Intermolecular Forces

Questions to Ponder?

• Why is water usually a liquid and not a gas?

• Why does liquid water boil at such a high temperature for
such a small molecule?
• Why does ice float on water?
• Why do snowflakes have 6 sides?
• Why is I2 a solid whereas Cl2 is a gas?
• Why are NaCl crystals little cubes?

All of these questions may be answered by

“Intermolecular Forces”
Intermolecular Forces
• The forces holding solids and liquids together are called
intermolecular forces.
• Intermolecular Forces are the attractions and repulsions
between molecules.
• They are NOT chemical bonds.
• The intermolecular forces of a substance may exhibit are
a function of:
1. charge (ions vs. neutrals)
2. polarity (molecular shape, dipoles)
3. molar mass
Intermolecular Forces
Intermolecular forces influence chemistry in many
ways:
• They are directly related to properties such as
melting point, boiling point, and the energy
needed to convert a solid to a liquid or a liquid to
a vapor.
• They are important in determining the solubility of
gases, liquids, and solids in various solvents.
• They are crucial in determining the structures of
biologically important molecules such as DNA
and proteins.
States of Matter
Analogy
 solid - students in class
 Ordered, in their seats, low kinetic energy

 liquid - students leaving this room

 Relatively close to each other but free to
pass other students, moderate kinetic
energy
 gas - students when not in chemistry class
Why Solid, Liquid or Gas?
 Balance of
 kinetic energy
 molecular motion
 intermolecular forces
 attractions between particles (atoms,
molecules, ions)
Intramolecular vs Intermolecular
 intramolecular forces – bonds
 molecular stability
 Ionic and covalent
 intermolecular forces - particle attractions
 bulk properties
 freezing point
 boiling point
 etc.
Intermolecular Forces
 Directly related to properties such as melting
point, boiling point and energy required to
convert solids to liquids, or liquids to vapors
 Very important in determining the solubility of
gases, liquids, and solids in various solvents
 Crucial in determining the structures of
biologically important molecules such as DNA
and proteins
Concept Check
Draw representations of the following

 Dipole
 A Polar molecule, showing the Dipoles
 An ion
 A water molecule
 A cation
 An Anion
 A cation in Water
Intermolecular Forces
collectively called “van der Waals” Forces

Force Strength Characteristics

Moderate Occurs between ions and

Ion-Dipole
(10-50 kJ/mol) polar solvents

Weak Occurs between polar

Dipole-Dipole
(3-4 kJ/mol) molecules

Occurs between ALL

Weak molecules. Strength
London Dispersion
(1-10 kJ/mol) depends on size and
polarizability

Occurs between
Moderate
Hydrogen Bond molecules with O-H, N-H,
(10-40 kJ/mol)
and F-H bonds
Covalent Bonding Forces for
Comparison of Magnitude

C=C (610 kJ/mol)

C–C (346 kJ/mol)

C–H (413 kJ/mol) CN (887 kJ/mol)

Covalent Bonding Forces for
Comparison of Magnitude
20 to 30 kJ/mol

D(H-Cl) = 432 kJ/mol

Intermolecular forces are much weaker than the bonds that

make up compounds.
Types of Intermolecular Forces
 Neutral atoms, molecules
 London dispersions
 Dipole-dipole
 Dipole/Induced Dipole
 H-bonding
 collectively called van der Waal’s
Forces
 Ion-Ion Forces: Formal Charges
The forces that govern charged particles are defined by
Coulomb’s law.
Q  Q
Fk 
r2
Q = the charges on the cation and
anion
r = the distance between
k = a constant
Greater charge = stronger attraction
Greater distance = weaker attraction
These are the strong forces that lead to salts with high melting
temperatures.
H2O, mp = 0 C NaCl, mp = 800 C MgO, mp = 2800 C
 Attractions Between Ions &
Permanent Dipoles

The polar nature of water provides for

attractive forces between ions and water.
Ions and Molecules with permanent
dipoles
 Introduce solvation energy
 ΔH
 Higher the negative (exothermic) value
the stronger the attraction
Solvation of Ions

When a cation exists in solution, it is surrounded

by the negative dipole ends of water molecules.
When as anion exists in solution, it is surrounded
by the positive dipole ends of water molecules.
Enthalpies of Hydration: A Measure of
Ion-Dipole Forces

As the size of the ion increases, the exothermicity of the process

decreases.
This is due to the weaker ion-dipole forces.
Attraction Between Ions & Permanent
Dipoles

Water is highly polar and can interact with positive ions to

give hydrated ions in water.
 Molecular Polarity
Molecular Geometry Non-Polar Molecule

Both atoms the same (outer the same for

Linear
linear tri-atomic)

Trigonal Planar All bonding groups the same

Tetrahedral All bonding groups the same

All bonding groups the same or both axial

Trigonal bipyramidal groups the same and all three equatorial
groups the same,
All bonding groups the same or all groups
Octahedral
trans to one another the same.

Any deviations of symmetry yield a polar molecule.

