PHYSICAL SCIENCE – CHEM
The nature of the phases and their changes are
due primarily to forces among the molecules.
 Intramolecular and Intermolecular
Forces arise from electrostatic
attractions between opposite charges.
 Bonding forces are due to the
attraction between cations and anions
(ionic bonding), nuclei and electron
pairs (covalent bonding), or metal
cations and delocalized valence
electrons (metallic bonding).
 Intermolecular forces, on the other
hand, are due to the attraction
between the molecules as a result of
partial charges, or the attraction
between ions and molecules.
EN Electron Negativity is the relative ability of a
bonded atom to attract the shared electrons
==> it is not the same as electron affinity (EA)
This difference is due to an electrostatic
(charge) contribution to the H-F bond energy.
This unequal sharing of electrons makes the F
end of the bond partially negative and the H
end partially positive.
The attraction between these partial charges
increases the energy required to break the
bond.
In HF, the unequal distribution of electron
density means the bond has partially negative
and positive poles
Polar covalent bond ==> depicted as a polar
arrow (+→) pointing toward the negative pole
or by δ+ and δ- symbols
But in H-H and F-F bonds, the atoms are
identical, so the bonding pair is shared equally
==> nonpolar covalent bond.
A covalent bond is polar when it joins atoms of
different electronegativity because the atoms
share the electrons unequally.
Molecules with a net imbalance of charge have
a Molecular Polarity.
In molecules with more than two atoms, both
shape and bond polarity determine molecular
polarity.
Dipole Moment (μ): is the product of the partial
charges and the distance between them ==>
debye (D) unit (1 D = 3.34E-30 cm).
Partial Ionic Character: A greater ΔEN results in
larger partial charges and a higher partial ionic
character
Bonding Forces are relatively strong because
they involve larger charges that are close
together.
Intermolecular Forces are relatively weak
because they typically involve smaller charges
that are farther apart.
Ion – Ion Forces
The strongest force, not listed, is the ion - ion
force and is considered later in the section on
ionic solids.
These forces (ion-ion) increase as the size of the
ion decreases and as the magnitude of the
charge increases. Remember that anions are
larger than the atoms they are derived from
and cations are smaller than the atoms they are
derived from.
Ion – Dipole Force
An ion and a nearby polar molecule (dipole) ==>
attract each other ==> ion-dipole force
Example: ionic compound dissolves in water.
The ions become separated because the
attractions between the ions and the oppositely
charged poles of the H2O molecules overcome
the attraction between the ions themselves.
Dipole – Dipole Force
From the orientation of polar molecules in an
electric field, when polar molecules lie near one
another, as in liquid and solid, their partial
charges act as tiny electric fields that orient
them and give rise to dipole-dipole forces (the
positive pole of one molecule attracts the
negative pole of another.
A nearby electric field can distort a cloud of
negative charge, therefore pulling electron
density toward a positive charge or pushing it
away from a negative charge.
In effect, the field induces a distortion in the
electron cloud
 For a nonpolar molecule, this distortion
creates a temporary induced dipole
moment.
 For a polar molecule, it enhances the
dipole moment already present.
The ease with which the electron cloud of a
particle can be distorted ==> POLARIZABILITY
Smaller atoms (or ions) are less polarizable than
larger ones, because their electrons are closer
to the nucleus and therefore are held more
tightly.
Polarizability increases down a group, because
size increases so the larger electron clouds are
farther from the nucleus, and thus more easily
distorted
Polarizability decreases from left to right
across a period, because the increasing Zeff
shrinks atomic size and holds the electrons
more tightly
 Cations are less polarizable than their
parent atoms because they are smaller
 Anions are more polarizable because
they are larger
 Ion-induced dipole and dipole-induced
dipole forces are the two types of
charge-induced dipole forces ==> most
important in solution.
Dispersion Forces
==> The intermolecular force primarily
responsible for the condensed states of
nonpolar substances ==> is dispersion force or
London force.
Dispersion forces are caused by momentary
oscillations of electron charge in atoms and
therefore are present between all particles
The strength of dispersion forces increases with
number of electrons which usually correlates
with molar mass.
As a result, boiling point increase down the
halogens and the noble gases.
Hydrogen Bonding
Hydrogen bonding is a special case of dipole -
dipole forces, and only exists between
hydrogen atoms bonded to F, N, or O, and F, N,
and O atoms bonded to hydrogen atoms.
H-bonding is especially strong in biological
systems — such as DNA.
DNA — helical chains of phosphate groups and
sugar molecules. Chains are helical
because of tetrahedral geometry of P, C,
and O.
Chains bind to one another by specific hydrogen
bonding between pairs of Lewis bases.
—adenine with thymine
—guanine with cytosine
Unusual Properties of Water:
Consequences of Hydrogen Bonding
 Water has a very high specific heat,
heat of fusion, heat of vaporization,
thermal conductivity, and dielectric
constant.
 Ice is less dense than liquid water (very
uncommon).
H-bonding is especially strong in water because
• the O—H bond is very polar
• there are 2 lone pairs on the O
atom
Accounts for many of water’s unique properties
H-bonding in H O open lattice like
2
structure of ice.
Ice density is less than that of liquid, and solid
floats on water.
H bonds ---> abnormally high specific heat
capacity of water (4.184 J/g•K).
This is the reason water is used to put out fires,
it is the reason lakes/oceans control
climate, and is the reason thunderstorms
release huge energy.
PROPERTIES OF LIQUIDS
 Molecules are in constant motion.
 There are appreciable intermolecular
forces.
 Molecules close together.
 Liquids are almost incompressible.
 Liquids do not fill the container.
 In the liquid state the molecules are
much closer together than in the
gaseous state, but they are still free to
move.
 Liquids occupy only the lower portion of
the container as it is filled.
Enthalpy of Vaporization
• Vaporization is an endothermic
process.
• Energy must be added to replace
the energy that is lost when the
fast moving molecules escape into
the vapor state.
• At higher temperatures, more of
the molecules have sufficient
energy to escape.
• Since vaporization is an
endothermic process,
condensation is an exothermic
process.
The magnitude of ΔH is related to the type
vap
and magnitude of the inter-molecular forces
found in the liquid.
The two key properties we need to describe are
EVAPORATION and its opposite
CONDENSATION
To evaporate, molecules must have sufficient
energy to break IM forces.
Breaking IM forces requires energy. The process
of evaporation is endothermic.
When molecules of liquid are in the vapor state,
they exert a VAPOR PRESSURE
EQUILIBRIUM VAPOR PRESSURE is the pressure
exerted by a vapor over a liquid in a closed
container when the rate of evaporation =
the rate of condensation.
The vapor pressure is the equilibrium pressure
of the vapor above the liquid at a given
temperature. Compounds with higher vapor
pressures are more volatile than those with
lower vapor pressures.
The stronger the intermolecular forces, the
lower the vapor pressure.
As the temperature increases, the vapor
pressure increases since there are higher
energy molecules at the higher temperature.
HEAT OF VAPORIZATION is the heat required
(at constant P) to vaporize the liquid.
BOILING POINT
The boiling point, T , is the temperature when
b
the equilibrium vapor pressure equals the
external pressure.
o
The normal boiling point, T , is the
b
temperature when the equilibrium vapor
pressure equals one atmosphere pressure or
760 torr.
A liquid boils when its vapor pressure equals
atmospheric pressure.
Boiling point at lower pressure
When pressure is lowered, the vapor pressure
can equal the external pressure at a lower
temperature.
Consequence of Vapor Pressure changes
When can cools, VP of water drops. Pressure in
the can is less than that of atmosphere, so can
is crushed.
Critical Temperature and Pressure
The critical temperature, T , is the temperature
c
at which the liquid state no longer exists since
all molecules have sufficient energy to be
separated from each other.
The critical pressure, P , is the pressure
c
corresponding to the critical temperature,
where no further increase in pressure will cause
the gas phase to condense into the liquid phase.

