Lesson 1: Kinetic Molecular Model of Liquids and Solids

The kinetic molecular theory of matter offers a description of the microscopic properties of atoms
(or molecules) and their interactions, leading to observable macroscopic properties (such pressure,
volume, as temperature). An application of the theory is that it helps to explain why matter exists in
different phases (solid, liquid, and gas) and how matter can change from one phase to the next.
Intermolecular forces are electrostatic in nature; that is, they arise from the interaction between
positively and negatively charged species.
Intermolecular forces 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.
When a solid melts, or a liquid boil, 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.

The different types of intermolecular forces are the following:

• Dispersion forces - these forces of attraction result from temporary dipole moments induced
in ordinarily nonpolar molecules. These forces are pre- sent between all types of molecules
due to the movement of electrons. As electrons move around the nucleus, an uneven
distribution causes mo- mentary charge separations. Slightly positive sides of a molecule are
at- tracted 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.
Polarizability of the atom or molecule refers to the ease with which the electron distribution
can be distorted. Generally, the larger the number of electrons and the larger or more diffused
the elec- tron cloud in the atom or molecule, the greater its polarizability. Thus, dis- persion
forces may be the weakest of intermolecular forces that can exist between two molecules,
but the larger the atoms present, the stronger the dispersion forces.

• For example, F2, the lightest halogen, is a gas, Br2 is a liquid, and the heavier 12,is a solid
at room conditions. Further, the more atoms that make up the molecules, the stronger are
the dispersion forces. Methane, CH4, is gaseous, but larger hydrocarbons like butane,
C4H10. is liquid, and those with larger number of carbon atoms, like the waxes, are solids at
room temperature.
An Illustration of London Dispersion Forces using Helium atoms (2 elec- trons)
❖ Consider atoms of helium. The average distribution of electrons around each nucleus is
spherically symmetrical. The atoms are nonpolar and pos- sess no dipole moment.
❖ At a given instant in time, the distribution of electrons around an indi- vidual 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.
• Dipole-dipole forces are 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 mol- ecules 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 is 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 electro- negative O,
N, or F atom. Hydrogen bonds
between water molecules are
particularly strong.
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 hydro- gen bond.
Examples of hydrogen bond- ing in water
(H_{2}*O) ammonia (N*H_{3}) and
hydrogen fluoride (HF):

Lesson 2: Properties of Liquids a Intermolecular Forces

Abstraction and Generalization
• Surface tension, capillary action, and viscosity are unique properties of liquids that depend on
the nature of intermolecular interactions. Surface tension is the energy required to increase the
surface area of a liquid.
• Surface tension is the measure of the elastic force in the surface of a liq- uid. 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.

 • 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

• 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.

• Capillary action is shown by water rising spontaneously in capillary tubes. A thin film of water
adheres to the wall of the glass tube as water molecules are attracted to atoms making up the
glass (SiO2). Surface tension causes the film of water to contract and pulls the water up the
tube.

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).
❖ 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 sur- face of the liquid is
concave.
▪ Example: water in a glass container
❖ 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 sur- face of the liquid is
concave.
▪ Example: water in a glass container

• Viscosity is a measure of a fluid's

resistance to flow. The greater the vis-
cosity, the slower the liquid flows.

• Viscosity is expressed in units of

centipoise. The table below gives viscosi-
ties 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
• 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 sur- face area of the
liquid in contact with the gas.

MOLAR HEAT OF VAPORIZATION

• The molar heat of vaporization
(AHvap) 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
con- verts into a gas. A more
complete definition includes the
vapor pressure, and this is given
below.
• A liquid boil 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 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 °C.

• 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 be- fore they can enter the vapor phase.
LESSON I-Phase Changes

• The three phases of matter namely, gas, liquid,

and solid are always involved in every reaction.
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.

• In regular, repeated patterns, the molecules which make up a solid are arranged. They are
held firmly in place but can vibrate within a limited area. The molecules that simply make a
liquid flow around one another. With attractive forces between them, they are kept from
flying apart. Liquid assumes the shape of their containers. Lastly, the molecules that make
up a gas fly in all directions at great speeds. They are so far apart that attractive forces
between them are insignificant.

The Types of Phase Changes:

1. The change from solid to liquid is melting.
2. Liquid to gas is vaporization.
3. Solid to gas is sublimation.

These changes take place when heat is absorbed (heat gained). They are endothermic
processes.

1. The reverse change from gas to liquid is condensation.

2. Gas to solid is deposition.
3. Liquid to solid is freezing.

Such modifications emit heat (heat lost) and are Exothermic processes.

