the solid to melt ahead of other parts.
The Crystal Lattice
Crystalline solids are characterized by a regular repeating structure called the crystal
lattice.
X-ray Diffraction - technique used to determine the
atomic and molecular structure of a crystal, wherein atoms cause
a beams of incident X-rays to diffract into many specific directions.
 A stream of X-rays directed at a crystal diffracts and scatters as it
encounters atoms. The scattered rays interfere with each other and
produce a pattern of spots of different intensities that can be
recorded on film, such as that shown in the figure below. X-ray
diffraction has provided much of our knowledge about crystal
structure. Below is an image of a diffraction pattern produced by an
8 keV electron beam incident on a graphite crystal.
(4) Types of Crystals
1. METALLIC CRYSTALS - Metallic crystals are made of atoms that
readily lose electrons to form positive ions (cations), but no atoms in the
crystal would readily gain electrons. The crystal is held together by
electrostatic interactions between the cations and delocalized electron.
These interactions are called metallic bonds. This model of metallic
bonding is called the “sea of electrons” model.
Explanation of properties:
 • High melting point – a large amount of energy is needed to melt the
crystal since the forces of attraction to be broken are numerous and
extend throughout the crystal.
 • Dense – atoms are packed closely together. Metals exhibit close-packing
structures, a most economical way by which atoms utilize space. •
Electrical conductivity – then delocalized electrons move throughout the
crystal.
 • Thermal or heat conductor – the delocalized electrons collide with each
other as they move through the crystal, and it is through these collisions
that kinetic energy is transferred .
 • Malleability/ductility – when stress is applied to the metal, the metal
cations shift in position, but the mobile electrons simply follow the
movement of the cations. The attractive forces between cations and
mobile electrons are not broken.
 • Luster – the motion and collisions of electrons allow it to gain and lose
energy, some of these in the form of emitted light that is observed as
luster.
2. IONIC CRYSTALS - are made of ions
(cations and anions).
 These ions form strong electrostatic interactions that hold the crystal
lattice together. The electrostatic attractions are numerous and
extend throughout the crystal since each ion is surrounded by several
ions of opposite charge, making ionic crystals hard and of high
melting points. The figure below shows a model of NaCl crystal,
where one Na+ ion is surrounded by six Cl- ions, and a Cl- ion is
likewise surrounded by six Na+ ions.
3. MOLECULAR CRYSTALS - are made
of atoms, such as in noble gases, or molecules, such as in
sugar, C12H22O11, iodine, I2, and naphthalene, C10H8.

 The atoms or molecules are held together by a mix of hydrogen

bonding/ dipole-dipole and dispersion forces, and these are the
attractive forces that are broken when the crystal melts.. Hence,
most molecular crystals have relatively low melting points.
4. COVALENT NETWORK CRYSTALS - are made
of atoms in which each atom is covalently bonded to its nearest neighbors.
The atoms can be made of one type of atom (e.g. Cdiamond and
Cgraphite) or can be made of different atoms (e.g. SiO2 and BN).

 In a network solid, there are no individual molecules and the

entire crystal may be considered one very large molecule. Formulas
for network solids, like those for ionic compounds, are simple ratios of
the component atoms represented by a formula unit.
Comparison of Types of Solids
Intermolecular Forces of Liquids
and Solids; Phase Changes
Fluid - A gas or a liquid; a substance that can flow.
Phase - A homogeneous part of a system in contact with other parts of the system, but separated by well-
defined boundaries.
Solid - A phase of matter with definite shape and volume.
Liquid - A phase of matter with definite volume but no definite shape.
Gas - A phase of matter with no definite shape or volume of its own.
Intermolecular forces - Intermolecular forces are attractive forces between molecules.
Phase changes - Transformations of matter from one phase to another.
Melting - A phase change from solid to liquid.
Vaporization - A phase change from liquid to gas. Sublimation A phase change from solid to gas.
Condensation - A phase change from gas to liquid.
Freezing - A phase change from liquid to solid.
Deposition - A phase change from gas to solid.
Exothermic process - Process that gives off or release heat to the surroundings.
Endothermic process - Process that absorbs heat from the surroundings.
Specific heat of a substance -The amount of heat needed to raise the temperature of 1 gram of a substance by
1 OC.
Phase Changes - are transformations of matter from one physical state to
another. They occur when energy (usually in the form of heat) is added or removed from a
substance. They are characterized by changes in molecular order; molecules in the solid
phase have the greatest order, while those in the gas phase have the greatest randomness
or disorder.

