Intermolecular forces

11-1
 States of Matter
 The fundamental difference
between states of matter is
the strength of the
intermolecular forces of
attraction.
 Stronger forces bring
molecules closer together.
 Solids and liquids are
referred to as the condensed
phases.

11-2
 Differences in the States of Matter

11-3
 Which State of Matter?
• The answer to this
question largely relies
on the
 balance between the
kinetic energies of the
particles.
 interparticle energies
of attraction.

11-4
 Intermolecular Forces

• The attractions between molecules are not nearly as strong

as the intramolecular attractions (bonds) that hold
compounds together.
• Many physical properties reflect intermolecular forces,
like boiling points, melting points, viscosity, surface
tension, and capillary action.
11-5
 Comparison of Bonding Forces

Basis of Energy
Force Model Attraction (kJ/mol) Example

Ionic Cation–anion 400–4000 NaCl

Nuclei–
Covalent 150–1100 H─H
shared e−pair

Cations–
Metallic delocalized 75–1000 Fe
electrons

11-6
 Comparison of Non-Bonding Forces
Basis of Energy
Force Model Attraction (kJ/mol) Example

Ion charge–
Ion–dipole 40–600
dipole charge

Polar bond to
H-dipole
H bond 10–40
charge (high
EN of N, O, F)

Dipole–dipole Dipole charges 5–25 l─Cl⋯l─Cl

Ion charge–
Ion–induced Fe2+⋯O2
polarizable e−cl 3–15
dipole
oud
Dipole charge–
Dipole–
polarizable e−cl 2–10 H─Cl⋯Cl─Cl
induced dipole
oud
Dispersion Polarizable
0.05–40 F─F⋯F─F
(London) e−clouds

11-7
 • There are three types on intermolecular forces that exist
between electrically neutral molecules:
1. Dispersion Forces
2. Dipole-Dipole Interactions
3. Hydrogen Bonding
• The first two forces are collectively called van der Waals forces.
• Another kind of attractive force, the ion-dipole force, is
important in solutions.
• All intermolecular interactions are electrostatic, involving
attractions between positive and negative species, much like
ionic bonds but much weaker

8
11-8
 Types of Intermolecular Force
• Strongest to weakest forces:
 dispersion forces (or London dispersion forces)
 dipole–dipole forces
 hydrogen bonding (a special dipole–dipole force)
 ion–dipole forces
o Note: The first two types are also referred to
collectively as van der Waals forces.

11-9
 1. Ion-dipole interaction
• Ion-dipole interaction are found in solutions of ions
• The strength of these forces is what makes it possible for ionic
substances to dissolve in polar solvents.
• Example: Interaction of sodium and chloride ions with water molecules
in an aqueous solution (NaCl (Ionic) + H2O)

11-10
 2. Dipole–Dipole Interactions
• Polar molecules have a more positive and a
more negative end–a dipole (two poles, δ+ and
δ−). CH3
• The oppositely charged ends attract each other.

11-11
 Question

11-12
 Dipole–Dipole Interactions

For molecules of approximately equal mass and

size, the more polar the molecule, the higher its
boiling point.
11-13
11-14
 3. Ion–induced dipole interactions
• An ion-induced dipole attraction is a weak attraction that results
when the approach of an ion induces a dipole in an atom or in a
nonpolar molecule by disturbing the arrangement of electrons in the
nonpolar species.

11-15
 4. Dipole–induced dipole Interactions
• A dipole-induced dipole attraction is a weak attraction that results when
a polar molecule induces a dipole in an atom or in a nonpolar molecule
by disturbing the arrangement of electrons in the nonpolar species.
• Any other example-?

