Chapter 3 Intermolecular Forces Between Molecules

1. Van der Waals’ forces

2. Hydrogen bonding

Van der Waals’ Forces

- used to explain the attractive forces between molecules and noble gas atoms.
- two groups of molecules :
(i) Polar molecules ( dipole-dipole forces)
(ii) Non-polar molecules ( temporary dipole-induced dipole forces)

(i) Polar Molecules

+ - + - Example :
H – Cl H – Cl
- +
Cl – H

- The weak attraction forces are Van der Waals’ forces ( dipole-dipole forces). These forces
are exist only when the molecules are close to each other.
(ii) Non-polar Molecule
Examples : N2, O2, Cl2, H2.
- Non-polar compounds and elements such as the noble gases can be liquefied and
solidified. This suggests that there are forces of attraction between atoms or molecules in
non-polar elements and compounds.
- Example : chlorine gas
+ +
+
Cl – Cl - Cl – Cl -
Cl – Cl -
(a) A fluctuation of the (b) The temporary dipole induces a dipole in a
electron cloud causes neighbouring molecule. This results a weak and
a temporary dipole. temporary forces of attraction between the two
molecules (Van der Waals’ forces).

The Effect Of Van der Waals’ Forces

1. The strength of Van der Waals’ forces as molecule size .
• •• the larger molecules with large and diffuse electron distributions have stronger
attractive forces between temporary dipole-induced dipole.
Molecule Number of electrons in molecule Boiling point/oC
H2 2 -253
O2 16 -183
Cl 34 -35
The Effect Of Van der Waals’ Forces
1. The strength of Van der Waals’ forces as molecule size .
• • the larger molecules with large and diffuse electron
distributions have stronger
attractive forces between temporary dipole-induced
dipole.

Molecule Number of electrons in molecule Boiling point/oC

H2 2 -253
O2 16 -183
Noble gases

• He Ne Ar Kr Xe
• 2 10 18 36 54

• CH4 C2H6 C3H8 C4 H10

2. In homologous series of organic compound,
the strength of Van der Waals’ forces as molecular size .
3. The branched chain isomers have lower boiling point than unbranched chain isomer.

Hydrogen Bonding
1. When hydrogen atom formed covalent bonding with atom which has high
electronegativity (such as O, N, and F), this high electronegative atom attracting electron
density from hydrogen. Therefore, the covalent bond is highly polarized.
HF -
+
2. Since the H is very small, it can approach the lone pair of electronegative atom and
+
results electrostatic force.
3. Examples :
H- F H - F (strong hydrogen bond)
•• ••
••

••

•• ••
H
F -••H O ••
••

••

•• H

-O–H Cl (weak
•• - hydrogen bond)
••

••
4. Hydrogen bonding is a special type of intermolecular attraction that exists
between the hydrogen atom in a polar bond (particular an H – F , H – O , or H –
N bond) and an unshared electron pair on a nearby electronegative ion or atom
(usually an F, O, or N atom on another molecule)
5. Hydrogen bonding ( 20 kJ – 80 kJ) is weaker than covalent bond (200 kJ – 400 kJ)
6. Hydrogen bonding influences the physical properties but not influences the chemical
properties.
7. The strength of hydrogen bonding :
X–H Y where X = N (3.0), O(3.5), or F(4.0)
Y = N(3.0), O(3.5), or F(4.0)
hydrogen bond

X Y The strength of Result

hydrogen bonding
Electronegativity Same Increase N-H Y< O-H Y < F-H Y
(i) increase
Same Electronegativity Decrease X-H F< X-H O < X-H N
(ii) increase
X same as Y – electronegativity Increase N-H N < O-H O < F-H F
(iii) increase
Same negative ion Increase F-H F- is the strongest
(iv) hydrogen bond
The Effect Of Hydrogen Bonding On The Physical Properties
1. Boiling Point
- Hydrogen bonding increases the attractive forces between molecules and therefore
increases the melting point and boiling point of molecular substances.
- Example (i) Boiling point of alcohol is higher than alkane for same size and
molecular mass.
Ethanol b.p. = 78oC , propane b.p. = -42oC
Explanation : In ethanol liquid, molecules interact between one and another with
hydrogen bonds.
H
CH3 – CH2 – O H – O – CH2 – CH3

hydrogen bond
H – O – CH2 – CH3
- Example (ii) Boiling point of butanol, CH3CH2CH2CH2OH (118oC) is greater than
butylamine, CH3CH2CH2CH2NH2 (77oC).
Explanation : oxygen is more electronegative than nitrogen therefore – O – H covalent
bond is more polarized than covalent bond in – N – H . The hydrogen bonds in butanol
are stronger than hydrogen bonds in butylamine.
- Example (iii) : The boiling points of the simple hydrides of group 14, 15, 16, and
17.
Boiling point/oC

Group 16 H2O
100 •
Group 17 HF H Te
• •SbH2

0 Group 15 NH3 H2Se • 3

• H2S • AsH3 •HI
•
HCl
• •
• HBr SnH
-100 •
PH3 •
•
GeH
4

4
Group 14 CH4 •
SiH 4

•
-200
1 2 3 4 5 6 number of period
2. Formation Of Dimer – Carboxylic acid
- In non-polar solvent (benzene), relative molecular mass of ethanoic acid is 120 and not
60. This is because of association between molecules by hydrogen bonds happened as
shown below :
O H–O
CH3 – C C – CH3 dimer
O–H O

3. Solubility In Water
- Solubility of organic compounds such as ethanol, ethanoic acid, and propylamine in water
are caused by hydrogen bonding between water molecules and organic molecules.
O H H
CH3 – CH2 – C O
O–H O H propanoic acid in water
H
4. The Structure And Properties Of Water And Ice
• The density of ice at 0oC (0.917gcm-3)is less than that of water at 0oC (1.00gcm-3).
• The hydrogen bonding interactions between water molecules are random in the liquid
whereas in solid state (ice), each oxygen atom in water molecule has two hydrogen bonds
with two O – H groups.
• The structure of ice permits the maximum number of hydrogen bonding interactions
between the H2O molecules. A given mass of ice occupies a greater volume than does the
same mass of liquid water.
• The melting point , boiling point, molar heat of fusion, molar heat of vaporisation for
water and ice are higher because the existence of hydrogen bonding in water and ice.

