Unit 10: Intermolecular Forces

Previously on General Chemistry…

Ionic Bond – transferred electron(s)
cation (metal) loses electron(s) to anion (nonmetal)

Covalent Bond – shared electron pair

each covalent bond has two electrons that are
shared by overlapping orbitals

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 1 Previously on General Chemistry…
Lewis Dot Structure of molecular compound Example:
1. Count total number of valence electrons (add CH2O
or subtract electrons if there is a charge) 12 valence e-
2. The central atom is the least electronegative 6 valence e-
atom (except H) and make a bond from 0 valence e-
central atom to each peripheral atom(s)
3. Distribute electrons to peripheral atom(s)
first, then to central if possible
4. If any atom does not have octet fulfilled, use
double bonds and triple bonds to satisfy all
atoms to have full octet (except H)
5. If there are resonance structures, use formal
charge to determine most stable structure

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2 Previously on General Chemistry…
Electronegativity: Ability of an atom to attract bonding
electrons
1. Draw the Lewis structure
2. Determine the steric number (SN) of the central atom
SN = (number of atoms bonded to central atom)
+ (number of lone pairs on central atom)
3. Use the SN to determine the geometry
around the central atom
4. Optimize molecular structure by determining the
number of lone pairs and bonding pairs of electrons
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3 Previously on General Chemistry…
Steric Number # Atoms Bonded # Lone Pairs Electron-Pair Geometry Molecular geometry
6 6 0 Octahedral Octahedral

5 1 Octahedral Square pyramidal

4 2 Octahedral Square planar
5 5 0 Trigonal Bipyramidal Trigonal Bipyramidal

4 1 Trigonal Bipyramidal See-saw

3 2 Trigonal Bipyramidal T-shaped

4 4 0 Tetrahedral Tetrahedral

3 1 Tetrahedral Trigonal Pyramidal

2 2 Tetrahedral Bent
3 3 0 Trigonal Planar Trigonal Planar

2 1 Trigonal Planar Bent

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2 0 Linear Linear
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 4 Previously on General Chemistry…
Polar vs. Nonpolar Molecules
Requirements for Polar Molecule:
1. Molecule must contain polar bonds (i.e., covalent bond
between atoms with ΔEN)
2. Orientation of polar bonds results in charge separation
from one part of the molecule to another

Nonpolar Polar

The vectors cancel out For H2O, a net vector points up

Its dipole moment is zero Water has a dipole moment 6
 7

Intramolecular Forces: forces that happen

Intramolecular vs within that keep the molecule or compound
together

Intermolecular Intermolecular Forces: interactions that

happen between two or more distinct
particles
 Types of Forces
Intramolecular Forces include:
– Ionic Bonds
– Covalent Bonds
– Metallic Bonding
Intermolecular Forces include:
– Ion-dipole interactions
– Dipole-dipole interactions
• Hydrogen bonds
– Dispersion forces (London forces)
– Ion-induced dipole interactions
– Dipole-induced dipole interactions
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 Ion-Ion Interactions
Coulomb’s Law:
Energy (E) of interaction is directly proportional to the
charges of the ions (Q1, Q2), and inversely proportional
to the distance (d) between them
(Q1 xQ2 )
E∝
d

Attractive force will increase as charge on ion increases

and decrease as ionic radius increases.
Smaller ionic radii = smaller distance (d) between ions
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Practice: Predicting Ion-Ion Attractions
Predict which salt in the following pairs exhibits
the greater ion-ion attractions.
a) MgO and NaF b) MgO and MgS

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 Intermolecular Forces
Involving Polar Molecules
Ion-Dipole:
– Interaction between an ion and the partial charge
of a molecule with a permanent dipole.
Sphere of Hydration:
– Cluster of water molecules surrounding an ion as
it dissolves in aqueous solution.
– Sphere of solvation if solvent other than H2O.