11-16
 5. Dispersion (London) Forces
• Dispersion forces or London forces arise when an instantaneous
dipole in one particle induces a dipole in another, resulting in an
attraction between them.
• There are electrostatic interactions between electrically neutral
atoms and/or molecules (such as liquified nonpolar gases).
• The average distribution of electrons around a nucleus is
symmetrical. However, the random motion of electrons in an
atom or molecule can create an instantaneous, or momentary,
dipole moment.
• In He atoms, for example, if both electrons happen to be on one
side of the atom, the atom has an instantaneous dipole.

17
11-17
 Instantaneous and induced dipoles in He atoms

• The tendency of an electron cloud to distort is called its

polarizability.
18
11-18
 Factors Which Affect Amount of
Dispersion Force in a Molecule
• number of electrons in an
atom (more electrons, more
dispersion force)
• size of atom or
molecule/molecular weight
• shape of molecules with
similar masses (more
compact, less dispersion
force)

11-19
Factors That Affect Amount of Dispersion Force in a
Molecule
 Number of electrons: the more electrons in an atom or
molecule, the greater the dispersion force.
 Increasing molecular weight: dispersion forces increase as
molecular weights increase.

 Figure to right shows

the differences in
boiling points
between nonpolar
halogen molecules
and noble gases in
the same periods.

20
11-20
 Molecular shape: the greater the intermolecular contact due to
shape, the greater the dispersion forces.
– For example, neopentane and n-pentane have same molecular formula
but differ in boiling points due to their shapes (linear vs spherical).

21
11-21
 Polarizability and Induced Dipoles
• A nearby electric field can induce a distortion in the electron
cloud of an atom, ion, or molecule.
– For a nonpolar molecule, this induces a temporary dipole moment.
– For a polar molecule, the field enhances the existing dipole moment.

• The polarizability of a particle is the ease with which its

electron cloud is distorted.

11-22
 Trends in Polarizability
• Smaller particles are less polarizable than larger ones because
their electrons are held more tightly.
• Polarizability increases down a group because atomic size
increases and larger electron clouds distort more easily.
• Polarizability decreases across a period because of increasing
Zeff.
• Cations are smaller than their parent atoms and less
polarizable; anions show the opposite trend.

11-23
 Intermolecular forces

• Vander wall forces * KJ/mole

• Hydrogen bonding < 42
• Weak interactions /secondary
interaction/secondary forces/Non bonding

11-24
 Dipole Moment and Boiling Point

Figure 12.14
11-25
 Hydrogen bonding

11-26
 Polar Molecules and Dipole-Dipole Forces

Figure 12.13
11-27
 Problem: Identify hydrogen bond

11-28
 Hydrogen bond

11-29
 Hydrogen bonds
• Hydrogen bonding refers to the formation of Hydrogen bonds, which are a special class of
attractive intermolecular forces that arise due to the dipole-dipole interaction between a hydrogen
atom that is bonded to a highly electronegative atom and another highly electronegative atom which
lies in the vicinity of the hydrogen atom. For example, in water molecules (H 2O), hydrogen is
covalently bonded to the more electronegative oxygen atom. Therefore, hydrogen bonding arises in
water molecules due to the dipole-dipole interactions between the hydrogen atom of one water
molecule and the oxygen atom of another H 2O molecule.

• Here, the location of the bond pair of electrons in the O-H bond is very close to the oxygen nucleus
(due to the large difference in the electronegativities of oxygen and hydrogen). Therefore, the
oxygen atom develops a partial negative charge (-δ) and the hydrogen atom develops a partial
positive charge (+δ). Now, hydrogen bonding can occur due to the electrostatic attraction between
the hydrogen atom of one water molecule (with +δ charge) and the oxygen atom of another water
molecule (with -δ charge). Thus, hydrogen bonds are a very special class of intermolecular
attractive forces that arise only in compounds featuring hydrogen atoms bonded to a highly
electronegative atom. Hydrogen bonds are mostly strong in comparison to normal dipole-dipole and
dispersion forces. However, they are weak compared to true covalent or ionic bonds.