• A phase diagram is a graphical depiction of a substance's physical states under varying

temperature and pressure conditions. It gives the potential combinations of pressure and
temperature at which a substance will be observed in certain physical condition or states. Each
substance has its own phase diagram. A typical phase diagram is shown below.
Phase diagrams are plots of pressure (usually in the atmosphere) vs temperature (usually in
degrees Celsius or Kelvin). The diagram is split between solid, liquid, and gaseous states. The
boundary between the liquid and gaseous regions stops at red dot, the critical point for the
substance. The lines that serve as physical state borders represent the combinations of pressures
and temperatures at which two phases can exist in equilibrium. In other words, these lines identify
points for phase transition.

There are two important points on the diagram – the triple point, and the critical point.
Triple point is a unique
combination of temperature and
pressure where all three phases
are in equilibrium together. At the
triple point, the lines depicting the
conditions of solid-liquid, liquid-
vapor, and solid-vapor equilibrium
meet.
Critical point terminates the
liquid/gas phase line and relates to
the critical pressure, the pressure
above which a supercritical fluid
form. The temperature and
pressure associated with the triple point lie below the standard temperature and pressure for most
compounds. While the pressure for the critical point lies above standard pressure. Therefore, most
substances changes from solid to liquid to gas at standard pressure as the temperature rises, and
most substances change from gas to liquid to solid at standard temperature as the pressure
increases.

• There is only one difference between

the phase diagram for water and the
other phase diagrams. The solid-liquid
equilibrium line (the melting point curve)
slopes backwards rather than forwards.

• For water, at greater pressures, the

melting point gets lower. The
explanation for this is that solid ice is
less compact 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. On the other hand, the only thing special about
the phase diagram of carbon dioxide 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). Therefore, solid carbon dioxide is also called "dry ice." Under normal conditions, there is no
liquid carbon dioxide - only the solid or the vapor.

Moving on, how does a change in energy affect phase changes? ✓ Phase changes occur when
heat is added or removed from a substance. The added energy is used by the substance in either
of two ways when a substance is heated: 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 between particles to break off attractive forces.
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. Conversely, in two ways, the
loss or release of heat results in: a. A decline in the particles' kinetic energy. The motion of the
particles slows down. A decrease in temperature is observed. b. Forces of attraction are formed,
and there may be a phase transition. No change in temperature is observed.
Energy is transmitted into it as the system is heated. The system shifts in response to the energy it
receives, for example, by increasing its temperature. If a material's temperature during heating is
monitored, it varies with time. The heating curve is called a plot of the temperature versus time.
• Between A & B, the material is a solid. The heat supplied to the material is used to increase the kinetic
energy of the molecules and the temperature rises.
• Between B & C, the solid is melting. Heat is still being supplied to the material but the temperature does
not change. Heat energy is not being changed into kinetic energy. Instead, the heat is used to change the
arrangement of the molecules.
• At point C, all of the materials have been changed to liquid.
• Between C & D, the heat supplied is again used to increase kinetic energy of the molecules and the
temperature of the liquid starts to rise. • Between C & D, the liquid is heated until it starts to boil.
• Between D & E, the liquid is still being heated but the extra heat energy does not change the
temperature (kinetic energy) of the molecules. The heat energy is used to change the arrangement of the
molecules to form a gas.
• At point E, all of the liquid has been changed into gas.
• Between E & F, the gas is heated and the heat energy increases the kinetic energy of molecules once
more, so the temperature of the gas increases.
When a system contains only one phase (solid, liquid, or gas), the temperature will increase when it
receives energy. The rate of temperature increase will be dependent on the heat capacity of the phase in
the system. When the heat capacity is large, the temperature increases slowly, because much energy is
required to increase its temperature by one degree. Thus, the slopes of temperature increase for the solid,
liquid, and gases are different. The figure below shows how to calculate the total energy change for such a
process. All the steps should be included.
LESSON III-COLLIGATIVE PROPERTIES OF SOLUTIONS
In the previous lessons we discover that a solution is described in terms of concentration of one or
more solutes present in it. There are some important physical properties of solution which are more
directly dependent on the concentration of solute particles. Previously, we looked at the different
concentration units and how they are utilized to determine the desired result. In this lesson, we will
examine the properties that are called colligative (latin, coligare – which means “tied together”)
properties which mean, they depend on the collective effect of the concentration of solute particles
present in the solution. These properties include: (1) vapor pressure lowering, (2) boiling point
elevation, (3) freezing point depression, and (4) osmotic pressure.
Because of their direct relationship to the number of solute particles, the colligative properties are
very useful for characterizing the nature of a solute after it is dissolved in a solvent and for
determining the molar masses of substances. The latter will be discussed in the next lesson. Effect
of solute concentration on the colligative properties of solutions the concentration or amount of
nonvolatile solute (i.e., a solute that does not have a vapor pressure of its own) in the solution
influences the colligative properties of solutions. The result will depend on the ratio between the
number of solute and solvent particles in the solution and not on the solute's identity. However, it is
necessary to consider whether the solute is an electrolyte or a nonelectrolyte.

