CHEM 1442

Chapter 11: Intermolecular Forces

11.1 Intermolecular Forces
 Intermolecular Forces, or Intermolecular Attractions are the forces that hold separate
molecules and atoms together in the liquid and solid states.
 All IMFs are coulombic, consisting of electrostatic attractions between oppositely
charged particles.
o Types of IMFs:
 Ion-Dipole
 Dipole-Dipole
 Hydrogen Bonds
 London Dispersion Forces
 Ion-Dipole Forces:
o between ionic molecules and polar molecules.
o ENERGY: 40-600 kJ/mol
 Dipole-Dipole Forces:
o between polar molecules. Increases in strength with increasing dipole moment.
o ENERGY: 5-25 kJ/mol
o For molecules of approximately equal molecular mass and size, dipole-dipole
attractions increase with increasing polarity.

Compound Molar Mass Dipole Moment (µ): Boiling Point(°C)

CH 3 CH 2 CH 3 44 g/mol 0.08 debye -42
CH 3 OCH 3 46 g/mol 1.3 debye -24
CH 3 CHO 44 g/mol 2.7 debye 20
CH 3 CN 41 g/mol 3.9 debye 82
 We can see here that:
 The boiling point correlates with dipole moment magnitude.
 Dipole Moment (µ): charge*distance between nuclei
 Hydrogen Bonds:
o between polarized hydrogen on one molecule (covalent bond) and a very
electronegative atom on another molecule (F,O, or N ONLY).
o ENERGY: 10-40 kJ/mol
o It is technically a very strong version of a dipole-dipole force. So when asked, if
hydrogen bonds are present, so are dipole-dipole forces.
 H-Bonds are responsible for many of the important properties of water
and DNA, such as:
 Unusually high boiling point for water.
 Ice having a lower density than water.
 DNA’s double helix structure.
 o Mainly happens in molecules with H-F, H-O, and H-N bonds in them.
 London Dispersion Forces:
o present between all molecules. If one of the above three is present, so is this
one.
o ENERGY: 0.05-40 kJ/mol
o Due to quantum mechanics, dipoles are sometimes temporarily induced,
allowing molecules to bond with each other.
 This is how nonpolar molecules can bond with each other.
 Also, a polar/ionic molecule’s electron cloud can disrupt a nonpolar
molecule’s electron cloud to temporarily induce a dipole in it, and
therefore bond with it.
o LDFs increase with increasing polarizability, which is the ease with which the
electron cloud of a particle can be distorted. Larger molecules have higher
polarizability, which means that the strength of London Forces increases with
the size of molecules.
 IMFs are relatively weak compared to chemical bonds, and are responsible for the state
(solid, liquid, gas, plasma, supercritical) that the substance is in.

ALL ELSE BEING EQUAL ( similar size/mass of molecules):

 Which intermolecular attractive force is the strongest?

o HYDROGEN BONDS
 Which intermolecular attractive force is the weakest?
o LONDON DISPERSION FORCES
 KEEP IN MIND: the ranges of energy levels that exist for these intermolecular forces may
overlap. It is possible, for example, to have a dipole-dipole interaction that is stronger than a
hydrogen bond interaction. But in general, H-Bonds can be considered the strongest
intermolecular force.

11.2 Phase Changes

 Phase Change: a change in the physical state of a substance
o Endothermic (absorb energy) phase changes:
 Melting/Fusion (solid to liquid)
 Vaporization ( liquid to gas)
 Sublimation (solid to gas)
o Exothermic (release energy) phase changes:
 Freezing (liquid to solid)
 Condensation (gas to liquid)
 Deposition (gas to solid)
 The Enthalpies of Fusion and Vaporization
o Enthalpy: a value equivalent to the change in heat. ( ∆ H )
°
 Enthalpy of Fusion(∆ H fus): also called the heat of fusion, it is the enthalpy
change that occurs when one mole of a pure solid is completely melted.
 °
 Enthalpy of Vaporization((∆ H vap): also called the heat of vaporization, it is the
enthalpy change that occurs when one mole of a pure liquid is completely
vaporized.
o Important Properties of ∆ H °vap and (∆ H °fus):
 The enthalpy of vaporization of a substance is generally much higher than its
enthalpy of vaporization, due to the fact that all intermolecular forces must be
overcome for a substance to attain gaseous form. When a substance transitions
from solid to liquid, it overcomes some IMFs, but not all of them, hence the
liquid molecules of the substance having more mobility than a solid, but less
than a gas.
 Consequently, the stronger the intermolecular forces present in a substance,
the higher the enthalpies of fusion and vaporization.
The Heating Curve