11-30
 • In a molecule, when a hydrogen atom is linked to a highly electronegative atom, it attracts the
shared pair of electrons more and so this end of the molecules becomes slightly negative while
the other end becomes slightly positive. The negative end of one molecule attracts the
positive end of the other and as a result, a weak bond is formed between them. This bond is
called the hydrogen bond.
• As a result of hydrogen bonding, a hydrogen atom links the two electronegative atoms
simultaneously, one by a covalent bond and the other by a hydrogen bond. The conditions for
hydrogen bonding are:
• The molecule must contain a highly electronegative atom linked to the hydrogen atom. The
higher the electronegativity more is the polarization of the molecule.
• The size of the electronegative atom should be small. The smaller the size, the greater is the
electrostatic attraction.

11-31
 Effects of Hydrogen Bonding on Elements

• Association
• The molecules of carboxylic acids exist as dimer because of the hydrogen bonding. The
molecular masses of such compounds are found to be double than those calculated from their simple
formula.
• Dissociation
• In aqueous solution, HF dissociates and gives the difluoride ion instead of fluoride ion. This is due
to hydrogen bonding in HF. The molecules of HCl, HBr, HI do not form a hydrogen bond. This
explains the non-existence of compounds like KHCl 2, KHBr2, KHI2.
• Why do compounds having hydrogen bonding have high melting and boiling points?
• The compounds having hydrogen bonding show abnormally high melting and boiling points. The
high melting and boiling point of the compound containing hydrogen bonds is due to the fact that
some extra energy is needed to break these bonds.
• The unusually high boiling point of hydrogen fluoride among the halogen acid is due to the
existence of hydrogen bonding.
• H2O is a liquid whereas H2S, H2Se and H2Te are all gases at ordinary temperature. In water,
hydrogen bonding causes linkages in the water molecules which result in the boiling point of water
is more than that of the other compounds.
• Ammonia has a higher boiling point than PH 3 because there is hydrogen bonding in NH 3 but not in
PH3.
• Ethanol has a higher boiling point than diethyl ether because there is hydrogen bonding in the
11-32
ethanol.
 HYDROGEN BONDING

• A special type of dipole-dipole interaction

between the hydrogen atom in a polar bond
and an unshared electron pair of an
element that is very electronegative usually
a F, O, or N atom on another molecule
• (note that all of these have very high EN’s
and small atomic radii).

33
11-33
 34
11-34
 HYDROGEN BONDING

35
11-35
 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).

36
11-36
 WHY HYDROGEN BONDING IS
EFFECTIVE
• F, O, & N are extremely small and very electronegative
atoms.

• Hydrogen atoms are very small and 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.
37
11-37
 The Hydrogen Bond
• Hydrogen bonding is possible for molecules that have a
hydrogen atom covalently bonded to a small, highly
electronegative atom with lone electron pairs, specifically N,
O, or F.
• An intermolecular hydrogen bond is the attraction between the
H atom of one molecule and a lone pair of the N, O, or F
atom of another molecule.

11-38
 Hydrogen Bonding and Boiling Point

Figure 12.15
11-39
 Sample Problem 12.4 – Problem and Plan
Drawing Hydrogen Bonds Between Molecules of a Substance
• PROBLEM: Which of these substances exhibits H bonding?
Draw examples of the H bonds between two molecules of each
substance that does. (a) C2H6 (b) CH3OH (c)

• PLAN: If the molecule does not contain N, O, or F, it cannot

form H bonds. If it contains any of these atoms covalently
bonded to H, we draw two molecules in the -B:⋯H-A-
pattern.

11-40
 Sample Problem 12. - Solution
• SOLUTION:
(a) No N, O, or F, so no H bonds can form.
(b) The H covalently bonded to the O in one molecule forms
an H bond to the lone pair on the O of an adjacent molecule:

(c) Two of these molecules can form one H bond between an

H bonded to N and the O, or they can form two such H bonds:

11-41