CHEMICAL BONDING

CHEMICAL BONDING
• WHY DO ATOMS BOND?
• WHAT IS OCTET RULE?
-atoms tend to lose , gain or share electrons in
order to achieve stable valence shell electron
configuration of 8 electrons.
• TYPES OF CHEMICAL BONDS
– IONIC BOND
– COVALENT BOND
 LEWIS DOT SYMBOLS
• Symbol of the element with one dot for each
valence electron
• Group no. of representative elements is equal
to the number of valence electrons in its last
shell.

Na Ca Al C

N O Cl Xe
 IONIC BONDING
• An ionic bond is the electrostatic force that
holds positive and negative ions together.
• Draw the bonding of the following atoms
1. Barium and Phosphorus
2. Lithium and Oxygen
3. Calcium and Chlorine
 COVALENT BONDING
• A bond in which two or more electrons are
shared by two atoms
• Idea of covalent bond was first suggested by
Gilbert Newton Lewis in 1916.
 COVALENT BONDING
• Illustrate the bonding of the following atoms
1. Carbon and Hydrogen
2. Nitrogen and Hydrogen
3. Oxygen and Hydrogen
 COVALENT BONDING
• SINGLE BOND: Sharing of a single pair of
electrons between bonded atoms .
• DOUBLE BOND: sharing of two pairs of
electrons between two atoms ( O = O)
• TRIPLE BOND: sharing of three pairs of
electrons between two atoms. (N N)
 TYPES OF COVALENT BONDING
• POLAR COVALENT BOND
electrons are not equally shared
• NON POLAR COVALENT BOND
equal sharing of electrons
• COORDINATE COVALENT BOND
a single atom contributes both of the electron
to a shared pair. (to be discussed in exceptions
to octet rule)
 COMPARISON OF PROPERTIES OF COVALENT
AND IONIC COMPOUNDS

PROPERTIES IONIC COVALENT

ATTRACTIVE Electrostatic •Bond energy holds atoms
FORCES forces between together (intramolecular forces)
ions that are •Intermolecular forces are
very strong prevalent between molecules
which are very weak
OTHER •Very high •Low melting point solids
PROPERTIES melting pt. •Do not conduct electricity
•Conduct •Most are not soluble in water
electricity as
molten liquid
 BOND POLARITY
• Recall that a polar bond has an asymmetric
distribution of electrons
– X-X is nonpolar
– X-Y is polar
• Polarity of a bond increases with increasing
difference in electronegativity between the
two atoms
• Bond is a dipole
– One end is (δ+), while the other is (δ-)
 Polarity - Molecules
• Molecules may also possess polarity
– Positive and negative poles
– Molecule is called a dipole
• Consider HF
– H is δ+ while F is δ–
• Consider BeF2
– Be-F bond is polar
– BeF2 is nonpolar
 ELECTRONEGATIVITY SCALES
• PAULING SCALE
relative scale used to measure electronegativity
• Atoms with vastly different electronegativity
 ionic compounds
• Atoms with somewhat different
electronegativity  polar covalent compound
(approximate cut off is a difference of 2.0 on
the Pauling Scale)
• Nonpolar compounds are electronically
symmetrical
 Determine whether the given
molecule is polar or nonpolar
1.SO2
2.BF3
3.CO2
 Writing Lewis Formulas:
The Octet Rule
• The octet rule states that representative
elements usually attain stable noble gas electron
configurations in most of their compounds.
• Lewis dot formulas are based on the octet rule.
• We need to distinguish between bonding (or
shared) electrons and nonbonding (or unshared
or lone pairs) of electrons.

14
 Writing Lewis Formulas:
The Octet Rule
• N - A = S rule
– Simple mathematical relationship to help us write Lewis dot formulas.
• N = number of electrons needed to achieve a noble gas configuration.
– N usually has a value of 8 for representative elements.
– N has a value of 2 for H atoms.
• A = number of electrons available in valence shells of the atoms.
– A is equal to the periodic group number for each element.
– A is equal to 8 for the noble gases.
• S = number of electrons shared in bonds.
• A-S = number of electrons in unshared, lone, pairs.

15
 Writing Lewis Formulas:
The Octet Rule
• For ions we must adjust the number of electrons available,
A.
– Add one e- to A for each negative charge.
– Subtract one e- from A for each positive charge.
• The central atom in a molecule or polyatomic ion is
determined by:
– The atom that requires the largest number of electrons to
complete its octet goes in the center.
– For two atoms in the same periodic group, the less
electronegative element goes in the center.