The figure below illustrates the difference in molecular order of

a substance in the solid, liquid and gaseous states.
The next figure shown below summarizes the types of phase
changes:
• The change from solid to liquid is melting, liquid to gas is
vaporization, and solid to gas is sublimation. These changes take
place when heat is absorbed (heat gained). They are endothermic
processes.
• The reverse change from gas to liquid is condensation, gas to solid is
deposition, and liquid to solid is freezing. These changes give off heat
(heat lost) and are exothermic processes.
How does a change in energy affect
phase changes?
 Phase changes occur when heat is added or removed from a substance.
When a substance is heated, the added energy is used by the substance
in either of two ways:
a. The added heat increases the kinetic energy of the particles and the
particles move faster. The increase in kinetic energy is accompanied by
an increase in temperature.
b. The added heat is used to break attractive forces between particles.
There is no observed increase in temperature when this happens. Often
a change in the physical appearance of the substance is observed, such
as a phase change.
c. Conversely, the removal or release of heat results in two ways:
1. A decrease in kinetic energy of the particles. The motion of the particles slow
down. A decrease in temperature is observed.
2. Forces of attraction are formed, and a phase change may occur. No change in
temperature is observed.
 In both the heating and cooling curves, there are certain portions where
the temperature changes as heat is being added or removed, and portions
where the temperature remains constant even if heat is being added or
removed. What is happening at these portions?
1. When heat change is accompanied by a change in temperature, a
change in kinetic energies of the particles in the substance is occurring. The
particles are either moving faster or slowing down.
2. When temperature remains constant during heat change, the
particles move at the same speed. The heat added or removed is involved in
breaking or forming attractive forces. A phase change occurs at this
temperature: solid melts or liquid freezes at the melting point, which is also
the freezing point; liquid boils, or gas condenses at the boiling point, which is
also the condensation point.
During phase changes, two physical states of the substance exist at
the same time. When addition or removal of heat is stopped at this
temperature, the two physical states will interconvert from one state to the
other, and will be at equilibrium.
MELTING AND FREEZING: SOLID-
LIQUID EQUILIBRIUM
 When a solid is heated, its temperature increases until it reaches its melting
point. At this temperature, the average kinetic energy of the molecules has
become sufficiently large to begin overcoming the intermolecular forces that
hold the molecules of a solid state together. The heat absorbed is used to
break apart more and more of the molecules in the solid. The transformation
of solid to liquid is called melting, and the reverse process is called freezing.
• During the transition, the average kinetic energy of the molecules does not change, so the
temperature stays constant. The melting point of a solid or the freezing point of a liquid is the
temperature at which solid and liquid phases coexist in equilibrium.
• Melting points are distinct for each substance. It is dependent on the strength of attractive
forces that hold the particles in the solid. The stronger the attractive forces that hold the
particles in the solid, the higher is the melting point of the substance.
• The melting (or freezing) point of a substance when the external pressure is 1 atm pressure is
called its normal melting (or freezing) point. For water, this is 0oC.
• At 0OC and 1 atm, the dynamic equilibrium for water and ice is represented by:
MOLAR HEAT OF FUSION AND MELTING POINT - Heat
of fusion is an extensive property. The actual amount of energy involved in the
transformation of a substance from solid to liquid is dependent on the amount of sample
used. Thus, this property is often expressed in terms of molar quantities of sample

