CHY 40 Intermolecular Forces of Attraction-1

CHY 40 • This interaction is effective only when

INTERMOLECULAR FORCES OF ATTRACTION polar molecules are close to each other. It is also generally weaker than ion-dipole force.
• For molecules with approximately equal mass and size, the strengths of dipole-dipole
Intermolecular Forces of Attraction (IMFA) - the forces that exist between molecules. attraction increase with increasing polarity.
They are generally much weaker than ionic or covalent bond (intramolecular - force within the
molecule). The relative strengths of intermolecular forces vary for different substances. They 3. London dispersion force - formed from instantaneous (momentary) dipole moment created
dictate the properties of liquids such as boiling points and melting points. by the motion of electrons in an atom or molecule.
It is the IMFA that exists between nonpolar molecules and is the weakest of all known
Types of intermolecular forces of attraction: intermolecular forces. It exists between all molecules but is generally overshadowed
1. Ion-dipole force - present in electrolyte solutions when stronger forces are present.
2. Dipole-dipole force
3. London dispersion No dipole-dipole force exists between nonpolar atoms and molecules because they do not
4. Hydrogen bonding have a dipole moment. The motions of electrons on one atom influence the motions of
electrons of its neighbors. The temporary dipole on one atom can induce a similar temporary
1. Ion-dipole force - exists between an ion and the partial charge on the end of a polar dipole on an adjacent atom causing the atoms to be attracted to each other. This attractive
molecule. Polar molecules have dipoles, that is, they have partial positive and partial interaction is significant only when the molecules are very close together.
negative ends. The partial positive end of a polar molecule is attracted towards an anion and
the partial negative end of a polar molecule is attracted to a cation. This forces is specially Polarizability - the ease with which the electron distribution in a molecule is distorted. The
important for solutions of ionic compounds in polar liquids such as that for an aqueous greater the polarizability of the electrons in a molecule the more easily is its electron cloud
solution of NaCl. can be distorted, hence, the stronger the London dispersion forces. In general, larger
molecules tend to have greater polarizabilities because they have a greater number of
Figure 1. electrons and their electrons are farther from the nuclei. Dispersion forces tend to increase in
Illustration of ion-dipole strength as the molecular weight increases due to increasing size and polarizability.
interaction
Relationships: Atomic / molecular size  polarizability
Poalrizability  London dispersion force

The shapes of molecules also influence the magnitudes of dispersion forces - the greater the
surface area available for contact, the greater the dispersion forces. Comparing between
2. Dipole-dipole force - exists between neutral polar molecules. Polar molecules attract each spherical and sausage-like molecules as that between neopentane and n-pentane,
other when the negative end of molecule is in close proximity with the positive end of another respectively, the overall attraction is greater for n-pentane because the molecules can come
molecule. in contact over the entire length of the long, somewhat-cylindrically shaped molecule.

4. Hydrogen bonding - the strongest type of IMFA. It is a special case of dipole-dipole

interaction occurring between the hydrogen atom attached in a polar bond (particularly H–F,
H–O, or H–N bond) and the nonbonding electron pair on a nearby small electronegative ion or
Figure 2. atom (usually an F, O, or N atom in another molecule). The small size of the H atom makes
Illustration of dipole-dipole the F, N, or O atom of one molecule approach the H atom of another molecule closely,
interaction sufficient to produce an attraction strong enough to be called a bond.
 CHY 40 Intermolecular Forces of Attraction-2
EXERCISE 5
1. Arrange the following types of interactions in order of increasing stability: covalent bond, van
der Waals force, hydrogen bonding, dipole-dipole interaction
Figure 3. Examples of hydrogen bonding Answer: van der Waals < dipole-dipole interaction < hydrogen bonding < covalent bond
2. Which has the highest boiling point: H2, He, Ne, Xe, CH4.
Answer: Xe. All are nonpolar molecules but Xe has the greatest van der Waals force
because it has the most electrons.
3. Which is expected to have the highest melting point: PH3, NH3, (CH3)3N? Explain why.
Answer: NH3 has the strongest intermolecular forces which is hydrogen bonding, thus, it
is expected to have the highest melting point.
4. Select from the following choices that is most closely related to the items given:
Consequences of hydrogen bonding in water Ion-dipole interaction Dipole-dipole force
Generally, solids are more closely packed than liquids and hence, are denser than liquids. Hydrogen bond London dispersion force
However, in ice, H2O molecules assume an open, ordered arrangement to optimize hydrogen a. Acetone f. HF
bonding interactions between molecules. Comparably, the hydrogen bonding in liquid water is b. ICl4- g. CCl4
more random than in ice. Consequently, liquid water has a more dense structure than ice, c. MgCl2 h. HCl in C6H6
meaning a given mass of water occupies a smaller volume than the same mass of ice. This d. KI in H2O i. I2 in CCl4
also explains why ice floats on water. e. Urea, CO(NH2)2, in acetone