16
 Writing Lewis Formulas:
The Octet Rule
• Example 7-2: Write Lewis dot and dash
formulas for hydrogen cyanide, HCN.
• N = 2 (H) + 8 (C) + 8 (N) = 18
• A = 1 (H) + 4 (C) + 5 (N) = 10
• S= 8
• A-S = 2
• This molecule has 8 electrons in shared
pairs and 2 electrons in lone pairs.
H ·· C ·· ·· ·· N ·· or H C N ··
17
 Writing Lewis Formulas:
The Octet Rule
• Example 7-3: Write Lewis dot and dash
formulas for the sulfite ion, SO32-.
N = 8 (S) + 3 x 8 (O) = 32
A = 6 (S) + 3 x 6 (O) + 2 (- charge) = 26
S = 6
A-S = 20
• Thus this polyatomic ion has 6 electrons in shared
pairs and 20 electrons in lone pairs.
• Which atom is the central atom in this ion?
You do it!
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 Writing Lewis Formulas:
The Octet Rule

• What kind of covalent bonds, single,

double, or triple, must this ion have so
that the six shared electrons are used to
attach the three O atoms to the S atom?
·· ·· ·· 2- ·· ·· ·· 2-
·· O · S ·· O ·· or ·· O S O ··
·
·· ·· ·· ·· ··
·· O ·· ·· O ··
·· ··

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 Resonance

• Example 7-4: Write Lewis dot and dash

formulas for sulfur trioxide, SO3.
You do it!
N = 8 (S) + 3 x 8 (O) = 32
A = 6 (S) + 3 x 6 (O) = 24
S = 8
A-S ··
· · · · = 16
· ··
·· O
· O · S·· O · or S O ··
·· ·· ·· ·· ··
·· O ·· ·· O ··
·· ·· 20
 Resonance

• There are three possible structures for SO3.

– The double bond can be placed in one of three places.
·· · ·· ·· ··
·· O S O· ·· O S O ·· ·· O S O ··
·· ·· ·· ·· ·· ··
·· O · ·· O ·· ·· O ··
·· · ··
oWhen two or more Lewis formulas are necessary to show the
bonding in a molecule, we must use equivalent resonance
structures to show the molecule’s structure.
oDouble-headed arrows are used to indicate resonance formulas.

21
 Writing Lewis Formulas:
Limitations of the Octet Rule
• There are some molecules that violate the octet rule.
– For these molecules the N - A = S rule does not apply:
1. The covalent compounds of Be.
2. The covalent compounds of the IIIA Group.
3. Species which contain an odd number of electrons.
4. Species in which the central element must have a share of
more than 8 valence electrons to accommodate all of the
substituents.
5. Compounds of the d- and f-transition metals.

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 Writing Lewis Formulas:
Limitations of the Octet Rule
• In those cases where the octet rule does not
apply, the substituents attached to the
central atom nearly always attain noble gas
configurations.
• The central atom does not have a noble gas
configuration but may have fewer than 8
(exceptions 1, 2, & 3) or more than 8
(exceptions 4 & 5).
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 Writing Lewis Formulas:
Limitations of the Octet Rule
• Example 7-5: Write dot and dash
formulas for BBr3.
– This is an example of exception #2.
You do it!
·· ··
.B ·· Br .
··
·· ·· ·· ··
·· Br · B · Br ·· ·· Br B Br ··
· · or
·· ·· ·· ·· ··
·· Br · ·· Br ··
·
·· ··
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 Writing Lewis Formulas:
Limitations of the Octet Rule
• Example 7-6: Write dot and dash
formulas for AsF5.
You do it!
·· ··
. As . ·· F .
. ··
·· ··
·· F ·· ·· F ·
·· ·· ·· · ·· · ··
·· F · As · F · or
·· F F ··
·· ··· ··· ·· ·· As ··
·· F· · F · ·· F · · F ·
·· · · ·· · ·· · · ·· ·
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 LEWIS STRUCTURES
Drawing Lewis Structures
1.List all the atoms and count the number of
valence electrons.
2.Pick a central atom. Never H. Often C
3.Connect all remaining atoms to the central
atom with a pair of electrons.
4.Give all outer atoms 8 electrons total. (Not H.)
5.Give the central atom 8 electrons total.
6.Count electrons in structure. If it matches Step
1, you are done.
Special Cases

