CHM 361

CHAPTER 1

INTERMOLECULAR FORCES IN
COVALENT COMPOUNDS
SHAFINAS BINTI ABDULLAH
TOPIC OUTLINE
Van der Waals
Hydrogen Bonding
Ion-dipole Interaction
Effect of These Forces on Boiling Point, Melting Point and solubility
LEARNING OUTCOMES
Explain the intermolecular forces

Identify the intermolecular forces

Differentiate the intermolecular forces

Explain the effects of the intermolecular forces to

the boiling point, melting point and solubility
 INTERMOLECULAR FORCES
 Attractive forces that holding molecules together in solids, liquids and gas
 Gas < Liquid < Solid
 All molecules experience intermolecular attractions
 Generally, intermolecular forces are weaker than intramolecular forces
(chemical bond)
 Energy required to break intermolecular
forces < energy required to break the
intramolecular forces

Hydrogen Bond
Intermolecular forces

London dispersion weak strong

Van der Waals forces
Dipole-dipole forces  Important roles in determine the
Ion dipole forces
properties of substances (boiling point,
melting point, vapor pressure, viscosities)
 VAN DER WAALS FORCES
Dipole – dipole forces
 Attractive forces between POLAR molecules
 Exist due to the difference in ELECTRONEGATIVITIES between 2 atoms of
different elements in molecule (dipole moment)
 The atom has permanently partially positive and partially negative
charges (permanent dipole)
 Arise from the attraction between positive end with negative end of another
molecule
 More POLAR molecule will have STRONGER dipole-dipole forces
 Example: CH3Cl

Dipole moment
polar molecules
greater dipole-dipole forces
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 London dispersion
 Also known as London dispersion forces/dispersion forces/instantaneous dipole
forces
 In NONPOLAR molecules, this is the only intermolecular forces that operates
 The WEAKEST intermolecular forces Occurs in ALL molecules
 Attractive forces between NON-POLAR molecule, caused by the temporary
dipole in atom or molecule
  Due to random movement of the
What is temporary ELECTRONS in an atom or molecule. The
dipole/instantaneous
dipole/induced dipole? electrons gathered at one side of the
molecule (temporary dipole)
 One side of the molecule has higher electron
density (∂-), other side has lower electron
density (∂+)
 The molecules becomes small instantaneous
dipole
 It will induce a dipole on neighboring molecule
(induced dipole), when close enough with
another molecule

 The likelihood of induced dipole depends on the POLARISABILITY of the atom or

molecule
 POLARISABILITY – the ease with which the distribution of electron cloud can be
distorted
 The larger the electron cloud (or the higher number of electrons), the easier
it is to be polarised
 Polarisability increased with increase of molar mass
 How to compare strength of
intermolecular interaction?

 Similar in weights and shapes,

differences is due to different
polarity of molecules, dipole-
dipole interactions will likely
be the dominating force.
 the higher polarity will have
greater intermolecular forces
 Molecules differ widely in weights,
dispersion forces will determine
the strengths of intermolecular forces
 the higher molecular weight will
have greater intermolecular forces

Intermolecular force Occurs between … Relative strength

Dipole-dipole Partially oppositely
Strongest
attraction charged ions
London dispersion Temporary or induced
Weakest
attraction dipoles
 Determine the
polarity
1. Draw the Lewis structure
2. If no lone pair on the central atom, and all the bonds to the central
atom are the same (the molecule is NON-POLAR)

3. If the central atom has at least one lone pair, and the group bonded
to the central atom are not identical (the molecule is probably
POLAR)
 Hydrogen bonding
A SPECIAL type of DIPOLE-DIPOLE interaction
Attraction between Hydrogen (H) with highly electronegative atoms - N,
O, F
Stronger than Van der Waals forces
The strength is proportional to the polarity of the bond
H-F > H2O > NH3 (order of electronegativity of the element)
N, O and F all have at least one lone pair to interact with H atom in other
molecules

A H… B or A H… A **A & B are N, O, or F

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 Ion – dipole forces
Attraction between an ION (cation or anion) with a POLAR molecule
The strength of this interaction depends on the charge of the ion, the dipole
moment of the molecule & the size of both
CATIONS interacts more strongly with dipoles than ANION with the same
magnitude
CATIONS with higher charge and smaller in size, interacts strongly with water
Hydration is an example of common ion-dipole interaction
The ion-dipole interaction of 2 different ions, Na+ and Mg2+ is shown here

 In aqueous solutions,
metal ions are usually
surrounded by water
molecules in octahedral
arrangement

 Mg2+ ion, with higher charge and smaller,

interacts strongly with water 11
 EXERCISE
Let’s try to identify the different kinds of intermolecular forces present in
some molecules.

1. H2S
2. CH3OH
3. C2H6
 Effect of intermolecular Forces on Boiling
Point, Melting Point and solubility
The strength of intermolecular forces present in a substance is related to
the boiling point and melting point of the substance.
Stronger intermolecular forces cause higher melting and boiling
points.

