Van Der Waals Forces

• These are intermolecular forces of attraction

between neutral molecules.
• The Nobel Prize in Physics 1910 (Johannes
van der Waals)
• "for his work on the equation of state for
gases and liquids"
INTER vs. INTRA molecular forces
• Intramolecular forces are the forces within a
molecule or ionic compound
Example: Individual therapy
NaCl Ionic bond between atom of Na and atom of
Cl
• Intermolecular forces are the forces between
molecules or ions and molecules
Example: couples therapy
Solid liquid gas
Strength
Intramolecular bonds > intermolecular forces
Intramolecular bonds are stronger because it
would take a lot more energy to overcome covalent
bonds and break apart the molecule than to DIPOLE-DIPOLE FORCES
overcome intermolecular forces in between the
atoms (to make it become a liquid or gas). • These are forces of attraction that occur
between polar molecules. (big difference in
electron negativity)
Phase Changes • These forces are effective only when polar
molecules are very close. As distance
• When a substance changes from solid to increase strength of bond decreases.
liquid to gas, the molecules remain intact.
• For molecules of approximately equal mass
• The changes in state are due to changes in and size, the strength of force of attraction
the forces among molecules rather than in increases as the polarity increases.
those within the molecules.
• Radius have an effect on strength of dipole.
• Molecules with larger dipole moments have
3 Types of van der Waals Forces higher melting and boiling points (hard to
break) than those with small dipole
• Dipole-Dipole forces
moments.
• London Dispersion forces
• Hydrogen bonding
• Dipole attractions are relatively weak and
tend to be liquids or gas at room
temperature.

HYDROGEN BONDING
• These types of bonds are super-humanly
strong.

• (4X stronger that dipole dipole)

WHY HYDROGEN BONDING IS

EFFECTIVE
• F, O, & N are extremely small and very
electronegative atoms.

• Hydrogen atoms have no inner core of

electrons, therefore, the positive side of
the bond dipole has the concentrated
charge of the partially exposed, nearly
bare proton of the nucleus

• …in other words, the atoms have a large

difference in electronegativity and their
nuclei can get really close.

IMPORTANCE OF HYDROGEN
BONDING
• Are important biologically, in stabilizing
proteins and keeping DNA together.

• Also explains why ice is less dense than

water (see text).
LONDON DISPERSION FORCES Draw two Lewis structures for the formula C 2H6O
and compare the boiling points of the two
• Fritz London molecules.
• These are forces that arise as a result of
temporary dipoles induced in the atoms or H H
molecules.( it’s a temporary accident!)
• All molecules have some degree of LD H C C O H
forces
H H H H
H C O C H
H H

Which gas would behave more ideally at the

same conditions of P and T?
CO or N2

• LD forces occur between neutral non-polar

molecules. (nobles gases and nonpolar
compounds)
• Occurs in all molecules, including nonpolar
ones.
• LD forces are weak
• The greater the number of electrons the
greater the LD force. (ie the greater the
melting and boiling pt.)
N-pentane vs neopentane
• LD force molecules have Low melting and
boiling pts
• The motion of electrons in an atom or
molecule can create an instantaneous dipole
moment.
• EX: in a collection of He (g) the average
distribution of electrons about a nucleus is
spherical, the molecules are non-polar and
there is no attraction.
• LD forces are generally the WEAKEST • BP = 309.4
intermolecular forces. K BP=282.7 K

• Molecules with more electrons will • Same atomic masses different structure
experience more LD forces

Generalizations Regarding Relative Strengths of

Which molecule is capable of forming stronger IM Forces
intermolecular forces?
• If molecules have comparable molecular
N2 H2O weights and shapes, dispersion forces are
approximately equal. Any difference in
 attractive forces is due to dipole-dipole Consider the following list of compounds. How
attractions. many of these have hydrogen bonding as their
principle IMF
• If molecules differ widely in molecular
weight, dispersion forces are the decisive HCl
factor. The most massive molecule has the
strongest attractions. NH3
CH3OH

