Chemistry, Principles of General Chemistry
6th Edition Silberberg
Liquids and Solids and
Intermolecular Forces
Intermolecular
Forces
OBJECTIVES
a. Describe the characteristic properties that
differentiate gas, liquids and solids.
b. Identify the molecular behavior that is
responsible for each property of gases,
liquids and solids.
c. Describe and differentiate the types of
intermolecular forces.
d. Predict the intermolecular forces possible for
a molecule.
e. Rank molecules according to its
Intermolecular
intermolecular forces. Forces
VOCABULARY
PHASE
- A homogeneous part of system in contact
with the other part of the system, but are
separated by a well-defined boundaries.
CONDENSED PHASE
- Phase of matter where the molecules are
close together. Example: liquids and solids.
Intermolecular
Forces
VOCABULARY
INTRAMOLECULAR FORCE
- Forces that hold the atoms together in a
molecule.
Ex. COVALENT, IONIC and METALLIC
INTERMOLECULAR FORCES
- Attractive forces between molecules
Ex. Ion-Dipole, hydrogen bond, dipole-
dipole and Dispersion Intermolecular
Forces
RECALL
KINETIC MOLECULAR
THEORY
a. All matter is made up of tiny
particles.
b. These particles are in constant
motion.
c. The speed of particles is
proportional to its temperature. Intermolecular
Forces
RECALL
KINETIC MOLECULAR
THEORY
d. There are spaces between particles
of matter
e. There are attractive forces between
atoms/molecules
Intermolecular
Forces
RECALL
MOLECULAR POLARITY
AND BOND DIPOLE
a. Cl2
b. NH3
c. CH3Br
d. CH4 Intermolecular
Forces
States of Matter
The fundamental difference between states of
matter is the distance between particles.
Intermolecular
Forces
States of Matter
The fundamental difference between states of
matter is the distance between particles.
Intermolecular
Forces
States of Matter
Because in the solid and liquid states
particles are closer together, we refer to them
as condensed phases.
Intermolecular
Forces
The States of Matter
• The state a substance is
in at a particular
temperature and
pressure depends on
two antagonistic entities:
– the kinetic energy of the
particles;
– the strength of the
attractions between the
particles. Intermolecular
Forces
Intermolecular Forces
The attractions between molecules are not
nearly as strong as the intramolecular
attractions that hold compounds together.
Intermolecular
Forces
Intermolecular Forces
They are, however, strong enough to control
physical properties such as boiling and
melting points, vapor pressures, and
viscosities.
Intermolecular
Forces
INTERMOLECULAR
FORCES
• Ion-Dipole Forces
• Dipole-dipole interactions
• Hydrogen bonding
• London dispersion forces
Intermolecular
Forces
Ion-Dipole Interactions
• Ion-dipole interactions are important in
solutions of ions.
• The strength of these forces are what make it
possible for ionic substances to dissolve in
polar solvents.
Intermolecular
Forces
Dipole-Dipole Interactions
• Molecules that have
permanent dipoles are
attracted to each other.
– The positive end of one is
attracted to the negative
end of the other and vice-
versa.
– These forces are only
important when the
molecules are close to
each other.
Intermolecular
Forces
Dipole-Dipole Interactions
The more polar the molecule, the higher
is its boiling point.
Intermolecular
Forces
© 2009, Prentice-Hall, Inc.
London Dispersion Forces
While the electrons in the 1s orbital of helium
would repel each other (and, therefore, tend
to stay far away from each other), it does
happen that they occasionally wind up on the
same side of the atom. Intermolecular
Forces
London Dispersion Forces
At that instant, then, the helium atom is polar,
with an excess of electrons on the left side
and a shortage on the right side.
Intermolecular
Forces
London Dispersion Forces
Another helium nearby, then, would have a
dipole induced in it, as the electrons on the
left side of helium atom 2 repel the electrons
in the cloud on helium atom 1.
Intermolecular
Forces
London Dispersion Forces
London dispersion forces, or dispersion
forces, are attractions between an
instantaneous dipole and an induced dipole.
Intermolecular
Forces
London Dispersion Forces
• These forces are present in all molecules,
whether they are polar or nonpolar.
• The tendency of an electron cloud to distort in
this way is called polarizability.
Intermolecular
Forces
Factors Affecting London Forces
• The shape of the molecule
affects the strength of dispersion
forces: long, skinny molecules
(like n-pentane tend to have
stronger dispersion forces than
short, fat ones (like neopentane).
• This is due to the increased
surface area in n-pentane.
Intermolecular
Forces
Factors Affecting London Forces
• The strength of dispersion forces tends to
increase with increased molecular weight.
• Larger atoms have larger electron clouds
which are easier to polarize.
Intermolecular
Forces
Sample Exercise 1. Comparing Intermolecular Forces
The dipole moments of acetonitrile, CH3CN, and
methyl iodide, CH3I, are 3.9 D and 1.62 D,
respectively.
(a) Which of these substances has greater dipole–
dipole attractions among its molecules? (b) Which of
these substances has greater London dispersion
attractions? (c) The boiling points of CH3CN and CH3I
are 354.8 K and 315.6 K, respectively. Which
substance has the greater overall attractive forces?