5. The Hardness Of Ionic Crystal

• Dehydrated calcium sulphate(VI) is very hard but hydrated calcium sulphate(VI) crystal
(CaSO4.2H2O) is soft.
• This is because hydrated calcium sulphate is consists of Ca 2+ ion and SO42- ion layers. Each
layer is hold together by weak hydrogen bonds, therefore the layers can slide past one
another easily.
• In dehydrated calcium sulphate, it is consists of Ca2+ ions and SO42- ions only.
Ice structure and water molecules
6. Hydrogen Bonding In Protein
• The present of C = O and - N – H groups in protein formed hydrogen bonds with water
molecules
=> protein is soluble in water.
• Hydrogen bonding also play an important role in - helix structure of protein.

7. Hydrogen Bonding Between molecules And In Molecules

• Boiling point of 4-nitrophenol (279oC) is higher than the boiling point of 2-nitrophenol
(214oC).
• This is because of 2-nitrophenol possess intramolecular hydrogen bonding
=> prohibit intermolecular hydrogen bonding.
2-nitrophenol
O–H hydrogen bond
+ ••
N–O
••

•• intramolecular hydrogen bond

O
• For 4-nitrophenol, intramolecular hydrogen bonding is impossible. Consequently,
intermolecular hydrogen bonding happened and caused higher boiling point.

O2N - -O H–O-
H
hydrogen bond
• 3 –nitrophenol has higher b.p than 2 –nitrophenol. This is because the 2 –
nitrophenol has intramolecular hydrogen bonding whereas 3 –nitrophenol has
intermolecular hydrogen bonding.
2 –nitrophenol 3 –nitrophenol
H
-O-H -O–H O-
•• O2N NO2
N – O hydrogen bond
••
hydrogen bond
••
O

• 2 –nitrophenol is not soluble in water because hydrogen bonding are formed in

molecules, therefore cannot form hydrogen bond with water molecules.
3-nitrophenol and 4 – nitrophenol are soluble in water because can form hydrogen bonds
with water molecules.
H
O–H O
O–H H

N–O
O NO2
2-nitrophenol 4 - nitrophenol
SUMMARY OF CHAPTER 3

• 1. IONIC BOND
• ELECTROSTATIC FORCES BETWEEN THE OPPOSITELY CHARGED IONS
• LEWIS STRUCTURE
• FACTORS AFFECTING STRENGTH OF IONIC BOND
• -
•-
• FACTORS AFFECTING FORMATION OF IONIC COMPOUNDS
• -
• -
•-
• PROPERTIES OF IONIC COMPOUNDS
2. COVALENT BOND
• A. 3 WAYS EXPRESSING
• 1. SHARING OF ELECTRON
• 2. OVERLAPPING OF ORBITAL
• MOLECULAR ORBITAL
• HYBRIDISATION
• 3. VSEPR THEORY

• B. LEWIS STRUCTURE
• SHAPE
• ANGLE
• C. POLAR AND NON-POLAR MOLECULES
• D. RESONANCE
• E. STRENGTH AND PROPERTIES
3. METALLIC BOND

• A. ELECTROSTATIC FORCE BETWEEN DELOCALISED ELECTRON AND

METAL ION(NUCLEUS)

• B. MOLECULAR ORBITAL BAND THEORY : OVERLAPPING OF ORBITAL

• C. CONDUCTOR , SEMI-CONDUCTOR, INSULATOR

• D. STRENGTH OF METALLIC BOND

4. INTERMOLECULAR FORCES

• A. Weak van der Waals Forces

• permanent dipole-permanent dipole (Polar molecule)
• Temporary/instantaneous dipole-induced dipole (non-polar
molecule)

• B. Hydrogen – Bond
• 1. N, O , F
• 2. effects
Q19(b) : 2014
answer

• b i. MgCl2 in solid state – ions in fixed postion / can’t move

• in ionic lattice / ionic bond

• Cu has delocalised / mobile electron in solid and molten state

• ii. In ice , water molecules – held apart in an open (lattice) structure

• by hydrogen bonds
• when melting occur – H-bond breaks
• when H-bond breaks – molecules become closer
Q18 : 2017
Q18 : 2017 Answer

• Shape : tetrahedral Shape : bent/ V-shape

• Angle : 109.5o Angle : < 109. 5o

• According to VSEPR theory

• repulsion ofelectron of
• lone-pair-lone pair > lonepair –bond-pair > bondpair-bond-pair
• Angle in amide ion is bigger because amide ion has 2 lone-pair and 2
bond-pair of electrons but ammonium ion has 4 bondpair of electrons
a(ii) No/ cannot
it has no lone pair of electrons
cannot form dative/coordinate bond with Cu 2+

• b. Ammonia is more polar

• both NH3 and PH3 have the same shape/ trigonal pyramidal
• N is more electronegative than P
• N-H bond is more polar than P-H bond