Dipole-Dipole Forces
Dipole-dipole forces bind molecules having
permanent dipoles to one another.
Dipole - Dipole forces
 Only present in polar molecules
 compare MW bp, C *
 C3H8 44 231 0.1
 CH3CHO 44 294 2.7
 CH3CN 41 355 3.9

 * is the bond dipole which a measure of

polarity of a bond in a molecule
Dipole – Dipole Forces
 Dipole-Dipole Forces
As the polarity for a Molar Mass
Dipole
BP
Compound Moment
given set of molecules (amu)
(D)
(K)
with similar molar CH3CH2CH3 44.1 0.1 231
masses increases, the CH3OCH3 46.07 1.3 248
boiling point increases. CH3Cl 40.49 1.9 249
CH3CN 41.05 3.9 355

400

350

300

250

Boiling point 200

150

100

50 BP

0 Dipole
Dipole Moment
1
molar Mass
2
3
Molar Mass 4
Hydrogen Bonding
A special form of dipole-dipole attraction, which enhances
dipole-dipole attractions.

H-bonding is strongest when X and Y are N, O, or F

Hydrogen Bonding
The water molecules
network with one
another.
H–bonding in water
brings about a
network of
interactions which
explain phenomena
such as:

capillary action surface tension why ice floats

Hydrogen Bonding
 Forms when
 small atoms
 high electronegativity
 lone pairs present
 N, O, F
 4 - 25 kJ/mol
Boiling Points of Hydrides

Where will H2O and

CH4 be?
Boiling Points of Hydrides
 Boiling Points of Simple Hydrogen-
Containing Compounds
18 g/mol Notice that water has an
unusually high bp for its Mwt...

20 g/mol

17 g/mol

This is a result of
hydrogen bonding!
16 g/mol
• Ice Floats because it is less dense than water
• The H-bonds allow the molecules in the liquid phase
to approach closer than normal for non H-bonding
liquids
• This is why water has a maximum density at 4 C
 Hydrogen Bonding in H2O
Ice has open lattice-like structure.
Ice density is < liquid and so solid floats on water.

One of the VERY few

substances where the solid
is LESS DENSE than the
liquid.
Hydrogen Bonding in DNA
Hydrogen Bonding in DNA
Dipole/Induced Dipole
 Polar molecules i.e. water can create or
induce dipoles in molecules that do not
have dipoles
Why is this important
 Various gases such as O2, N2, H2, and
CO2 are not very soluble in water
because they are essentially non-polar
 But, oxygen must be dissolved in water
to sustain fish life
 This is due to these Dipole induce
Forces
Forces Involving Induced Dipoles
How can non-polar molecules such as O 2 and I2
dissolve in water?
The water dipole INDUCES a dipole in the O2 electron
cloud.

Dipole-induced
dipole
Induced Dipole Forces
Induced Dipole Forces
The degree to which electron cloud of an atom or
molecule can be distorted is measured by its
polarizability.
The larger the molecule, the more easily it is polarized.

As the electrons in a molecule become more loosely

held and more spread out, the greater the degree of
polarizibility in the molecule.
The explains the trend we see in solubility.
Forces Involving Induced Dipoles
Formation of a dipole in two nonpolar I2 molecules.

Induced dipole-induced
dipole
London Dispersions
Sometimes called induced dipole/induced
dipole
present in all atoms, molecules, ions
 due to unsymmetrical distribution of e –
cloud
London force Strength Proportional to
 Higher molecular mass
 More e–
London Dispersion Forces
• London dispersion forces exist between all
molecules.
• London dispersion forces are a function of molecular
polarizability.
• The Polarizability of a molecule is measured by the
ease with which an electron cloud can be distorted.
• The larger the molecule (the greater the number of
electrons) the greater polarizability. The greater the
surface area available for contact, the greater the
dispersion forces.
• London dispersion forces therefore increase as
molecular weight increases.
Polarizability
 Ease with which the charge distribution
in a molecule can be distorted
 A measure of its “squishiness”
Boiling Point
What does Boiling Point tell us?
 Intermolecular forces increase with
increasing polarization of bonds.
 Strengths of forces impact boiling point.
 Boiling point increases with molecular
weight and with surface area.
Table of Boiling Points
 BP KK
 He
F2
4.6
85.1

 Ne
Cl 27.3
238.6
2

 Ar 87.5
 Br2 332.0
 Kr 120.9
 I2 457.6
 Xe 166.1
Summary of Intermolecular Forces
Intermolecular Forces
 Summary of Intermolecular Forces
Interacting Particles

Are polar No Yes Are polar

Are ions No
No molecules molecules
involved?
involved? involved?

Are Hydrogen Yes

No atoms bonded to O, Yes
N or F involved?

London
Dipole-
Forces Hydrogen Ion-Dipole Ionic
Dipole
(induced Bonding forces Bonding
forces
dipoles)
Comparing IM forces; which has
higher bp?
 A. O
B. N22
Comparing IM forces; which has
higher bp?
 A. O
B. N22
 90 K
77 K
 nonpolar molecule; only London forces
 lower molecular
higher molecularweight
weight
Comparing IM forces; which has higher
bp?
 B. Ar
A. HCl
 37. 5g/mol
39.9 g/mol
Comparing IM forces; which has
higher bp?
 B. Ar
A. HCl
 37. 5g/mol
39.9 g/mol
 188KK
87
 London forces only
+ dipole-dipole
interactions
Comparing IM forces; which has
higher bp?
 A. N
B. NH2O3
Comparing IM forces; which has
higher bp?
 A. N
B. NH2O3
 17 g/mol
44
Comparing IM forces; which has
higher bp?
 A. N
B. NH2O3
 44 g/mol
17
 polar
Comparing IM forces; which has
higher bp?
 A. N
B. NH2O3
 44 g/mol
17
 polar
 H bonds
 240 K
185