Intermolecular
Forces
Sample Exercise 1. Comparing Intermolecular Forces
Solution
(a) Dipole–dipole attractions increase in magnitude as the dipole
moment of the molecule increases. Thus, CH3CN molecules attract
each other by stronger dipole–dipole forces than CH3I molecules do.
(b) When molecules differ in their molecular weights, the more
massive molecule generally has the stronger dispersion attractions.
In this case CH3I (142.0 g/mol) is much more massive than CH3CN
(41.0 g/mol), so the dispersion forces will be stronger for CH3I. (c)
Because CH3CN has the higher boiling point, we can conclude that
more energy is required to overcome attractive interactions between
CH3CN molecules. Thus, the total intermolecular attractions are
stronger for CH3CN, suggesting that the energies resulting from
dipole–dipole forces are decisive when comparing these two
substances. Nevertheless, the attractive interactions due to dispersion
forces play an important role in determining the properties of CH3I.
Intermolecular
Forces
Practice Exercise
Of Br2, Ne, HCl, HBr, and N2, which is likely to
have (a) the largest intermolecular dispersion
forces, (b) the largest dipole–dipole attractive
forces?
Intermolecular
Forces
How Do We Explain This?
• The nonpolar series
(SnH4 to CH4) follow
the expected trend.
• The polar series
follows the trend
from H2Te through
H2S, but water is
quite an anomaly.
Intermolecular
Forces
Hydrogen Bonding
• The dipole-dipole interactions
experienced when H is bonded to
N, O, or F are unusually strong.
• We call these interactions
hydrogen bonds.
Intermolecular
Forces
Hydrogen Bonding
• Hydrogen bonding arises
in part from the high
electronegativity of
nitrogen, oxygen, and
fluorine. (F,O,N)
Also, when hydrogen is bonded to one of those
very electronegative elements, the hydrogen
nucleus is exposed. Intermolecular
Forces
Sample Exercise 2 Identifying Substances that Can Form Hydrogen Bonds
In which of the following substances is hydrogen
bonding likely to play an important role in
determining physical properties: methane (CH4),
hydrazine (H2NNH2), methyl fluoride (CH3F), or
hydrogen sulfide (H2S)?
Intermolecular
Forces
Sample Exercise 2 Identifying Substances that Can Form Hydrogen Bonds
Solution
Analyze: We are given the chemical formulas of four
substances and asked to predict whether they can
participate in hydrogen bonding. All of these
compounds contain H, but hydrogen bonding usually
occurs only when the hydrogen is covalently bonded
to N, O, or F.
Plan: We can analyze each formula to see if it
contains N, O, or F directly bonded to H. There also
needs to be a nonbonding pair of electrons on an
electronegative atom (usually N, O, or F) in a nearby
molecule, which can be revealed by drawing the Intermolecular
Lewis structure for the molecule.
Forces
Sample Exercise 2 Identifying Substances that Can Form Hydrogen Bonds
Solution
Solve: The criteria listed above eliminate CH4 and H2S,
which do not contain H bonded to N, O, or F. They also
eliminate CH3F, whose Lewis structure shows a central C
atom surrounded by three H atoms and an F atom.
(Carbon always forms four bonds, whereas hydrogen and
fluorine form one each.) Because the molecule contains
C—F a bond and not a H—F bond, it does not form
hydrogen bonds. In H2NNH2, however, we find bonds. If
we draw the Lewis structure for the molecule, we see that
there is a nonbonding pair of electrons on each N atom.
Therefore, hydrogen bonds can exist between the
molecules as depicted below.
Intermolecular
Forces
Sample Exercise 11.2 Identifying Substances that Can Form Hydrogen Bonds
Solution (continued)
Check: While we can generally identify substances
that participate in hydrogen bonding based on their
containing N, O, or F covalently bonded to H,
drawing the Lewis structure for the interaction, as
shown above, provides a way to check the prediction.
Practice Exercise
In which of the following substances is significant
hydrogen bonding possible: methylene chloride
(CH2Cl2), phosphine (PH3), hydrogen peroxide
(HOOH), or acetone (CH3COCH3)?
Answer: HOOH
Intermolecular
Forces
Summarizing Intermolecular Forces
Intermolecular
Forces
Sample Exercise 3 Predicting the Types and Relative Strengths of Intermolecular
Attractions
List the substances BaCl2, H2, CO, HF, and Ne in order of increasing boiling
points.
ANSWER
H2 < Ne < CO < HF < BaCl2
Check: The actual normal boiling points are H2 (20 K), Ne (27
K), CO (83 K), HF (293 K), and BaCl2 (1813 K)—in
agreement with our predictions.
Intermolecular
Forces
Practice Exercise
(a) Identify the intermolecular attractions present in the
following substances, and (b) select the substance with
the highest boiling point: CH3CH3, CH3OH, and
CH3CH2OH.
Answer: (a) CH3CH3 has only dispersion forces,
whereas the other two substances have both dispersion
forces and hydrogen bonds; (b) CH3CH2OH
Intermolecular
Forces