Because melting points (MPs) and boiling points H2S

(BPs) of covalent molecules increase with the
CH4
strengths of the forces holding them together, it is
common to use MPs and BPs as a way to compare PH3
the strengths of intermolecular forces.
This is shown below, with the molecular formulas,
molar masses and normal BPs of the first five Which of the following statements are false or
straight-chain hydrocarbons. correct and why?
O2 is dipole dipole

Molecular Formula Molar Mass HCl is hydrogen bonding

Normal BP (C)
CO2 is dipole dipole
CH4 16
- 161.5 NH3 is hydrogen

C2H6 30
- 88.5 ION-DIPOLE FORCES
C3H8 44 • Attraction between an ion and the partial
- 42.1 charge on the end of a polar molecule.
C4H10 58
- 0.5
C5H12 72
- 36.1

Which noble gas element has the lowest boiling

point?
He
The magnitude of attraction increases as either
Ne the charge of the ion increases or magnitude of
the dipole moment increases.
Ar
• Ion-dipole forces are important in solutions
Kr of ionic substances in polar liquids (e.g.
Xe water)
•

The chemical forces between HCl is/are ION-DIPOLE FORCES AND THE SOLUTION
PROCESS
• Dispersion
• Covalent bond
• Hydrogen bond
• Dipol-dipole
• Two of the above
 • Intermolecular forces that bind a substance
to a surface.
SURFACE TENSION
• A measure of the inward forces that must be
overcome in order to expand the surface
area of a liquid.
• The greater the forces of attraction between
molecules (IMF) of the liquid, the greater
the surface tension.
• Surface tension of a liquid decreases with
ANSWER increasing temperature.
• The stronger the intermolecular forces the
stronger the surface tension.
CAPILLARY ACTION
• Another way surface tension manifests.
• The rise of liquids up very narrow tubes.
This is limited by adhesive and cohesive
forces.
Formation of meniscus
• Water : adhesive forces are greater than
cohesive forces
• Mercury: Cohesive are greater than adhesive
forces.
10.2 Properties of liquids
VISCOSITY
• Liquids are vital to our lives.
• The resistance of a liquid to flow.
• Water is a means of food preparation
• The less “tangled” a molecule is expected to
• Cooling machines n industrial processes be, the less viscous it is.
• Recreation • Viscosity decreases with increasing
• Cleaning temperature (molecules gain kinetic energy
and can more easily overcome forces of
• Transportation attraction).

CHARACTERISTICS OF LIQUIDS • Viscosity Increases as pressure increases.

• Surface tension • Liquids with strong IMF have a higher

viscosity.
• Capillary action
10.3 Structure of Solids
• Viscosity
• Two ways to categorize solids
COHESIVE FORCES
– Crystalline
• Intermolecular forces that bind like
molecules to one another (e.g. hydrogen – Amorphous
bonding).
Crystalline Solid
Convex Meniscus Formed by Nonpolar Liquid
Mercury • Ridged and long range order of its atoms.

• Which force dominates alongside the glass • Solids have flat surfaces
tube – cohesive or adhesive forces? • Sharp melting points
ADHESIVE FORCES • EX: Quartz, diamond, sodium Chloride.
Amorphous Solid Changes in state
• Lack a well defined arrangement  LiquidàGas = Vaporization
Endothermic
• No long range order
• GasàLiquid = Condensation Exothermic
• IMF vary in strength
• SolidàGas = Sublimation Endothermic
• DO NOT have sharp melting points.
EX: rubber, glass • Gas à Solid = Deposition Exothermic
Unit Cell • SolidàLiquid Melting Endothermic
• The smallest part of a crystal that will • Liquid à Solid Freezing Exothermic
reproduce the crystal when repeated in a
three dimensions. The energy involved it phase changes is
calculated using
• Three types
• Heat of fusion (solid à liquid or
– Simple /primitive cubic cell liquidà solid)
– Face centered cubic cell • Heat of vaporization (liquidà gas or
– Body Centered gasà liquid)

Energy Changes and Phase Changes

Heat of Vaporization:
Vaporization is an endothermic process ( it requires
heat). Energy is required to overcome
intermolecular forces to turn liq to gas.
Hvap is an Indicator of strength of IMF
Larger molecule…greater IMF…greater Hvap

X-Ray How much energy does it take to vaporizer 111 g of

Diffraction water?