 Molar heat of fusion (ΔHfus) is the energy required to melt 1 mole of a

solid.
 For water, the molar heat of fusion is 6.01 kJ / mol. and its vaporization is
40.7 kJ/mol. If the heat input is constant, a longer period is needed for
one mole of water to evaporate than the time needed for the ice to melt.
An 18-gram sample of ice at 0oC will need 6.01 kJ of energy to be
completely transformed into liquid water, still at 0oC.
 Like melting points, heats of fusion are influenced by the strength of
attractive forces that exist between particles in the solid. The stronger
the attractive forces that hold the particles of the solid together, the
larger is the heat of fusion.
 The molar heat of fusion is equal to the amount of energy released when
one mole or 18 grams of liquid water at 0oC freezes to ice, still at 0oC.
Cooling a substance has the opposite effect of heating it, as can be seen
from the cooling curve.
 If heat is removed from a liquid at a steady rate, its temperature should
decrease until the freezing point is reached. As the solid is being formed,
heat is given off by the system, as attractive forces form and become
stronger between particles. Even if heat is being removed, the
temperature of the system remains constant over the freezing period.
 After all the liquid has frozen, the temperature of the solid drops.
 The heat change (q) for a given sample during freezing or melting may be
calculated using the following equation: is given by
BOILING AND CONDENSING: LIQUID-
VAPOR EQUILIBRIUM
In the liquid phase, there are still attractions among its particles. The particles are still in contact with each
other but are not locked into fixed positions and are free to move past each other. Although they lack the total
freedom of gaseous molecules, these molecules are in constant motion.
 When a liquid is heated, its temperature increases as the kinetic energy of the molecules increases. When
the molecules have sufficient energy to escape from the surface, a phase change occurs. Evaporation or
vaporization is the process in which a liquid is transformed into a gas. The temperature at which this
occurs is the boiling point of the substance. While the liquid vaporizes, the temperature remains constant.
 The boiling point is a characteristic of each substance, and is dependent on the strength of attractive forces
that hold the particles or molecules in the liquid state. It is also dependent on the external or atmospheric
pressure. The boiling point of a liquid at 1 atm pressure is called its normal boiling point. For water, this is at
100oC.
 The reverse of vaporization or boiling is called condensation, the change from the gas phase to the liquid
phase. Condensation occurs because a molecule strikes the liquid surface and becomes trapped by
intermolecular forces in the liquid. This process occurs at the same temperature when the liquid vaporizes
into the gaseous state. The boiling point can thus be also called condensation point (dew point), and occur
at the same temperature.
 At the boiling point, both liquid and gaseous states of the substance are present, and the transformations of
liquid to gas and gas to liquid happen at the same time.
 At 100 OC and 1 atm, the dynamic equilibrium for water and steam is represented by

