(Lec4) Intermolecular and Intramolecular Interactions
(Lec4) Intermolecular and Intramolecular Interactions
(Lec4) Intermolecular and Intramolecular Interactions
intramolecular interactions
Introduction
Intramolecular forces are the forces that hold atoms together within a molecule.
Intermolecular forces are forces that exist between molecules.
Intermolecular Forces
Intermolecular forces are attractive forces between molecules.
Intramolecular forces hold atoms together in a molecule.
Intermolecular vs Intramolecular
• 41 kJ to vaporize 1 mole of water (inter)
• 930 kJ to break all O-H bonds in 1 mole of water (intra)
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Types of Chemical Bonds
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GIANT IONIC CRYSTAL LATTICE
Oppositely charged ions held in a regular
3-dimensional lattice by electrostatic attraction
The arrangement of ions in a crystal lattice depends on the relative sizes of the ions
Cl-
Chloride ion
Na+
Sodium ion
The Na+ ion is small enough relative to a Cl¯ ion to fit in the
spaces so that both ions occur in every plane.
GIANT IONIC CRYSTAL LATTICE
Oppositely charged ions held in a regular
3-dimensional lattice by electrostatic attraction
The arrangement of ions in a crystal lattice depends on the relative sizes of the ions
Strength
Very brittle Any dislocation leads to move the ionic layers and similar
ions become adjacent. The repulsion of similar ions splits
the crystal.
- + - + - + - +
+ - + - - + - +
SOLID IONIC Cl- Na+ Cl- Na+ IONS ARE HELD STRONGLY TOGETHER
COMPOUNDS DO
Cl- Na+ Cl- + IONS CAN’T MOVE TO THE CATHODE
NOT CONDUCT Na+
ELECTRICITY Na+
Cl-
Na+
SOLUTIONS OF IONIC Cl- DISSOLVING AN IONIC COMPOUND
COMPOUNDS IN Na+ IN WATER BREAKS UP THE
WATER DO CONDUCT STRUCTURE SO IONS ARE FREE TO
Cl- MOVE TO THE ELECTRODES
ELECTRICITY
Octet Rule
Octet rule – Atoms tend to gain, lose or share electrons until
they are surrounded by eight valence electrons.
Covalent Bonds
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Covalent Bonding results from the sharing of two electrons between
two atoms (usually non-metals) resulting in molecules
H + H H H
number of electrons around each atom = He
Cl + Cl Cl Cl
number of electrons around each atom = Ar
Triple bond
N + N N N
number of electrons around each atom = Ne
Boiling point Low - intermolecular forces (van der Waals’ forces) are
weak; they increase as molecules get a larger surface area
Some boiling points are higher than expected for a given mass
because of additional forces of attraction
DATIVE (CO-ORDINATE) COVALENT BONDING
Boron has an incomplete shell in BF3 and can accept a share of a pair of
electrons donated by ammonia. The B becomes -ive as it is now shares a
pair of electrons (i.e. it is up one electron) it didn’t have before.
GIANT (MACRO) MOLECULES
DIAMOND, GRAPHITE and SILICA
GENERAL PROPERTIES
STRENGTH STRONG
each carbon is joined to four other C atoms in a rigid
structure Coordination Number = 4
ELECTRICAL NON-CONDUCTOR
No free electrons - all 4 carbon electrons used for bonding
GIANT (MACRO) MOLECULES
GRAPHITE
STRENGTH SOFT
each carbon is joined to three other C atoms in a layered
structure Coordination Number = 3
Layers are held by weak van der Waals’ forces
Layers can slide over each other
ELECTRICAL CONDUCTOR
Only three carbon electrons are used for bonding which
leaves the fourth to move freely along layers
DIAMOND GRAPHITE
GIANT (MACRO) MOLECULES
SILICA
STRENGTH STRONG
Each silicon atom is joined to four oxygens - C No. = 4
Each oxygen atom are joined to two silicons - C No = 2
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The polarity of a bond depends on the difference between the
electronegativity values of the atoms forming the bond.
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The three major types of intramolecular bonds can be described by
the electronegativity difference:
Due to low
electronegativities,
low effective nuclear
charges and large
diffuse orbitals,
electrons can flow
freely from one atom
to the next.
Metallic Bonding
Zn Cu Zn Fe Fe Fe
C C
Cu Zn Cu Fe Fe Fe
Li+ Na+ K+
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Molecular Shapes
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Molecular Shapes
Valence Shell Electron Pair Repulsion Theory (VSEPR)
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Predicting the Shape of the Molecule
Sum the Number of Electron Domains around the Central Atom
in the Lewis Structure; Single = Double = Triple Bonds = Non-
Bonding Lone Pair of Electrons = Considered as One Electron
Domain
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Molecular Shapes
Predicting Molecular Geometries
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Molecular Shapes
Predicting Molecular Geometries
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Molecular Shapes
Molecules with Expanded Valence Shells
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Molecular Shapes
Molecules with Expanded Valence Shells
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Intermolecular Bonding
Electronegativity
‘The ability of an atom to attract the electron pair in a covalent bond to itself’
INCREASE
values decrease down groups
fluorine has the highest value
INCREASE
H
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Br
0.8 2.8
Bond Polarity and Electronegativity
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Polarity of Molecules
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Polarity of Molecules
Dipole Moments of Polyatomic Molecules
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Polarizability
Ion-dipole attractions become stronger as either the charge on the ion increases, or
as the magnitude of the dipole of the polar molecule increases.
Interaction Between Water and Cations
Hydration
in solution
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Ion-Dipole interactions
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Dipole – Dipole Interactions
Higher the dipole-dipole interactions, higher the energy to
separate molecules. This results in higher boiling point than
expected for a given mass
Boiling points Mr °C Mr °C
CH4 16 -161 H2O 18 +100
of hydrides
SiH4 32 -117 H2S 34 -61
GeH4 77 -90 H2Se 81 -40
SnH4 123 -50 H2Te 130 -2
Group 4A hydrides
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The average strength of hydrogen bond is ~ 40KJ/mol.
The strength of hydrogen bond depends on the electronegativity of
atoms.
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HYDROGEN BONDING - ICE
• this is why…
hydrogen bonding
a) water has a maximum density at 4°C
b) ice floats.
One of the most remarkable consequences of H-bonding is found in the lower
density of ice in comparison to liquid water, so ice floats on water. In most
substances the molecules in the solid are more densely packed than in the
liquid. A given mass of ice occupies a greater volume than that of liquid water.
This is because of an ordered open H-bonding arrangement in the solid (ice) in
comparison to continual forming & breaking H-bonds as a liquid.
HYDROGEN BONDING - HF
¯ ¯
F + F +
+ +
H ¯ H
¯ H
H
F F
hydrogen bonding
Ionic Covalent
Intermolecular Forces
Strength of inter molecular forces
e
58.8 Dispersion forces
Bromin
e
2. Surface area of molecule
pentane molecules
larger contact area 2,2-dimethylpropane molecules
smaller contact area
Pentane (C5H12)
Boiling point
= 36.1C
RMM = 58.0,
b.p. = 50C
H2 H2
C CH3 C CH3
H3 C C H3 C C
H2 H2
Dispersion forces
RMM = 58.0, only
b.p. = 0C
Other examples : -
1. Graphite layers of large surface area
strong van der Waals’ forces
2. Polyethylene vs ethene
(m.p. > 100C) (m.p. = −169C)
What type(s) of intermolecular forces exist between each of the
following molecules?
HBr
HBr is a polar molecule: dipole-dipole forces. There are
also dispersion forces between HBr molecules.
CH4
CH4 is nonpolar: dispersion forces.
S
SO2
SO2 is a polar molecule: dipole-dipole forces. There are
also dispersion forces between SO2 molecules.
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End of lecture