The Kinetic Molecular Theory

Condensed Phases
-Liquids
-Solids

-Intramolecular forces hold atoms together within a molecule.

-Intermolecular forces are attractive forces between molecules.

Types of Intramolecular Forces of Attraction

1.Ionic bond: This bond is formed by the complete transfer of valence electron(s) between
atoms. It is a type of chemical bond that generates two oppositely charged ions. In ionic
bonds, the metal loses electrons to become a positively charged cation, whereas the
nonmetal accepts those electrons to become a negatively charged anion.

2. Covalent bond: This bond is formed between atoms that have similar electronegativities
—the affinity or desire for electrons. Because both atoms have similar affinity for electrons
and neither has a tendency to donate them, they share electrons in order to achieve octet
configuration and become more stable.

A nonpolar covalent bond is formed between same atoms or atoms with very similar
electronegativities—the difference in electronegativity between bonded atoms is less than
0.5.

A polar covalent bond is formed when atoms of slightly different electronegativities share
electrons. The difference in electronegativity between bonded atoms is between 0.5 and
1.9. Hydrogen chloride, HCl; the O – H bonds in water, H2O; band hydrogen fluoride, HF, are
all examples of polar covalent bonds.

1. If bond is polar, then the molecule can either be polar or non-polar.

2. I f bond is non-polar, then the molecule is automatically non-polar.

Dipole moments occur in any system in which there is a separation of positive and negative
electrical charges; therefore, they can be found in both ionic and covalent bonds. A dipole
moment is a result of unequal electron distribution, which occurs due to differences in
electronegativity between chemically-bonded atoms Greater differences in electronegativity
will consequently lead to larger dipole moments.

Molecular Geometry
- three-dimensional arrangement of atoms in a molecule.

POLAR MOLECULE
- In more complex molecular shapes, if the dipole moments do not add up to zero
or do not cancel out, a net dipole moment is present, making the molecule polar.
- NH3, H20, ClF3, SO2,
NON-POLAR MOLECULE
- If the dipole moments do cancel out, the molecule is non-polar. Carbon
tetrachloride, CCl4 is one example. Even if the C-Cl bonds are polar, their
tetrahedral arrangement allows the bond dipoles to cancel each other.
- XeF4, BF3, CO2, CH4, N2, O2, O3, H20, PCL3, HF

GENERAL TYPES OF INTERMOLECULAR FORCES

LONDON DISPERSION FORCES

- Named after Fritz Wolfgang London
- present in molecules, regardless of the polarity.
- The only force present in non-polar molecules
- It is the weakest among the IMFAs.
- Br2, Cl2, CH4

DIPOLE-DIPOLE FORCES
- These forces occur when the partially positively charged part of a molecule
interacts with the partially negatively charged part of the neighboring molecule.
The prerequisite for this type of attraction to exist is partially charged ions—for
example, the case of polar covalent bonds such as hydrogen chloride, HCl.

HYDROGEN BOND
- Hydrogen bond is a special type of dipole-dipole interaction that occurs in
molecules having a hydrogen atom bonded to an electronegative atom such as
FLUORINE, OXYGEN, or NITROGEN. It is the strongest intermolecular force of
attraction among the three.

SPECIAL PROPERTIES OF LIQUIDS

1. Surface Tension
- It is a force that tends to pull adjacent parts of a liquid’s surface together,
thereby decreasing surface area to the smallest possible size. Surface tension
results from the attractive forces between particles of a liquid. The higher the
force of attraction, the higher the surface tension. Surface tension causes liquid
droplets to take on a spherical shape because a sphere has the smallest possible
surface area for a given volume. With gravity, however, the droplet sags and
assumes the teardrop shape that we know. It also allows water striders walk on
water.

2. Viscosity
- measure of the resistance of a liquid to flow. The greater the viscosity, the slower
the liquid flows. Viscosity increases with stronger intermolecular forces caused
by an increase in the molecular weight, and decreases with higher temperature.
3. Capillary action
- the attraction of the surface of a liquid to the surface of a solid. A liquid will rise
quite high in a very narrow tube if a strong attraction exists between the liquid
molecules and the molecules that make up the surface of the tube. It 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. 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.

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.

When both adhesive and cohesive forces are equal, the surface is horizontal.

4. Vapor Pressure
- the pressure exerted by the vapor when the liquid and gaseous states are in
equilibrium. 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.
Vapor pressure is affected by temperature. The higher the temperature, the
higher the vapor pressure.

5. Molar Heat of Vaporization

- Molar heat of vaporization is the amount of heat required by one mole of a
substance to change from liquid to gas. The process by which a liquid or a solid
change to gas is vaporization. Evaporation is a form of vaporization. Evaporation
occurs because the particles of a liquid have different kinetic energies. As the
temperature increases, the kinetic energy of molecules also increases. In order
for a molecule to break free from the liquid and go into the gaseous phase, its
kinetic energy must be greater than the intermolecular forces holding it within
the liquid. Some liquids vaporize fast; others vaporize rather slowly. The ability of
a liquid to vaporize depends on the intermolecular forces of attraction. Liquids
 that vaporize easily are said to be volatile. On the other hand, those that do not
vaporize easily are known as nonvolatile liquids. Examples include peanut oil and
Glycerol.