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 Ion-Dipole Interactions

Ion-Dipole Interactions Sphere of Hydration

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 Dipole-Dipole Interaction
Interaction of two molecules that have dipole
moments
– opposite ends of dipole align

Example: CH3COCH3 (acetone)

δ- δ-
δ+ δ+

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 Hydrogen Bonding
Hydrogen Bond:
Special class of dipole-dipole
interactions due to strength
One polar molecule is attracted
to H- from another polar
molecular that is covalently
bonded to strongly
electronegative atom (N, O, or F)
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Examples of H-Bonding

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Hydrogen • H-bonding in complementary
Bonding in DNA nucleotide bases

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 Induced Dipoles
Ion or dipole induces a dipole on an otherwise
nonpolar molecule
Ion-induced dipole Dipole-induced dipole

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 Induced Dipoles
Dipole Example
Proximity of polar molecule = Dipole − Induced Dipole

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 Interactions of Nonpolar Molecules
(London) Dispersion forces:
– Caused by temporary (or induced) dipoles
in molecules
Induced dipole:
– Separation of charge in an atom or molecule due
to a momentary uneven distribution of electrons

Qualitative explanation: instantaneous dipole on one

molecule induces dipole on another molecule
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London Dispersion Forces

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 Strength of Dispersion Forces
Factors affecting strength of dispersion:
Size of Atoms/Molecules:
– Polarizability: Relative tendency of electron density of an atom
or molecule to be distorted by a charged particle
– Larger atoms/molecules more polarizable than small
atoms/molecules
– Dispersion increases with polarizability
Shape of Molecules:
– Increased surface area = increased interactions between
molecules
– Linear molecules have higher dispersion than branched
molecules of similar MW
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 Effect of Molar Mass on Dispersion
As molar mass increases, dispersion forces increase

Halogen Mm State of
(g/mol) Matter
F2 38 Gas
Cl2 71 Gas
Br2 160 Liquid
I2 254 Solid

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Effect of Shape on Dispersion

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 van der Waals Forces
Loosely, collection of attractive forces that hold
molecules together

• Or collection of attractive and repulsive forces

• Or dipole-dipole, London dispersion, and

hydrogen bonding forces

• Or dipole-dipole, London dispersion

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 Magnitude of Forces
Attraction between two particles
Energy
Particle 1 Particle 2 Interaction
(kJ/mol)
Ion Ion Ionic bond 500-3000
Atom Atom within same molecule Covalent bond 150-1000
Ion Polar Ion-dipole 40-600
H- in polar molecule that is Hydrogen
Polar 4-50
bonded to N, O, F Bonding
Polar Polar Dipole-dipole 5-25
Ion-induced
Ion Nonpolar 3-15
dipole
Dipole induced
Polar Nonpolar 2-10
dipole
Nonpolar Nonpolar Dispersion forces 0.05-40
van der Waals Forces 25
 Intermolecular Force and Physical
Properties of Liquids and Solutions

Increase intermolecular forces will affect

– Boiling/melting point
– Vapor pressure
– Surface tension
– Viscosity

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 Boiling point

The boiling point is the temperature at which the vapor

pressure is equal to the pressure on the liquid, usually
atmospheric pressure. At this temperature, bubbles of gas form
within the liquid. The normal boiling point is measured at 1
atmosphere pressure.

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Effect of Dispersion vs H-Bonding on Boiling Points

Hydrocarbon Alcohol
Molecular M Boiling Point Molecular M Boiling Point
Formula (g/mol) (°C) Formula (g/mol) (°C)
CH4 16.04 -161.5
CH3CH3 30.07 -88 CH3OH 32.04 64.5
CH3CH2CH3 44.09 -42 CH3CH2OH 46.07 78.5
CH3CH(CH3)CH3 58.12 -11.7 CH3CH(OH)CH3 60.09 82
CH3CH2CH2CH3 58.12 -0.5 CH3CH2CH2OH 60.09 97

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 The Effect of Hydrogen Bonding
What we might expect (based mass):

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 The Effect of Hydrogen Bonding
Experimental
What we observe:

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 States and Degrees of Freedom
The molecules in a gaseous state have complete freedom
of motion
– Kinetic energy overcomes the attractive forces
between molecules

The molecules in a liquid state have limited freedom

– they have enough kinetic energy to overcome
some of the attractive forces, but not enough to
escape each other and form a gas

The molecules in a solid state are locked in place

– molecules don’t have enough thermal energy to
overcome the attractive forces
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 Review of End of CHEM104
Phase Change Enthalpy
The heat of fusion, DHfus, is the heat needed to melt a
solid. It is given in kJ/mol.
H2O (s) → H2O (l); ΔHfus = 6.01 kJ/mol
For ice, the phase change is represented by

The heat of vaporization, DHvap, is the heat needed to

vaporize a liquid. It is given in kJ/mol.

For water,
H Othe phase
(l) → H Ochange is represented
(g); ΔH by
= 40.7 kJ/mol
2 2 vap

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Phase Changes
The molecules in a gaseous
state have complete freedom of
motion

The molecules in a
liquid state have
limited freedom
(Liquefaction)

The molecules in a
solid state are locked
in place

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 States of Matter
Kinetic Energy vs Attractive Forces
Kinetic Energy (KE)
highest intermediate lowest
Intermolecular Forces (IMF)
lowest intermediate highest

Gas Liquid Solid

KE > all IMF KE > some IMF KE < all IMF

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 Vapor Pressure
Vapor pressure:
– Pressure exerted by a gas in equilibrium with its
liquid
– Rates of evaporation
and condensation are
equal (Dynamic equilibrium)

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 Vapor Pressure vs Temperature: IMF

(Increasing attractive forces)

Normal boiling point: the temperature at which the

vapor pressure of a liquid equals 1 atm (760 mmHg)
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 Vapor Pressure vs Temperature
When vapor pressure is plotted When the natural log (ln P) of the vapor
versus temperature, a curve is pressure is plotted against the reciprocal of
obtained temperature (1/T), a straight-line graph is
obtained
Pvap vs Temp lnPvap vs 1/Temp

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 Vapor Pressure vs Temperature
Δ𝐻𝑣𝑎𝑝 1
Clausius–Clapeyron: ln 𝑃𝑣𝑎𝑝 =− +𝐶
𝑅 𝑇

Plot of ln(P) vs 1/T yields

straight line:
Slope = −ΔHvap/R
Intercept = constant (C)

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Vapor Pressure vs Temperature: Clausius–Clapeyron
Clausius–Clapeyron Equation:
Δ𝐻𝑣𝑎𝑝 1
ln 𝑃𝑣𝑎𝑝 =− +𝐶
𝑅 𝑇

The Clausius–Clapeyron equation describes the straight line graphs

For a given solvent at two different temperatures:

𝑃𝑣𝑎𝑝,𝑇1 Δ𝐻𝑣𝑎𝑝 1 1
ln = −
𝑃𝑣𝑎𝑝,𝑇2 𝑅 𝑇2 𝑇1

R = 8.314 J/(mol K)
ΔHvap must be given in J/mol
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 Practice Problem
Carbon disulfide, CS2, is a volatile, flammable
liquid. It has a vapor pressure of 400.0 mmHg at
28.0˚C and a normal boiling point of 46.5˚C.
a) What is the heat of vaporization of this
substance in kJ/mol?

b) At which pressure would CS2 have a boiling

point of 75˚C?
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 Factors Affecting Physical States
Intermolecular forces:
– Strength of attractive forces compared
to kinetic energy of atoms/molecules

Temperature:
– Affects kinetic energy of atoms/molecules

Pressure:
– Affects distance between atoms/molecules

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Phase Diagram Basics

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 Physical State and Phase Transformations
Phase diagram:
A graphic representation of the stabilities of physical states of a
substance as a function of temperature and pressure
– Triple Point: Temperature/pressure where all three phases
coexist
– Critical Point: Specific temperature/pressure at which the liquid
and gas phases have the same density
– Supercritical region: fourth state of matter above the critical
temperature and pressure with properties intermediate
between gas and liquid
– Equilibrium lines: represent phase changes between
solid/liquid, liquid/gas, and solid/gas under specific conditions
(T, P)
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 Supercritical fluid
The critical point gives the temperature (critical temperature, TC) at which the
liquid state can no longer exist and the pressure at that temperature (critical
pressure). Above this temperature and pressure, there is only one state, a
supercritical fluid. This is illustrated below for CO2, for which TC = 31°C.