• X-Ray crystallography lead to the discovery Given: Hvap water= 40.67 kJ/mol
of DNA
111 g H2O 1 mol x 40.6kJ = 250kJ
Changes of state
18g 1mol
• Transformation from one state to another

Heat of Fusion: the enthalpy change associated

with melting. (Solid to liquid.)
• Hfusion water= 6.01 kJ/mol
NOTE: heat of fusion is always
smaller than heat of
vaporization. This makes sense
think about the level of “order”
in the molecules in these phases.

Heating Curve
 • A plot of the temperature versus time Evaporation
• Molecules at the surface break away and
become gas.
• Only those with enough KE
escape
Hea
t of
• Evaporation is a cooling
Vap
process.
oriz
• It requires heat.
• Endothermic. atio
Condensation n
Change from gas to liquid
Achieves a dynamic equilibrium with vaporization
in a closed system.
What the heck is a
“dynamic equilibrium?”
Critical Stuff
• Critical Temperature: The temperature Dynamic equilibrium
above which it is impossible to liquefy the
gas under study no matter how high the When first sealed the molecules gradually escape
applied pressure. the surface of the liquid

• Critical Pressure: The pressure required to As the molecules build up above the liquid some
liquefy a gas as at its critical temperature condense back to a liquid.

NOTE: the critical temp of a gas gives an indication As time goes by the rate of vaporization remains
of the strength of the IMF of that gas. A substance constant
with weak attractive forces would have a low
but the rate of condensation increases because there
critical temp.
are more molecules to condense.
Vapor Pressure (vp)
Equilibrium is reached when
Vapor Pressure: Pressure exerted by molecules that
Rate of Vaporization = Rate of Condensation
have enough energy to escape the surface.
As T ↑ VP ↑evaporation ↑
In a closed container
Liquids with high VP are volatile (alcohol
the number of
evaporates easily) partials changing
Liquids that have strong IMF have low vapor
pressures. from liquid  vapor
(take a lot of energy to overcome IMF so it can
evaporate)
will eventually equal
• Liquids with high VP are volatile (alcohol
the number changing
evaporates easily)
from vapor  liquid.
• Liquids that have strong IMF have low
vapor pressures.
• (take a lot of energy to overcome IMF so it
can evaporate)
 • Ionic solids have strong intermolecular
The vapor pressure forces so a high mp.
of the liquid = air • Covalent/molecular solids have weak
pressure above the intermolecular forces so a low mp.

liquid Phase Diagram

• A graphical way to summarize the
How to make something boil conditions under which equilibrium exists
between different states of matter.
1. Increase the VP of the liquid (heat it) so that
the VP of the liquid is > that of the • Allows you to predict
the phase of a substance
Not Water that is stable at a given
temperature and
atmosphere. pressure.

2. Lower the atmospheric pressure (pressure

above the liquid) (put a lid on it)
Boiling Point
↑ boiling pt by
↑ in IMF
Or
↓ VP
At high altitudes (low air pressure) water boils at a

Critical Point: The temp

beyond which the
,molecules of a
substance have to
much kinetic energy to
stick together to form a
liquid.

lower temperature
Normal Boiling Point
• Temperature at which something boils when
the vp =1 atm
• Note the lower the external pressure the
lower the boiling point.
Freezing point/melting point
• They are the same but in opposite directions.
• When heated the particles vibrate more
rapidly until they shake themselves free of
each other.