 The above graph shows a heating curve. It is a plot of the temperature of a substance vs the
amount of heat absorbed by the substance.
o For the most part, the temperature of a substance increases as heat is added. However,
when it is at a melting point, the temperature does not change until all of the substance
is melted. The added thermal energy goes into partially overcoming the IMFs. This also
happens at a boiling point: the substance will not increase in temperature until all of the
substance is vaporized.
o Melting Point: the temperature at which the solid and liquid states coexist in
equilibrium. At the melting point, which is the same as the freezing point, the rate of
melting equals the rate of freezing.
 Vapor Pressure and Boiling Point
 Vapor Pressure: the pressure exerted by a vapor in equilibrium with its solid or
liquid state. Meaning evaporation and condensation are happening at the same
rate.
  Solids that sublime can also exhibit vapor pressure, but the
equilibrium is between the gas and solid.
 Vapor pressure is dependent on temperature. The higher the
temperature, the higher the vapor pressure exhibited by a substance.
 Volatility: the ease with which a substance can be vaporized.
o Substances that exhibit higher vapor pressures are considered
volatile because they can vaporize easily. This is because of
weaker IMFs creating weaker bonds between their molecules.
o Substances with lower vapor pressures are considered
nonvolatile because this indicates they do not easily vaporize.
This is because they generally have stronger intermolecular
bonds.
 Boiling Point: the temperature at which the vapor pressure of the liquid equals
the external pressure.
 Normal Boiling Point: the temperature at which the boiling point of a
liquid equals 1 atm/760 torr/760 mmHg (standard pressure).
 Boiling points increase in proportion to the intermolecular forces
present.

11.3 Phase Diagrams

 The above graphs are called Phase Diagrams. They represent the most stable state of a
substance at any given temperature and pressure.
o Legend for Phase Diagrams:
 A line/ curve on a phase diagram represents an equilibrium between the two
phases it splits apart.
 Fusion Curve: where solid and liquid are at equilibrium
o Note that the fusion curve for water has a negative slope. This
is unique to water because ice is less dense than liquid water.
Every other substance, with few exceptions, has a positively
sloped fusion curve.
 Sublimation Curve: where solid and gas are at equilibrium
 Vaporization Curve: where liquid and gas are at equilibrium
  There are also points on the curve that should be noted:
o Triple Point: the temperature and pressure at which all three physical states are at
equilibrium with each other.
o Critical Point: where a substance transforms into a supercritical fluid, a somewhat
intermediate between liquid and gas states.
 Critical Temperature and Critical Pressure are the “coordinates” for the critical
point. After this temperature and pressure is surpassed, the substance goes
supercritical.

11.4 Properties of Liquids

 Surface Tension: the energy required to increase the surface area of a liquid by a unit amount.
o Liquids tend to have the smallest surface area possible because molecules in the interior
of a liquid experience more intermolecular attractions and are thus lower in energy than
those on the surface.
o In general, the stronger the intermolecular attractions, the greater the surface tension.
 Viscosity: a measure of the resistance to flow of a liquid. It occurs because the intermolecular
attractive forces within a liquid prevent the molecules from moving around as freely as they
could in the absence of those forces.
o Viscosity tends to increase with increasing molecular size and complexity, and tends to
decrease with temperature.
 Capillary Action: the spontaneous rising of a liquid against the pull of gravity through a narrow
tube. It occurs as a result of the interplay between cohesive and adhesive forces.
o Cohesive Forces: the intermolecular forces within a liquid.
o Adhesive Forces: the intermolecular attractions between liquid molecules and the walls
of the tube.