EXAMPLES:

CH4 - Methane: has only very weak London dispersion forces (lowest b.p. &
m.p.)
CHCl3 - Chloroform: has dipole-dipole interaction (moderate b.p. & m.p.)
NH3 - Ammonia: has hydrogen bonding and dipole-dipole interaction
(high b.p. & m.p.)

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 Effect of van der Waals on boiling and melting
point

Trend in boiling points of H Halides:

HCl, - 85˚C
HBr, -67˚C
HI, -15˚C

Stronger intermolecular forces result in higher boiling points. The dipole moments
increase with the polarity of the H-X bond
The strength of London forces increases with the number of electrons -Cl is more
ELECTRONEGATIVE than I so HCl should have a greater boiling point but this data
suggests that London forces dominate dipole-dipole interactions for these molecules
since Iodine is larger than Cl.
HF is an exception because of the stronger force of attraction between HF
molecules resulting from hydrogen bonds acting between the HF molecules. So HF
has higher boiling point than the other molecules in this series.
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 Effect of London dispersion on boiling and
melting point
Dispersion forces - then the more electrons
the molecule has the stronger the dispersion
forces

Consider the hydrides of Group IV, all of

which are non-polar molecules, so only
dispersion forces act between the molecules.

CH4 (molecular mass ~ 16)

SiH4 (molecular mass ~32)

GeH4 (molecular mass ~ 77)

SnH4 (molecular mass ~ 123)

As you can see in this table, the boiling / melting

point increase with the increase of molar mass of
the molecules
 Effect of dipole-dipole on boiling and melting
point

The more polar the molecule, the higher is its boiling point

• The table demonstrates the effect of the dipole moment on the boiling point of
several substances.
• Acetonitrile has highest bp among others
• Greater dipole moment, more polar (high polarity),
• Higher boiling point
• Has highest dipole-dipole forces
Effect of hydrogen bond on boiling and melting
point
H2O > H-F > NH3 (boiling point HF lower than H2O. Explain.

• NH3, H2O and HF have abnormal high bp, because the presence of
Hydrogen bonds between molecules.
• H2O has high bp than NH3: Oxygen atom has 2 lone pair e. So each atom
O can form 2 H-bond. Each molecule H2O can form 4 intermolecular
hydrogen bond
• F is more electronegative than O and 3 lone pair, But, molecule of HF
can only form 2 H-bonds. HF has low bp than H2O.
Effect of intermolecular forces on boiling and
melting point

• DISPERSION FORCES:
 Increase with the increasing of molar mass/no of electron of the molecule.
 Increase with the increasing of size/form/surface area of molecule (isomer)

• DIPOLE-DIPOLE FORCES:
 Increase with the increasing of polarity (greater dipole moment).

• HYDROGEN BONDING
 Increases with the increasing of the electronegativity of the elements.
 Higher if there are more H-bonding per molecule.
 Effect of Intermolecular Forces on
Solubility

In general like dissolves like:

NON-POLAR SOLUTES dissolve in NON-POLAR SOLVENTS

POLAR SOLUTES such as glucose (C6H12O6) will dissolve in POLAR SOLVENTS

IONIC SOLUTES such as sodium chloride (NaCl) will generally dissolve in POLAR
SOLVENTS but not in non-polar solvents, since the positive ion is attracted the
partially negatively charged atom in the polar solvent molecule, and the negative
ion of the solute is attracted to the partially positively charged atom on the solvent
molecule.

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 summary

In general, the strength of intermolecular forces increase in this order:

dispersion < dipole-dipole < hydrogen bond < ion-dipole

DISPERSION FORCES operates on all molecules and depend only on molar

mass

DIPOLE-DIPOLE operates on polar molecules, but compete with dispersion

(The contribution of dipole-dipole forces in polar molecules is usually smaller
than dispersion forces)

However, if HYDROGEN BOND is present, it makes a significant contribution

to intermolecular interaction between molecules
summary
 summary
 Boiling and melting points of compounds depend on the type and strength of
the intermolecular forces present, as tabulated below:

Intermolecular forces Relative order of boiling

Type of compound
present and melting points

Ion to ion attraction between

Ionic compounds 1, highest
ions, London dispersion forces

Covalent compounds
Hydrogen bonds, London
containing hydrogen 2
dispersion forces
bonds
Dipole-dipole attraction
between dipoles created by
Polar covalent compounds 3
partially charged ions, London
dispersion forces
Nonpolar covalent
London dispersion forces 4, lowest
compounds
 Sample problem

For each pair of substances, identify the key intermolecular forces(s) in

each substance, and select the substance with the higher boiling point:

a) CH3NH2 or CH3F
b) CH3OH or CH3CH2OH
c) MgCl2 or PCl3
 Plan to solve problem

1. Examine the formula and picture the structure difference to identify

the key difference
2. Are ion presents? Polar or non polar? Is N, O, F bonded to H?
3. Do the molecules have different masses or shape?

Remember that !!

Bonding forces are stronger than intermolecular forces

Hydrogen bonding is a strong type of dipole-dipole force.

Dispersion are always present, but they are decisive when the

differences is molar mass or molecular shape