As heat is absorbed, some water will boil off but the temperature remains at 100 OC (373.15 K) until
all the liquid has vaporized. The amount of heat absorbed by the sample as the liquid transforms into
gas is called heat of vaporization. When all of the sample has turned into gas, further heating will
cause the temperature of the gas to increase again.
MOLAR HEAT OF VAPORIZATION
(ΔHvap) AND BOILING POINT
 The heat of vaporization is an extensive property and is thus
dependent on the amount of sample undergoing phase change.
Hence, published quantities of heats of vaporization specify the
amount of substance, and is often expressed as molar heat of
vaporization.
 Molar heat of vaporization (ΔHvap) is defined as the energy
(usually in kilojoules) required to vaporize 1 mole of a liquid at a
given temperature, usually, at the boiling point. The molar heat of
vaporization of water at 100oC is 40.8 kJ/mol.
 Both the boiling point and molar heat of vaporization of a
substance are influenced by the strength of attractive forces
that hold the particles in the liquid state. This can be seen
from the table given below. • The boiling point is related to
molar heat of vaporization: the higher ΔHvap , the higher the
boiling point, as shown in the table.
SOLID-VAPOR EQUILIBRIUM
In a solid, the particles may be in fixed positions, but they
are able to vibrate in place and with increasing intensity as
temperature increases. When particles are able to acquire
enough energy to break attractive forces with adjacent particles,
the energetic particles may move into the gaseous state. This
phase change is called sublimation. One of the most familiar
examples of sublimation is that of dry ice. The figure below
shows iodine subliming into a purple gas.
Sublimation
 Sublimation is the process in which molecules go directly from solid
into vapor phase. The reverse process is called deposition, where
molecules make a transition directly from vapor to solid. The process
may be represented by the following equilibrium:
 MOLAR HEAT OF SUBLIMATION
 Molar heat of sublimation (ΔHsub) of a substance is the amount of energy that must be
added to a mole of solid at constant pressure to turn it directly into a gas, without passing
through the liquid phase. This enthalpy change associated with sublimation is always greater
than that of vaporization even if both sublimation and evaporation involve changing a
substance into its gaseous state because in sublimation, the starting physical state of the
substance is the solid state, which is lower in energy than the liquid state where vaporization
starts.
 Sublimation requires that all the forces are broken between the molecules (or other species,
such as ions) in the solid as the solid is converted into a gas.. A comparison of the magnitudes
of these thermochemical quantities can be seen from the heating curve shown below.
HEAT CHANGE WITH CHANGE IN TEMPERATURE
 When a system contains only one phase (solid, liquid, or gas), the
temperature will change when it receives energy during heating or when
energy is removed during cooling. The amount of heat received or removed
from the sample to effect a given change in temperature can be calculated
using the specific heat of the substance. This is the amount of heat needed
to raise the temperature of 1 gram of a substance by 1OC. It is also equal to
the amount of heat lo0st by 1 gram of substance when its temperature drops
by 1oC. The specific heat of a substance differs for the solid, liquid, and
gaseous states. Water as an example, has the following specific heat at
different phases:
H2O(l) = 4.18 J / g OC
H2O(s) = 2.06 J / g OC
H2O(g) = 2.02 J / g OC
The heat change (q) for this process is given by:

where m = mass of sample in grams

S = specific heat of the sample in the appropriate
physical state
T = change in temperature
Intermolecular Forces of Liquids
and Solids; Phase Diagrams
 Sublimation (or deposition) curve - The curve on a phase
diagram which represents the transition between the gaseous and
solid states.
 Triple point - The point on a phase diagram at which the three
states of matter coexist.
 Critical point - The point in temperature and pressure on a phase
diagram where the liquid and gaseous phases of a substance merge
together into a single phase. The temperature and pressure
corresponding to this are known as the critical temperature and
critical pressure.
 Normal melting and boiling points - Melting and boiling points
when the pressure is 1 atm.
Phase Diagram
 A phase diagram is a graphical representation of the physical states
of a substance under different conditions of temperature and
pressure. It gives the possible combinations of pressure and
temperature at which certain physical state or states a substance
would be observed. Each substance has its own phase diagram. A
typical phase diagram is shown below.
Features of a Phase Diagram
A. The Three Areas
 The three areas are marked solid, liquid, and vapor. Under a set of conditions in the
diagram, a substance can exist in a solid, liquid, or vapor (gas) phase. The labels on
the graph represent the stable states of a system in equilibrium.
 Suppose a pure substance is found at three different sets of conditions of
temperature and pressure corresponding to A, B, and C as shown in the following
diagram:

Under the set of conditions at A in the diagram, the substance would be a solid as
it falls into that area of the phase diagram. At B, it would be a liquid; and at C, it
would be a vapor (gas).
B. Three Lines (Curves)
The lines that serve as boundaries between physical states represent the
combinations of pressures and temperatures at which two phases can exist in
equilibrium. In other words, these lines define phase change points.
1. The green line divides the solid and liquid phases, and represents melting (solid
to liquid) and freezing (liquid to solid) points.
Melting (or freezing) curve – the curve on a phase diagram which represents the
transition between liquid and solid states. It shows the effect of pressure on the melting
point of the solid. Anywhere on this line, there is equilibrium between the solid and the
liquid.
 2. The blue line divides the liquid and gas phases, and
represents vaporization (liquid to gas) and condensation (gas to liquid)
points
Vaporization (or condensation) curve - the curve on a phase diagram
which represents the transition between gaseous and liquid states. It shows
the effect of pressure on the boiling point of the liquid. Anywhere along this
line, there will be equilibrium between the liquid and the vapor.
 3. The red line divides the solid and gas phases, and represents
sublimation (solid to gas) and deposition (gas to solid) points.

Sublimation (or deposition) curve – the curve on a phase diagram

which represents the transition between gaseous and solid states. It
represents the effect of increased temperature on a solid at a very low
constant pressure, lower than the triple point.
C. Two Important Points - There are two important points on the
diagram, the triple point and the critical point.
The triple point The triple point is the combination of pressure
and temperature at which all three phases of matter are at equilibrium.
It is the point on a phase diagram at which the three states of matter
coexist. The lines that represent the conditions of solid-liquid, liquid-
vapor, and solid-vapor equilibrium meet at the triple point
It is a unique combination of temperature and pressure where
all three phases are in equilibrium together.
The critical point The critical point terminates the liquid/gas
phase line. It is the set of temperature and pressure on a phase
diagram where the liquid and gaseous phases of a substance merge
together into a single phase. Beyond the temperature of the critical
point, the merged single phase is known as a supercritical fluid.
The temperature and pressure corresponding to this are known as
the critical temperature and critical pressure.
If the pressure on a gas (vapor) is increased at a temperature lower than
the critical temperature, the liquid vapor equilibrium line will eventually
be crossed and the vapor will condense to give a liquid.
How is the normal melting and boiling
points determined in a phase diagram?
The normal melting and boiling points are those when the pressure is 1
atmosphere.

These can be found from the phase diagram by drawing a line

across pressure at 1 atm.
The Phase Diagram for Water
 There is only one difference between the phase diagram for water
and the other phase diagrams discussed. The solid-liquid equilibrium
line (the melting point curve) slopes backwards rather than forwards.
 For water, the melting point gets lower at higher pressures. This is
because solid ice is less dense than liquid water. This phenomenon is
caused by the crystal structure of the solid phase. In the solid forms
of water and some other substances, the molecules crystallize in a
lattice with greater average space between molecules, thus resulting
in a solid occupying a larger volume and consequently with a lower
density than the liquid. When it melts, the liquid water formed
occupies a smaller volume
 An increase in pressure will move the above equilibrium to the side
with the smaller volume. Liquid water is produced. To make the
liquid water freeze again at this higher pressure, the temperature
should be reduced. Higher pressures mean lower melting (freezing)
points.
Identifying data from the phase diagram
of water:

 Notice that the triple point for water occurs at a very low pressure,
0.006 atm and at 273.2 K temperature. Also notice that the critical
temperature is 647 K (374°C). It would be impossible to convert
water from a gas to a liquid by compressing it above this
temperature. The critical pressure is 218 atm.
 The normal melting and boiling points of water are found in exactly
the same way as we have already discussed - by determining where
the 1 atm pressure line crosses the solid-liquid, and then the liquid-
vapor equilibrium lines. The normal melting point of water is 273 K
(0 oC), and its normal boiling point is 373 K (100 oC).
The Phase Diagram for Carbon Dioxide
 The only thing special about this phase diagram is the position of the
triple point, which is well above atmospheric pressure. It is impossible
to get any liquid carbon dioxide at pressures less than 5.2
atmospheres.
 At 1 atm pressure, carbon dioxide will sublime at a temperature of
197.5 K (-75.5 °C). This is the reason why solid carbon dioxide is
often known as "dry ice." There is no liquid carbon dioxide under
normal conditions - only the solid or the vapor.