Intermolecular

Forces, Liquids &

Solids
•Some of the characteristic
properties of solids, liquids,
gases can be understood in
terms of the energy of motion of
the particles of each state,
compared to the energy of
intermolecular interactions
between those particles.
•gases – energy of attraction <<
kinetic energy
•liquids - attractive forces not
strong enough to keep particles
from moving past one another
•solids - intermolecular attractive
forces are strong enough to hold
particles close together and to lock
them virtually in place.
•The state of a substance
depends largely on the balance
between the kinetic energies of
the particles and the
interparticle energies of
attraction
•can change state of substance by
heating or cooling - changes ave.
KE of particles
•increasing the pressure on a gas
forces the molecules closer
together, which in turn increases
the strength of the intermolecular
forces of attraction.
•At room temperature:
●Gases have weaker interparticle
attractions than those that are
liquids.
•INTERMOLECULAR FORCES
● Generally much weaker than ionic
or covalent bonds. eg. H2O
●<15% as strong
●Less energy is required to evaporate
a liquid than to break the covalent
bonds.
●When a substance change from solid
to liquid to gas, the molecules
themselves remain in tact.
•Many properties of liquids
reflect the strengths of the
intermolecular forces.
•Boiling Point
●Liquid boils when bubbles of its
vapor form within the liquid.
•The molecules must overcome the
attractive forces to separate and
form a vapor.
•The stronger the attractive forces
are, the higher the temperature at
which the liquid boils.
•3Types of Intermolecular
Attractions (neutral molecules)
•Dipole-dipole attractions
•London dispersion forces
•Hydrogen bonding

•VS. ion-dipole interactions

•All
of these are electrostatic in
nature – involve attractions
between positive and negative
species.
•Polar molecules are dipoles
●Have a positive end and a
negative end.
●eg. H2O, HCl
•How to know if molecules are
polar or not?
•Examine the bond polarities
●Electronegativity – ability of an
atom in a molecule to attract
electron to itself.
•ΔEN = 0 (nonpolar covalent) – F2
•ΔEN = 1.9 (polar covalent) - HF
•ΔEN = 3.0 (ionic) – LiF
•ΔEN = 2.1 (ionic) - NaCl
•When the bond is polar, the
molecule is a dipole.
•Whenever a distance separates
two electrical charges of equal
magnitude but opposite sign, a
dipole is established.
•The quantitative measure of the
magnitude of a dipole is called
dipole moment, denoted by µ.
•Dipole-Dipole Attractions
●Neutral polar molecules attract
each other when positive end of
one molecule is near the negative
end of another.
●Effective only when polar
molecules are very close together.
4
●Varies as 1/d
Dipole-Dipole Forces
•Two molecules that are
attracting each other spend
more time near each other than
do two that repelling each
other.
●Effect: net attraction.
•Trend: For molecules of
approximately equal mass and
size, the strengths of
intermolecular attractions
increase with increasing polarity.
•BP increases as dipole moment
increases.
•Nonpolarmolecules (and
atoms) do not have a dipole
moment.
●Nonpolar gases like argon and
helium can be liquefied.
•Helium forms no stable chemical bonds
•Expected to remain a gas right down to 0
K.
•Condenses to a liquid at 4 K
•Freezes to a solid at 1 K, 25 atm
pressure
•Intermolecular forces, even though very
weak, must exist among He atoms.
London Dispersion Forces
•The motion of electrons in an
atom or molecule can create an
instantaneous, or momentary,
dipole moment.
•London Dispersion Forces
●Motions of electrons on one atom
influence the motions of electrons
on its neighbors. The temporary
dipole on one atom can induce a
similar temporary dipole on an
adjacent atom, causing atoms to
be attracted to each other.
Dispersion Forces
•London Dispersion Forces
•Significant only when
molecules are very close
together.
7
•Vary as 1/d
•Strength of dispersion forces
depends on the ease with which
the charge distribution in a
molecule can be distorted
(polarizability) to induce a
momentary dipole.
•Polarizability - term used to
describe the relative tendency for
a charge distribution (electron
cloud) to distort from its normal
shape in an atom or a molecule.
•aka squishiness
•More polarizable molecules have
larger dispersion forces.
•Dispersion forces tend to
increase in strength with
increasing molecular weight.
•Shape influences dispersion
forces - more contact, higher
interactions.
•In terms of surface area…
Neopentane: bp = 9.5 °C
Pentane: bp = 36.1 °C
•Dispersionforces operate
between all molecules, whether
polar or nonpolar.
•Dispersion forces between polar
molecules commonly contribute
more to IMA than do dipole-dipole
forces.
•eg. liquid HCl – dispersion forces
account for around 80% of the
total attractions between
molecule.
•Generalization
•1.When the molecules of two
substances have comparable
MWs and shapes, dispersion
forces are approximately equal.
The more polar molecules have
stronger attractions.
•Generalization
•2.When molecules of two
substances differ widely in
MWs, dispersion forces tend to
be decisive in determining
which substance has the
stronger IMA.
To be continued…
•Hydrogen Bonding
•attraction between hydrogen atom in a polar
bond (particularly an H-F, H-O or H-N) and
nonbonding electron pair on a nearly
electronegative ion or atom (usually an F, O,
or N atom in another molecule.) (small but
terrible atoms)
• > can be considered as unique dipole-dipole
interactions
• > N, O, F are so electronegative - bond
between H and any of these is quite polar
•Case Study: Water
•> In most substances the molecules in
the solid are more densely packed than
in the liquid.
• > density of ice at 0 deg. C (0.917 g/ml)
is less than that of liquid water at 0 deg.
C (1.00 g/ml)
• > ice floats on liquid water.
• > "This is just the tip of the iceberg."
•> In ice, water molecules assume
an ordered, open arrangement
(open structure)
• > this optimizes the H bonding
interactions between molecules
• > H bonding in the liquid is more
random than in ice - has a more
dense structure than in ice.
•> each water molecule forms 4 H
bonds to 4 other water molecules
•> O atoms are arranged in bent
hexagonal rings arranged in
layers - characteristic pattern is
similar to the hexagonal shapes of
snowflakes
Hydrogen Bonding
• volume expansion of water
upon freezing - causes water
pipes to break in freezing
weather
To be continued…
Viscosity
Flow of Honey vs Water?
•Honey is more viscous than
water at the same T.
Viscosity
•Resistance of a liquid to flow
●Depends on the attractive
forces between molecules.
●Depends on structural features
that cause molecules to
“entangled”
Viscosity
Octane, viscosity in kg/m-s
-4
•7.06x10 at 0 deg.C
-4
•4.33x10 at 40 deg.C
 Viscosity
•Increases with molecular
weight.
•Decreases with increasing
temperature.
Viscosity
•At higherT, greater ave. KE
of molecules more easily
overcome attractive forces
between molecules
 Surface Tension
•Interior molecules have more
neighbors and experience more
attractive IMA than surface
molecules.
•There is imbalance of
intermolecular forces at the surface
of the liquid.
 Surface Tension
•The resultant inward force pulls
molecules from the surface into
the interior, thereby reducing the
surface area, and making the
molecules at the surface pack
closely together.
 Surface Tension
•Increased number of attractions by
neighboring molecules places an
interior molecule in a more stable
environment than a surface molecule.
•As many molecules as possible tend to
enter the bulk of a liquid, while as few
as possible remain at the surface.
 Surface Tension
•Liquids tend to maintain a
minimum surface area.
•For a given volume, a sphere has
the least possible surface area
•Drops of liquid tend to assume
spherical shapes.
Surface
Tension
Surface Tension
Surface
Tension
Surface
Tension
 Surface Tension
•Toincrease the SA of a liquid requires that
molecules be moved from the interior to the
surface of a liquid
•This requires that work be done.
•Steelneedle remains suspended on the surface
of water because energy is required to spread
the surface of the water over the to of the
needle.
 Surface Tension
•Surface Tension - the energy, or work,
required to increase the surface area of a
liquid.
•SI units are N/m (also J m^-2)
•Increase T - increase molecular motion - IMF
become less effective.
• > T vs Surface Tension?
Surface Tension