5. Pick from each pair the one that will exhibit the given property to the greater extent.
a. Vapor pressure HCl HF
b. Boiling point Ne Kr
c. Melting point NH3 PH3
d. Solubility in H2O NH3 PH3

Liquids
Intermolecular forces are strong enough to hold the molecules close together but are not
strong enough to keep the molecules from moving past one another. Hence, the
consequences include:
1. Liquids flow and assume the shape of their container.
2. Liquids are denser than gases - 70% of the volume of liquids is occupied by liquid
molecules.
3. Liquids are incompressible. They do not expand to fill the container.
4. Diffusion with a liquid occurs slowly.

Some properties of liquids

1. Viscosity - resistance of a liquid to flow. The more viscous the liquid is, the slower it flows.
This property is related to the ease with which individual molecules of the liquid can move
with respect to one another. It depends on the IMFA that exist in the liquid and whether
structural features exists that cause the molecules to become entangled.
Viscosity decreases with increasing temperature. At higher temperature, the average kinetic
energy of the molecules is greater. Hence, it more easily overcomes the IMFA that exists
between liquid molecules.
Relationships: Complexity of a molecule  Viscosity
Figure 4. Flowchart for determining intermolecular forces Strength of IMFA  Viscosity

1 Phase changes (changes of state) - each
T
Vis cos ity
For example, H2O is more viscous than CH3CH2OH since it can form two hydrogen bonds.
Meanwhile, oil is more viscous than H2O due to the complexity of the structure of oil.
2. Surface tension
The surface tension of water behaves almost as if it had an elastic skin. This behavior is due
to an imbalance of intermolecular forces at the surface of the liquid. The molecules in the
interior are attracted equally in all directions, whereas those at the surface experience a net
inward force. This pulls the molecules from the surface into the interior, thereby reducing the
surface area and making the molecules at the surface pack closely together.
Figure 5. Molecular-level view of surface and
interior IMFA in a liquid
The surface tension is the energy required to increase the surface area of a liquid by a unit
amount. It is the measure of the inward force in liquids. The stronger the IMFA, the larger the
surface tension.
Consequences of surface tension:
a. Cohesion and Adhesion
Cohesive force - IMFA that binds similar molecules.
Adhesive force - IMFA that binds different molecules or between the molecules of a
substance and a surface.
Meniscus - curved upper surface of a liquid.
Cohesion > Adhesion → meniscus concave down.
Cohesion < Adhesion → meniscus concave up.
b. Capillary action - the rise of a liquid up a narrow tube. The surface area is increased
when H2O rises up a narrow tube. The H2O levels stop rising until the adhesive and
cohesive forces is balanced by the gravitational pull.
CHY 40 Intermolecular Forces of Attraction-3
state of matter can change into either the two other states.
1. Vaporization / Evaporation - passage of molecules from liquid to a gaseous state. The
rate of vaporization increases with increased T and decreased IMFA.
2. Vapor pressure - the escaping tendency of the liquid. It is the pressure exerted by a vapor
over the liquid when the liquid and vapor state are in dynamic equilibrium (equal rates of
evaporation and condensation).
• Liquids with weak IMFA have high vapor pressure, hence, they evaporate easily and are
said to be volatile.
• Vapor pressure increases with temperature. The higher the temperature, the higher also
is the vapor pressure
Relationships: T  VP
1
IMFA 
VP
1
Boiling point 
VP
3. Boiling Point - the temperature at which the vapor pressure of a liquid equals the external
pressure acting on its surface. During boiling, every heat absorbed is used to convert the
liquid to gas and T remains constant until all the liquid has been converted to gas.
Normal boiling point - boiling point at which the external pressure is equal to 1 atm. For
example, water boils at 100oC under ordinary conditions.
Critical temperature, Tc - the highest temperature at which a liquid can exist. The greater
the IMFA, the more readily a gas is liquefied, hence, the higher the Tc.
Critical pressure, Pc - the minimum pressure required to bring about liquefaction.