This (T , P ) point is called the critical point on

c c
the vapor pressure graph.

Movement of water up a piece of paper

Surface tension is the result of the
intermolecular force acting at the surface of a
liquid.
Surface tension is the amount of energy
required to stretch or increase the surface of a
liquid by a unit area.
Capillary action is rising of a fluid in a very small
diameter tube, results from the combination of
adhesive forces, between a solid (like glass) and
the liquid and the cohesive forces, between the
molecules of the liquid.
 If the cohesive forces are stronger, the
liquid forms an upward rounded
meniscus.
 A downward rounded meniscus forms if
the adhesive forces are stronger.
 Viscosity is the resistance to flow, and is
at least partially a function of the
intermolecular forces.
depends on H-bonds between H O and the OH
2
groups of the cellulose in the paper.
Cohesion is the intermolecular attraction
between like molecules.
Adhesion is an attraction between unlike
molecules.
Viscosity is a measure of a fluid’s resistance to
flow.
A crystalline solid possesses rigid and long-
range order. In a crystalline solid, atoms,
molecules or ions occupy specific (predictable)
positions.
An amorphous solid does not possess a well-
defined arrangement and long-range molecular
order.
A unit cell is the basic repeating structural unit
of a crystalline solid.

Molecules at surface behave differently than

those in the interior.

Molecules at surface experience net INWARD

force of attraction.

This leads to SURFACE TENSION — the energy

required to break the surface.

SURFACE TENSION also leads to spherical liquid

At lattice points:
droplets.
• Atoms
IM forces also lead to CAPILLARY action and to • Molecules
the existence of a concave meniscus for a water • Ions
column.
Types of Crystals Molar heat of vaporization (DH ) is the energy
vap
Ionic Crystals – Ion-Ion interactions are the
required to vaporize 1 mole of a liquid.
strongest (including the “intermolecular forces”
(H bonding, etc.)
Molar heat of fusion (DH ) is the energy
• Lattice points occupied by cations and fus

anions required to melt 1 mole of a solid substance.