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 Phase Diagram for H2O
The phase diagram for water
illustrates the components
described on the previous
slide.

The slope of the BD line,

which shows the equilibrium
between solid and liquid,
slants to the left. This is
because the density of the
liquid is greater than the
density of the solid.
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 Density
Density of water decreases when it freezes.

H-bonding results in cage-like

structure in solid state; less dense
than liquid state.

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 Phase Diagram for CO2
The phase diagram for
CO2 (carbon dioxide) is
given at right. Note the
solid-liquid equilibrium
has a positive slope.

At STP, carbon dioxide

is never a liquid. That is
why carbon dioxide
sublimes directly from
solid to gas.

101.3 kPa = 1 atm

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 Practice: Phase Diagrams
Describe the phase changes that occur when the
temperature of CO2 is increased from −100°C to
200°C at a pressure of 2.5 x 103 kPa.

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 Phase Diagram for Sulfur
The phase diagram for S
(sulfur) shows some
interesting characteristics.
The existence of two different
solid structures for sulfur,
rhombic and monoclinic,
gives rise to more than one
triple point.

Both Solids

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 Problem to Consider
When camping at a high altitude, you need to pay particular
attention to changes in cooking times for foods that are boiled
in water. If you like eggs that are boiled for 10 minutes near sea
level, would you have to cook them for a longer or a shorter
time at 3200 m to get the egg you like? Explain your answer.

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 Properties of Liquids
Surface Tension:
– Resistance of liquid to any increase in surface area

Viscosity:
– Measure of resistance of a liquid to flow

Related to Intermolecular Forces:

– As attractive forces increase, surface tension and
viscosity also increase
– Related examples: meniscus, capillary action 51
 Factors Affecting Surface Tension
Increase intermolecular attractive forces, increase
surface tension

Increase temperature, decrease surface tension

– raising the temperature of the liquid increases the average
kinetic energy of the molecules
– the increased molecular motion makes it easier to stretch
the surface

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 Surface Tension
Water has high surface tension
– large attractive intermolecular force because of
hydrogen bonding
– objects float on water because it takes energy to
break the water surface

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 Viscosity
Viscosity:
– Measure of resistance of a liquid to flow
– Increase intermolecular attractive forces, increase
viscosity

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 Cohesive vs Adhesive Forces: Meniscus
Cohesive forces: interactions
between like particles

Adhesive forces: interactions

between unlike particles

Meniscus: Curvature of liquid surface due to adhesive and cohesive

forces:
Concave: adhesive forces  cohesive forces (e.g., water on glass)
Convex: Cohesive forces > adhesive forces (e.g., mercury on glass)
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 Capillary Action
Capillary action:
– The rise of a liquid up a narrow tube due to adhesive
forces between the liquid and the tube and cohesive
forces within the liquid.

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 Intermolecular Force and Physical
Properties of Liquids and Solutions

Increase intermolecular forces

– Increases boiling/melting point
– Decreases vapor pressure
– Increases surface tension
– Increases viscosity

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 Learning Objectives
● Intermolecular forces
○ comprehend intermolecular forces and identify those available
in a species based on structure: ionic, dipole, induced dipole,
London dispersion, van der Waals and hydrogen bonding
interactions in liquids
○ predict liquid properties based on intermolecular interactions
● Phase diagrams
○ identify liquid, solid, gaseous regions of phase diagram
○ contrast and compare phase diagrams of water and carbon
dioxide
○ identify and comprehend triple point and critical point
○ interpret phase transitions when temperature or pressure is
held constant