7. If there are too many electrons in your

structure, then create double and triple bonds
between C, N, and O atoms until the number of
electrons is correct.
8. For polyatomic ions with negative charges, add
to the number of electrons by the amount of
the charge. Sulfate has a -2 charge, so the total
number of electrons will have 2 added to it.
(Ammonium has a +1 charge, so we subtract 1
from its total.)
9. For ionic structures we show the transfer of
electrons and draw the atoms as separate ions.
 WRITING LEWIS STRUCTURES
1. NH3
2. PF3
3. SiBr4
4. CS2
5. HCN
6. CO32-
 FORMAL CHARGE
• Formal charges are analogous to oxidations
numbers:
– They are not actual charges
– They keep track of electron ownership
 Formal Charges
• Formal charges are determined by getting the
sum of the number of valence electrons (X), and
then subtracting the total of the number of lone
electrons (Y) plus half the number of bonding
electrons (Z/2)

Z
Cf X Y
2
Table 7.2 BeF2 and BF3
 Rules Governing Formal Charge
• The quality of a Lewis structure can be determined
by the distribution of formal charge
– Minimize charges
• Best to have no Cf or small Cf
– Watch electronegativity
• The most electronegative atoms should have the most
negative formal charge
– Minimize separation of charge
 EXCEPTIONS TO THE OCTET RULE
• INCOMPLETE OCTET (ELECTRON DEFICIENT
MOLECULES)
- These molecules have an even number of outer
electrons but do not have enough electron to form
octets about each atom (BF3, BeH2)
-when BF3 combines with NH3, coordinate covalent
bonding happens.
• ODD-ELECTRON MOLECULES(Free radicals like NO
and NO2)
• EXPANDED OCTET
-central atom is surrounded by more than four pairs
of valence electrons like XeF4, PCl5 and SF6
- The central atoms have d orbital available for
bonding.
 RESONANCE
• Multiple bonds result to multiple Lewis
structures
• Resonance structure represents one of two or
more Lewis structures for a single molecule
that cannot be represented accurately by only
one structure
• EXAMPLE
H–C=O ↔ H–C–O
O O
Benzene
 Notes on Resonance Structures
1. Resonance forms are not different molecules, nor
are they representations of electron shifting
2. Resonance structures arise when two Lewis
structures are equally plausible
3. Only electrons can be shifted in resonance
structures. Atoms cannot be moved.
 MOLECULAR GEOMETRY AND
HYBRIDIZATION OF ATOMIC ORBITALS
 Molecular Geometry
• Diatomic molecules are the easiest to visualize in
three dimensions
– HCl
– Cl2
• Diatomic molecules are linear
 Figure 7.4 – Ideal Geometries
• There is a fundamental geometry that
corresponds to the total number of electron pairs
around the central atom: 2, 3, 4, 5 and 6

linear trigonal tetrahedral trigonal octahedral

planar bipyramidal
Valence Shell Electron Pair Repulsion Theory
• The ideal geometry of a molecule is determined
by the way the electron pairs orient themselves in
space
– The orientation of electron pairs arises from electron
repulsions
– The electron pairs spread out so as to minimize
repulsion
PREDICTING MOLECULAR GEOMETRIES

1. Draw Lewis structure

2. Determine the number of electron pairs
around the central atom. Count a multiple
bond as one pair.
3. Arrange electron pairs as shown in the next
slide
Two electron pairs
• Linear
• Bond angles
– The bond angle in a linear
molecule is always 180

Three electron pairs

• Trigonal planar
• The electron pairs form an
equilateral triangle around the
central atom
• Bond angles are 120
Four Electron Pairs
• Tetrahedral
• Bond angles are 109.5

Five Electron Pairs

• Trigonal bipyramid
• Bond angles vary
– In the trigonal plane, 120
– Between the plane and apexes, 90
– Between the central atom and both
apexes, 180
Six Electron Pairs
• Octahedron
• The octahedron is a square bipyramid
• Bond angles vary
– 90 in and out of plane
– 180 between diametrically opposite atoms and the
central atom
NO. OF PAIRS Arrangement GEOMETRY BOND <s
2 B–A–B linear 180
3 B trigonal
B–A planar 120
B
4 B tetrahedral 109.5
B–A–B
B
5 B B 120
A–B Trigonal 90
B B bipyramid 180
6 B B B octahedral 90
A 180
B B B
Figure 7.5 - Molecular Geometry Summarized - 1
Figure 7.5 - Molecular Geometry Summarized, 2
 EXAMPLES
Illustrate the geometry of the following
molecules:
1. BeH2
2. CH4
3. BF3
4. PCl5
5. SF6
EFFECT OF NON BONDING ELECTRONS
ON BOND ANGLES
• Lone pairs exert greater repulsive forces on
adjacent electron regions resulting to
compression of bond angles
• Electron pair repulsions occur between lone
pairs and other lone pairs and with bonding
pairs.
• Order of degree of repulsion
lone pair- lone pair > bonding pair –lone pair
> bonding pair – bonding pair
 Bond Angles and Lone Pairs
• Ammonia and water show smaller bond angles
than predicted from the ideal geometry
– The lone pair is larger in volume than a bond pair
– There is a nucleus at only one end of the bond so the
electrons are free to spread out over a larger area of
space
Compare:
H
H C H N O
H H H H H H
109.5 107 104.5
 The A-X-E Notation
• A denotes a central atom
• X denotes a terminal atom
• E denotes a lone pair
• Example
– Water
• H2O
• O is central
– Two lone pairs
– Two hydrogens
• AX2E2
Table 7.3 - Molecular Geometry Summary with Lone Pairs
Included
 Multiple Bonds
• For molecular geometry purposes, multiple bonds
behave the same as single bonds
– All of the electron pairs are located in the same place
(between the nuclei)
– The geometry of the molecule is determined by the
number of terminal atoms, which is not affected by the
presence of a double or triple bond
• Electron pairs for multiple bonds exert a greater repulsive
force on adjacent electron regions than do single bonds.
Cl 124. 3
111.4 C=O
Cl 124.3
Figure 7.8 - Molecular Geometry Summary 1
Figure 7.8 - Molecular Geometry Summary 2
 EXAMPLES
Write the Lewis structure and the molecular
geometry of the following molecules.
1. NO2- 6.SO2
2. ClF3
3. PBr5
4. CO2
5. SCl6
 Atomic Orbitals and Hybridization
• Valence Bond Model
– Linus Pauling
• Nobel Prize, 1954
– Orbital diagrams
• Isolated F atom (↑↓) (↑↓) (↑↓)(↑↓)(↑ )
1s 2s 2p
• F atom in HF (↑↓) (↑↓) (↑↓)(↑↓)(↑↓)
1s 2s 2p
 Valence Bond Theory
• Unpaired electrons from one atom pair with
unpaired electrons from another atom and give
rise to chemical bonds
• Simple extension of orbital diagrams
 Figure 7.12 - Atomic Orbital
Mathematics
• Two atomic orbitals produce two hybrid orbitals
– One s + one p  two sp

WHAT HAPPENS TO THE ORBITALS OF THE CENTRAL

ATOM DURING HYBRIDIZATION?
Table 7.4 - Hybrid Orbitals and
Geometry
 Hybrid Orbitals and Electron Occupancy
• Same rules we have seen before
– In an atom, an orbital holds two electrons
– In a molecule, an orbital also holds two electrons
• What electrons go into hybrid orbitals?
– Lone pairs
– One pair per bond
• Even for a double bond, only one pair goes into the hybrid
orbital
 EXAMPLES
Write the hybridization of the central atoms of
the following molecules.
1. ClF3
2. SO3
3. NH3
4. SCl6
5. CH4
6.BCl3
 Multiple bonds
• Sigma (σ) bonds
– Electron density is located between the nuclei
– One pair of each bond is called a sigma pair
• Pi bonds (π)
– Electron density is located above and below or in front
of and in back of the nuclei
• One pair of a double bond is called pi (π)
• Two pairs of a triple bond are called pi (π)
Figure 7.13 - Ethylene and Acetylene
 SUMMARY
• Number of hybrid orbitals formed is always
equal to the number of atomic orbitals mixed
• Hybrid orbitals form sigma bonding schemes
• Unhybridized atomic orbitals may form both
sigma and pi bonding schemes.
• For double and triple bonds, electron pairs in
excess are not located in hybrid orbitals
• Only one pair in a multiple bond is hybridized
which means only one bond can be a sigma
bond and the rest are pi bonds.
 SUMMARY
SPECIES TYPE GENERAL HYBRIDIZATION
GEOMETRY
AX2 Linear sp
AX3, AX2E Trigonal planar sp2
AX4, AX3E , Tetrahedral sp3
AX2E2
AX5, AX4E, Trigonal dsp3
AX3E2 , AX2E3 bipyramidal
AX6, AX5E, AX4E octahedra d2sp3