• Held together by electrostatic attraction
• Hard, brittle, high melting point Molar heat of sublimation (DH ) is the energy
sub
• Poor conductor of heat and electricity required to sublime 1 mole of a solid.
Covalent Crystals – Stronger than IM forces but
generally weaker than ion-ion
• Lattice points occupied by atoms Hsub = Hfus + Hvap
• Held together by covalent bonds
• Hard, high melting point Hess’s Law
• Poor conductor of heat and electricity
A phase diagram summarizes the conditions at
Molecular Crystals
which a substance exists as a solid, liquid, or
• Lattice points occupied by molecules
gas.
• Held together by intermolecular forces
• Soft, low melting point
The triple point is where all 3 phases meet.
• Poor conductor of heat and electricity
Metallic Crystals – Typically weaker than
covalent, but can be in the low end of covalent
• Lattice points occupied by metal atoms
• Held together by metallic bonds
• Soft to hard, low to high melting point
• Good conductors of heat and electricity
An amorphous solid does not possess a well-
defined arrangement and long-range molecular
order.
A glass is an optically transparent fusion
product of inorganic materials that has cooled
to a rigid state without crystallizing.

The equilibrium vapor pressure is the vapor

pressure measured when a dynamic equilibrium
exists between condensation and evaporation.
Uniqueness of Water - H2O
Water molecule is composed of H and O atoms.
Each atom attains a filled outer level by sharing
electrons in single covalent bonds.
With two bonding pairs and two lone pairs
around the O atom and a large electronegativity
difference in each O-H bond, the H2O molecule
is bent and highly polar.
Because it has two O-H bonds and two lone
pairs, one H2O molecule can engage in as many
as four H bonds to surrounding H2O molecules,
which are arranged tetrahedrally. Water is
highly polar and can interact with positive ions
to give hydrated ions in water.
Solvent Properties: The great solvent power of
water is due to its polarity and exceptional H-
bonding ability.
It dissolves ionic compounds through ion-dipole
forces that separate the ions from the solid and
keep them in solutions.
Water dissolves many polar nonionic
substances, such as ethanol (CH3CH2OH) and
glucose (C6H12O6), by forming H bonds to
them.
It even dissolves nonpolar gases, such as those
in the atmosphere, to a limited extent, through
dipole-induced dipole and dispersion forces.
Thermal properties: Water has an exceptionally
high specific heat capacity, higher than almost
any other liquid.
When a substance is heated, some of the
energy increases the average molecular speed,
some increases molecular vibration and
rotation, and some is used to overcome
intermolecular forces. Because water has so
many strong H bonds, it has a high specific heat
capacity.
Surface Properties: The H bonds that give water
its remarkable thermal properties are also
responsible for its high surface tension and high
capillarity. Water’s unique properties comes
from the strong attractive forces between
molecules.
Water's high capillarity, as a result of its high
surface tension, is crucial to land plants and
animal life.
Water expands on freezing because of its H
bonds, which lead to an open crystal structure
of ice. Many metal ions are hydrated. It is the
reason metal salts dissolve in water.
 No species can live without water.
 Plays a key role in shaping the earth’s
surface, moderating climate, removing
and diluting wastes.
 Takes huge amount to provide food,
shelter and other needs.
 71% of our planet
Water unique Properties
Liquid over wide temperature range: without its
high boiling point the oceans would have
evaporated long ago.
Changes temperature slowly: high specific heat
means slow temperature changes. Helps
moderate climate.
High heat of evaporation: evaporation takes a
lot of heat. This explains why sweating makes
you feel cooler.
Great dissolving power: known as the universal
solvent because so many things dissolve well in
it. Leads to pollution problems as well.
Filters out ultraviolet radiation: protecting
aquatic organisms from sun’ rays.
Adhesion and cohesion: strong forces of
attraction between molecules allows water to
rise up inside plants from roots to leaves.
Expands when it freezes: most substances
contract when frozen, not water. Water
expands and is less dense in its solid form.
Hence, ice floats.
Water is also one of few substances found
commonly as a solid, liquid and gas.
Water Cycle: Renewing water
Surface water
Surface runoff: precipitation that does not
infiltrate the ground or return to the
atmosphere.
Reliable runoff: the amount of water that can
be counted on each year as a stable source.
Watershed: the region of land from which
surface water drains into a river, lake, wetland
or other body of water.

Ground Water
 One of the most important source of
water.
 Precipitation filters down through pores
and cracks in soil and rocks.
 Groundwater found within 1km of the
surface contains 100 times more water
than all the rivers, streams and lakes

Uses of Water Resources

Humans use about 54% of reliable runoff.
Agriculture: worldwide about 70% of water is
used to irrigate crops.
85% of that is not returned to the water ways.

Agriculture
38%

Power
cooling
38% Industry 11%

20% of water withdrawn each year is used by

industry.
Domestic: 10% is used by cities and residencies.