•at 20 deg. C, J m^-2

•water = 7.28x10^-2
•mercury = 47.2x10^-2
Surface Tension
 Surface Tension
•When a drop of liquid spreads into a film
across a surface = the liquid wets the
surface.
•Whether it wets a surface or retains its
spherical shape and stands on the surface
depends on strengths of 2 types of IMF
 Surface Tension
•cohesive forces - forces between
molecules
•adhesiveforces - forces between liquid
molecules and the surface
•(cohesion-adhesion)
 Surface Tension
•cohesive > adhesive = drop maintains its
shape
•adhesive > cohesive = energy
requirement for spreading the drop into a
film is met through work done by the
collapsing drop.
Surface Tension
 Surface Tension
•water wets many surfaces like glass and
certain fabrics.
•essential to its use as a cleaning agent.
•adding detergent to water
•1. detergent solution dissolves grease to
expose a clean surface
•2. detergent (a wetting agent) lowers the
surface tension of water - lowering the
energy required to spread drops into a film.
Meniscus – the
interface between
liquid and air above it.

Water – curved in
(concave)
Mercury – curved out
(convex)
 Surface Tension
•liquid
water in the glass tube - water is
drawn slightly up the walls of the tube
by adhesive forces bet. water and glass.
•liquidmercury - cohesive forces in
mercury - metallic bonds bet. Hg atoms
are strong
•mercury DOES NOT wet glass.
Surface
Tension
 Capillary Action
•Capillary tubes - tubes of small diameter
•Liquidclimbs until the force of gravity
on the liquid balances the adhesive and
cohesive forces.
 Capillary Action
•Capillaryaction helps water and
dissolved nutrients move upward
through plants