Effect of solute concentration on the colligative properties of solutions

1. Vapor Pressure Lowering A direct measure of the escaping capacity of molecules is vapor pressure. A pure
liquid (solvent) can achieve equilibrium with its vapor in a closed container. And the pressure exerted by the
vapor is called vapor pressure until the equilibrium is attained. A substance that does not have a noticeable
vapor pressure is nonvolatile, whereas one that has a vapor pressure is volatile. If a liquid evaporates readily,
a significant amount of the molecules would be present in the gas phase, resulting in a high vapor pressure.
A surface filled by liquid molecules is seen on the left, some of which have evaporated and formed a vapor.
On the right, a nonvolatile solute like salt or sugar has been dissolved into the solvent, having the effect of
diluting the water. The addition of a non-volatile solute resulted in lowering of the solvent's vapor pressure.
The lowering in vapor pressure depends on the amount of dissolved solute particles. The molecular essence
of the solute is not taken into consideration since the vapor pressure is simply a solvent's physical property
and does not undergo a chemical reaction with the solvent and does not escape into the gas phase by itself.

It should be remembered that the decrease in the vapor pressure of the solution in this case is directly
proportional to the fraction of the volatile molecules in the oil, which is the solvent’s mole fraction. It is
possible to assess this decreased vapor pressure using Raoult’s Law (1886).
Recall from the definition of mole fraction that in a two-component solution (a solvent and a single solute),
Xsolvent = 1 – Xsolute. While the chemical nature of the solute is not a factor to consider, it is important to
take into consideration whether the solute is an electrolyte or nonelectrolyte. Ionic compounds such as
sodium chloride, NaCl, are strong electrolytes that dissociate into ions, resulting in a greater number of
dissolved particles when they
dissolve in solution. Consider two
distinct equivalent concentration
solutions: one is made of ionic
compound NaCl, and the other is
made of molecular compound
glucose (C6H12O6). The equations
below show what happens when
these solutions dissolve:

The sodium chloride, NaCl dissociates into 2 ions, while glucose does not dissociate. Thus, twice as many
dissolved particles as in the case of NaCl would result in equal concentrations of each solution. In the NaCl
solution (electrolyte), the vapor pressure of the solvent can be reduced twice as much as that of the solvent
in the glucose (nonelectrolyte) solution. Since the salt solution surface is now filled with more solvent
particles, there is less space for solvent molecules to evaporate, decreasing the solvent's water vapor
pressure.
1. Boiling Point Elevation
The addition of a non-volatile solute decreases the vapor pressure of the solution, so that the vapor pressure
of the solution is returned to a value conforming to the pure solvent, the temperature must be increased. In
fact, the temperature at which the vapor pressure is 1 atm is greater than the normal boiling point by an
amount known as the boiling point elevation.
Figure 3 below shows the phase diagram of a solution and the effect that the lowered vapor pressure has on
the boiling point of the solution compared to the solvent. In this case the sucrose solution has a higher boiling
point than the pure solvent. Since the vapor of the solution is lower, more heat must be supplied to the
solution to bring its vapor pressure up to the pressure of the external atmosphere. The boiling point
elevation is the difference in temperature between the boiling point of the pure solvent and that of the
solution.

The molal boiling point elevation constant kb, has a specific value depending on the identity of the
solvent.
 2. Freezing point depression
The freezing point of a
substance is the temperature
at which the solid and liquid
forms can coexist indefinitely,
at equilibrium. Under these
conditions molecules pass
between the 2 phases at equal
rates because their escaping
tendencies from the two
phases are identical. Figure 5
below shows the phase
diagram for a pure solvent and
how it changes when a solute
is added to it. The solute
lowers the vapor pressure of
the solvent resulting in a lower freezing point for the solution compared to the pure solvent. The
freezing point depression is the difference in temperature between the freezing point of a pure
solvent and that of a solution. On the graph, tf represents the freezing point depression

If a substance is applied to a solvent such as water at a given temperature, the solute-solvent interactions
prohibit the solvent from entering the solid phase, causing the temperature to drop further until the
solution solidifies. As a result, more energy must be removed from the solution to freeze it and the
freezing point of the solution is power than that of the pure solvent. The degree of the freezing point
depression is directly proportional to the solution's molality. Thus: