Chapter 2
Molecular structure – chemical bond
ATOMs ? Molecule
s
Chemical
bonds
- Covalent bonds
- Ionic bonds
- Other bonds (metallic, hydrogen, Van der Walls)
2.1. Basic Concepts
1. Bond energy (Eb, kj/mol or kcal/mol): is the average value of the
gas-phase bond dissociation energies.
Eb is the measure of bond strength in a chemical bond.
Eb ↑ → bond strength ↑
2. Bond length (db): is the average distance between nuclei of
two bonded atoms in a molecule
db ↑ → stability ↓
3. Bond Angles:
2.1. Basic Concepts
4. Bond Order (B.O): is the number of chemical bonds between a pair
of atoms
B.O = 1 B.O = 2 B.O = 3
B.O = 1.5 ?
B.O ↑ → db ↓ → Stability ↑
2.1. Basic Concepts
5. Electronegativity (χ): The ability of an atom in a molecule to attract
shared electrons to itself. Covalent or
ionic bonds
ATOMs Molecules
s
Ionic bonds (Metal-
nonmetal):
Δχ > 1.7
Covalent bonds
(nonmetal-nonmetal):
0≤ Δχ ≤1.7
Δχ = 0: nonpolar
Δχ > 0: polar
2.1. Basic Concepts
6. Covalent molecules including nonpolar and polar molecules.
A polar molecule is electrically asymmetrical, resulting in charges
at two points. The molecule is said to have a molecular dipole
(lưỡng cực) or dipole moment.
O O C O
H Cl O
H H C
H3C CH3
NOT all molecules that contain polar bonds will be polar molecules!
2.2. Covalent Bond
Two main Theories for forming Covalent
Bond:
1. Valence Bond (VB)
2. Molecular Orbital (MO)
Valence Bond (VB) theory
The basic idea
Two half-filled orbitals overlap to form a covalent bond.
The electrons in this new
probability density are then
shared by both atoms (equally
attracted to both nuclei).
Arrange themselves to have maximum overlap of
their half filled orbitals, producing a bonding orbital of
lowest energy
Types of Covalent Bonds
Orbitals can overlap in two main
ways creating two different types
of covalent bonds
Sigma bonds (σ)
Pi bonds (π)
The σ Bonds
The σ bonds are formed from overlapping of AO
according to bond axis
The σ bonds are the strongest type of covalent
chemical bond
The π Bonds
The π bonds are required two lobes (thùy) of one
involved AO overlapping two lobes of the other AO
The π bonds are usually weaker than σ bonds
Formation of Covalent Bonds
Octet rule: Chemical compounds tend to form that each atom, by
gaining, losing, or sharing electrons, has an octet of electrons (or
doublet in Hydrogen case).
F-F
H : Cl
Lewis structure
Comments on Octet Rule
2nd period elements C, N, O, F observe the octet rule. However, 2nd
row elements B and Be often have fewer than 8 electrons around
themselves → they are very reactive.
3rd period and heavier elements CAN exceed the octet rule using
empty valence d orbitals.
Ex. Clo (Z= 17) explain why Clo possesses various oxidation
numbers: Cl-, Cl+, Cl+3, Cl+5, Cl+7
Lewis Structures
Shows how valence electrons are arranged among atoms in a
molecule.
Reflects central idea that stability of a compound relates to noble
gas electron configuration.
Lewis Structures
Completing a Lewis Structure -CH3Cl
Make carbon the central atom
Add up available valence electrons: C = 4, H =
(3)(1), Cl = 7 Total = 14
Complete octets on
atoms other than H
hydrogen with remaining .
..
electrons
H C
..
.
Cl
. ..
H
Types of Bonds
Single bond = 1 σ bond
Double bond = 1 σ + 1 π bond
Two pairs of shared electrons
Triple bond = 1 σ + 2 π bonds
Three pairs of
shared electrons
Types of Bonds
Resonance
Occurs when more than one valid Lewis structure can be
written for a particular molecule.
These are resonance structures. The actual structure is an
average of the resonance structures.
Neither structure is correct.
Question?
Lets look at a molecule of
methane, CH4.
What is the expected orbital notation of carbon
in its ground state?
C (Z = 6): 1s22s22p2
Can you see a problem with this?
How to form bonds of carbon according to octet rule?
Promotion & Hybridization (kích thích & lai hóa)
Certain atoms can change their electron configuration to bond
and form a wide variety of compounds. → two steps:
Promotion of an electron to a higher energy orbital &
hybridization or blending of orbitals creating a new type of
orbital for bonding
Most of the time atoms exist in their “ground state” but, in
certain cases the instant before bonding promotion takes
place allowing more bonding spaces:
Promotion
Hybridization (Lai hóa)
Hybridization is the combining of two or more orbitals of
nearly equal energy within the same atom into orbitals of
equal energy.
No orbitals are “lost” due to merging – if we blend one s
orbital and one p orbital, we will end up with TWO hybrid
orbitals!
Covalent bonds are formed by:
Overlap of hybrid orbitals with atomic orbitals
Overlap of hybrid orbitals with other hybrid orbitals
Types & Names of hybrid orbitals
The type of hybrid orbital depends upon the orbitals which
have been blended
sp3
sp2
sp
Others (sp3d, sp3d2,…)
sp3 hybrid Orbitals (CH4)
In the case of CH4, they call the
hybridization sp3, meaning that an
s orbital is combined with three p
orbitals to create four equal hybrid
orbitals.
These new orbitals have slightly
MORE energy than the 2s orbital.
and slightly LESS energy than the
2p orbitals.
Bond angle is 109o28
sp2 hybrid Orbitals (C2H4, BF3,…)
The sp2 combines two orbitals from a p sublevel with one
orbital from an s sublevel.
Bond angle is 120o
Notice that one p orbital remains unchanged.
sp hybrid Orbitals (C2H2, BeCl2,…)
The sp hybridization includes one s orbital combining
with a single p orbital.
Bond angle is 180o
Notice that this produces two hybrid orbitals, while
leaving two normal p orbitals
Hybridization Involving d Orbitals
promote
3s 3p 3d 3s 3p 3d
unhybridized P atom vacant d orbitals
P = [Ne]3s23p3 hybridize
Ba
F
F Be five sp3d orbitals 3d
P F Be
F
Be degenerate
F orbitals
Ba (all EQUAL)
Trigonal bipyramidal
Summary
Ionic Bond
Electrons are transferred
Electronegativity differences are generally greater than
1.7
The formation of ionic bonds is always exothermic!
Ionic Bond
Ionic compounds are NOT molecule. They are
called salts or crystal
ALWAYS formed between metals and non-metals
[METALS ]+ [NON-METALS ]-
Lost e-
Gained e-
Metallic Bond
Occurs between like atoms of a metal in the
free state
Valence e- are mobile (move freely among all
metal atoms)
Positive ions in a sea of electrons
Hydrogen Bonding
Bonding between hydrogen and more electronegative neighboring
atoms such as O, N and F
Intermolecular (liên pt) bonding: melting
point, boiling point, acidicity, solubility
are high.
Intramolecular (nội pt) bonding: melting
point, boiling point, solubility are low
Van de Waals bond
Van der Waals bond are the residual attractive or repulsive
forces between molecules or atomic groups that do not arise
from a covalent bond, or ionic bonds.
Non-polar molecules can exist in liquid and solid phases
because of van der Waals forces
Example: Exist between CO2, CH4, CCl4, CF4, diatomics and
monoatomics
Van de Waals bond