6. Boiling point
- of a substance is the temperature at which its vapor pressure equals the external
pressure acting on the surface of the liquid. A liquid boil only when its vapor
pressure is the same as the external pressure. The boiling point of a substance is
also affected by IMF. Polar substances tend to have higher boiling points than
nonpolar substances because polar molecules have stronger attraction between
them. The normal boiling point of any liquid is always measured against an
external pressure of 1 atm. This means that the external pressure affects the
boiling point of a liquid. 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.

Special Properties of Solids

Solids can be categorized into two groups:

• crystalline solids
• 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.

a. CRYSTALLINE SOLID- produced from a regular repeating three-dimensional structure

called a crystal lattice. Crystalline solids are arranged in fixed geometric patterns or lattices.
Examples:
•ice
•sodium chloride (NaCl)
•copper sulfate (CuSO4)
•Diamond
•Graphite
•sugar (C12H22O11)
The ordered arrangement of their units maximizes the space they occupy and are essentially
incompressible.

X-ray Diffraction is a 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.

Examples of crystalline solids and how they are formed

There are two main methods for obtaining salt, evaporation from sea water and mining salt
from the earth. Most common table salts and salts used for industrial purposes are obtained
through mining, while specialty or gourmet salts are still produced via evaporation of sea
water.

Cane stalks are shredded and squeezed to extract its natural juice, which is boiled until it
thickens and molasses– rich sugar crystals begin to settle. The molasses-rich crystals are
sent to a rapidly spinning centrifuge to remove molasses and leave pure, naturally white
sugar crystals. The sugar crystals are then dried.

Amethyst is formed in silica-rich liquids deposited in gas cavities of lava that occur in
crystalline masses. Such cavities occur in the earth's crust for several reasons such as gas
bubbling in circular cavities or filling of veins. In nature amethyst crystals are mainly formed
in the inner surface of an amethyst geode.

Uric acid is the byproduct of protein digestion, and among healthy individuals, it is removed
from the blood stream and excreted by the kidneys. Excess uric acid is deposited in the
joints in crystal form and creates a painful arthritic condition known as gout.

Snow is formed when temperatures are low and there is moisture - in the form of tiny ice
crystals in the atmosphere. When these tiny ice crystals collide they stick together in clouds
to become snowflakes. If enough ice crystals stick together, they'll become heavy enough to
fall to the ground.

Crystallization refers to the formation of solid crystals from a homogeneous solution. It is

essentially a solid-liquid separation technique and a very important one at that.

Four Types of Crystals

1. Ionic Crystals
- These 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. Generally, ionic crystals form when Group 1 or Group 2 metals combine
with Group 16 or Group 17 nonmetal ions.

2. Covalent network crystals

- In covalent network crystals, the sites contain single atoms. Each atom is
covalently bonded to its nearest neighboring atoms.

3. Metallic crystals
- Metallic crystal structure consists of metal atoms surrounded by a sea of valence
electrons. The electrons are donated by the metal atoms and belong to the
crystal as a whole. The freedom of the outer-structure electrons to move
throughout the crystal explains the high electric conductivity of metals. The
melting points of metallic crystals vary greatly.
4. Molecular crystals
- 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.

b. AMORPHOUS SOLID
– arranged in no particular order or randomly arranged. The word amorphous comes from
the Greek for “without shape.”
Examples:
• Glass
• Plastic
• Coal
• Rubber

They are considered super-cooled liquids where molecules are arranged in a random
manner similar to the liquid state.

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 change from solid to liquid is melting, liquid to gas is evaporation, 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.
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.

Conversely, the removal or release of heat results in two ways:

a. A decrease in the kinetic energy of the particles. The motion of the particles slows down.
A decrease in temperature is observed.

b. Forces of attraction are formed, and a phase change may occur. No change in
temperature is observed.

The change in temperature of a substance as it is being heated can be shown in a graph

called the heating curve. The heating curve is a plot of temperature and heat added to the
substance. Often, time is used instead of heat added in the abscissa, because it is assumed
that heat is uniformly added per unit time.
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.

The amount of heat needed to convert the solid to the liquid state at the melting point is
called the heat of fusion (ΔHfus) of the substance.

The amount of heat absorbed by the sample as the liquid transforms into gas is called 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.

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.

HEAT CHANGE WITH CHANGE IN TEMPERATURE (q=mSΔt)

Take note of the following:

Hfus of water = 6.01 kJ/mol

Hvap of water = 40.79 kJ/mol
Specific heat (ice): 2.06 J/g·°C
Specific heat (water): 4.18 J/g·°C
Specific heat (steam): 2.02 J/g·°C

Phase diagram
- It 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.

3 Features 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.

B. Three Lines (Curves)

- The green line divides the solid and liquid phases, and represents melting (solid to
liquid) and freezing (liquid to solid) points.
- The blue line divides the liquid and gas phases and represents vaporization (liquid to
gas) and condensation (gas to liquid) points.
- The red line divides the solid and gas phases, and represents sublimation (solid to
gas) and deposition (gas to solid) points.

C. Two Important Points

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.

The critical point

It 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 normal melting and boiling points are those when the pressure is 1 atmosphere.