Chemical Bonding PDF

CHEMICAL
BONDING
INTENDED LEARNING OUTCOMES
• Describe the chemical bond
• Describe the octet rule
• Write the Lewis structure of elements and compounds
• Describe the formation and nature of the metallic bond
• Describe the formation and nature of ionic bonds and covalent bonds
• Discuss the properties of bonds such as bond length, bond strength, bond
order and bond polarity
• Determine molecular geometry and predict polarity of molecules
• Explain chemical bonding using the Valence Bond Theory / MOT

Nature of Bonds
Chemical Bonding
•Chemical Bonding: the joining of two
atoms in a stable arrangement
•Chemical bonds: attractive forces that
hold atoms together in a compound
•Why do atoms bond together?
Through bonding, atoms attain a
complete outer shell of valence electrons
(stable noble gas configuration).
4
TYPES OF CHEMICAL BOND
•Ionic bonds: result from the transfer of

electrons from one element to another.
•Covalent bonds: result from the sharing of

electrons between two nuclei.
CHEMICAL BONDS
HOW?
◦an atom gains, loses or shares electrons in
chemical bonding until they are surrounded
with 8 valence electrons
OCTET RULE
The Octet Rule and
Lewis Symbols
OCTET RULE
valence electron configuration
ns np
2 6
METALS
1e-
Na: [Ne]3s 1 Na + [Ne]
11 11
2e-
Mg 2+ [Ne]
12Mg: [Ne]3s2 12
3e-
Al3+ [Ne]
13Al: [Ne]3s23p1 13
METALLOIDS
4e-
14Si: [Ne] 3s23p2 14Si 4+ [Ne]
+ 4e- Si 4- [Ar]
14Si: [Ne] 3s23p2 14
NON-METALS
7N: [He]2s22p3 + 3e- 5N3- [Ne]
8O: [He]2s 22p4 + 2e- 8O 2- [Ne]
9F: [He] 2s 22p5 + 1e- 9F- [Ne]

LEWIS STRUCTURE
Gilbert N. Lewis
ØAmerican Chemist
Ø method of representing
elements/compounds and
their valence electrons
LEWIS STRUCTURE
Øconsists of:
◦a chemical symbol
◦1 dot for each valence electron
He
O
N
Fe
H •
ü Number and arrangements of electrons in
the outermost shells of atoms: determine
the chemical and physical properties of
elements as well as the kinds of chemical
bonds they form”
Metallic Bond - Sea of
Electron Model
The Electron Sea Model of Metals
ØSolid metal: consists of a lattice of closely packed cations
ØCations: closely packed and occupy fixed positions in the
lattice
ØElectrons removed from the atoms suffuse the array of
cations
ØElectrons move freely in the lattice
Ø“Sea of electrons” in which the array of cations is
submerged
METALLIC BONDING
ØThe forces which hold the cations in their fixed positions in
the lattice are the attractive forces between the cations and
the electrons.
ØThe “sea of electrons” act like a glue that hold the cations
together.
How does the Electron Sea Model explain the
properties of metals:
High density:
The metal atoms are closely packed.
High melting point
Strong forces between particles consist of attraction between the negative
electrons and the positive cations.
Malleable and ductile
Hammering or pulling a piece of wire causes the cations to be displaced
from their original positions in the lattice; electrons move along with them,
thus maintaining the bonding; the metal only deforms but does not shatter to
pieces.
Electrical Conductivity
üElectrons which suffuse the cations are
free to move over the entire metal and
serve as carrier of electrical charge.
ü A voltage applied across a piece of metal
imposes an electric field which makes the
electrons move in accordance with the
applied field.
Thermal Conductivity
üHeat conductivity in metals is brought
about by both electron delocalization and
particle motion
ü Increased movement of particles on the
heated end causes a ripple of movement
through the metal
Luster
The light that strikes the surface is
absorbed by the electrons but is quickly
reemitted.
Ionic Bond and
Lattice Energy
IONIC BONDING
◦formed when an atom that loses electrons
relatively easily reacts with an atom that
has high affinity for electrons.
Ionic compound:
Metal + Non-metal
(+) (-)
(cation) (anion)
Ionic bond: the electrostatic force that

holds ions together
Example: Na+ and Cl-
Predicting formulas of Ionic compounds
Ca : [Ar] 4s2 ® Ca2+ : [Ar]

O : [He] 2s2 2p4 ® O2- : [Ne]
Ca2+ + O2- ® CaO

+2 -2 = 0
Compound should have same number of + and – charge (neutral)
Another example:
Al: [Ne] 3s2 3p1 Al3+ : [Ne]
S: [He] 2s2 2p4 O2- : [Ne]
Al3+ + O2- ® Al2O3

2(+3) + 3(-2) = 0
Common ions with Noble Gas electron
configurations in Ionic Compounds
Group 1: H-, Li+, Na+, K+, Rb+, Cs+

Group 2: Be2+, Mg2+, Ca2+, Sr2+, Ba2+
Group 13: Al3+
Group 16: O2-, S2-, Se2-, Te2-
Group 17: F-, Cl-, Br-, I-
Lewis Dot Symbol (by Gilbert Lewis)
Ø consists of the symbol of the element
and one dot for each valence electron in
an atom of the element.
IONIC BOND
Example: NaCl
Na• Na +
Na+ [ Cl ]-
Cl Cl
IONIC BOND
Example: KBr
K• K+
K+ [ Br ]-
Br Br
Practice
Draw the Lewis Structures of the following
ionic compounds:
a. NaBr
b. BaF2
c. Rb2S
Formation of Binary Ionic Compounds
LATTICE ENERGY – the change in energy that

takes place when separated gaseous ions are packed
together to form an ionic solid:
M+ (g) + X- (g) ® MX (s)
the energy released when an ionic solid forms from
its ions
(-) negative
exothermic
The Born-Haber Cycle for determining
Lattice Energies
Ødeveloped by Max Born and Fritz
Haber
Øbased on Hess’s law
Ørelates lattice energies of ionic
compounds to ionization energies,
electron affinities, and other atomic
and molecular properties
Born-Haber Cycle for NaCl
Born-Haber Cycle for NaCl
Summary:
Process Energy change (KJ)
Na (s) ® Na (g) 108
Cl2 (g) ® 2Cl (g) 122
Na (g) ® Na+ (g) 496
Cl (g) ® Cl- (g) - 349
Na+ (g) + Cl- (g) ® NaCl (s) - 788
_______________________________
Na (s) + ½ Cl2 (g) ® NaCl (s) - 411
Born-Haber Cycle for the formation of NaCl
Na+ (g) + Cl- (g)
Na (g) + 2Cl (g)
Na (s) + ½ Cl2 (g) NaCl (s)

Covalent Bond
COVALENT BONDING
Covalent bond – a bond in which two
electrons are shared by two atoms
Covalent compounds – compounds that
contain only covalent bonds
Formation of the H2 molecule:
Formation of Cl2 and HCl
Electron pairs could either be:
Lone pairs – pairs of electrons localized
on an atom
Bonding pairs – those found in the
space between the atoms
2 bonding pairs and 2 lone pairs
3 bonding pairs and 1 lone pair
4 bonding pairs, no lone pair
Types of Covalent Bonds
Single bond - two atoms held by
one e- pair
Double bond – two atoms held
by 2 e- pairs
Triple bond – two atoms held by
3 e- pairs
LEWIS STRUCTURE OF COVALENT COMPOUNDS
SOME GUIDELINES
¤for most covalent compounds, the
representative elements follow the
octet rule (except H and He)
¤Hydrogen: follows DUET RULE

Strict followers of the Octet Rule
Atom # of valence Max. # of
e-’s bonds
C 4 4
N 5 3
O 6 2
F 7 1
LEWIS STRUCTURE OF COVALENT COMPOUNDS
SOME GUIDELINES
üC, N, O may form double or triple
bonds
üS can form double bonds with C, N,
or O
DRAWING LEWIS STRUCTURES
STEPS
1. Count the number of valence electrons.
2. Write the skeletal structure for the
molecule.
3. Place one pair of e-s (single bond)
between each bonded atoms.
STEPS
1. Count the number of valence electrons.
For polyatomic anions:
◦add the number of negative charges to the total # of
valence e-’s
For polyatomic cations:
◦subtract the number of positive charges from the total # of
valence e-’s
STEPS
4. Place lone pairs around surrounding
atoms to satisfy Octet rule.
5. Place remaining electrons around central
atom as lone pairs.
6. Move electrons to form double or triple
bond to satisfy Octet rule for the central
atom.
7. Assign formal charges to all atoms.
FORMAL CHARGE OF ATOMS IN A MOLECULE: apparent electronic

charge of each atom (not real charges); helps determine the
most likely structure
56
Helpful Reminders in Drawing Lewis structures:
1. Know the covalencies of each atom in the

molecule.
2. Give every second-row element no more than
eight electrons.
Draw the Lewis structure of:
1. PCl3
2. CH2Cl2
PCl3
Cl P Cl
1 P : 5
3 Cl : 3 x 7
26 e- Cl
CH2Cl2
H
1 C : 4
2 H : 2 x 1
2 Cl : 2 x 7 H C Cl
20 e-
Cl
Exceptions to the Octet Rule
The Incomplete Octet
Beryllium, Be
1s2 2s2
Lewis structure of BeH2 :
H – Be – H
Boron, B 1s2 2s2 2p1
Lewis Structure of BF3

The Expanded Octet
Elements in the 3 period
rd
have 3d orbitals that can be

used for bonding.
(e.g. S, P, Cl)
Sulfur, S [Ne] 3s2 3p4
Lewis Structure of SF6
Other examples:
PCl5
ClF3
I3 -
Draw the Lewis structure of the ff.:
1. BrF3
2. SeO2
Resonance
ØThe use of two or more Lewis
Structures to represent a particular
molecule or ion.
ØCan be written for molecules/ions
having a double or a triple bond and
single bond(s).
Resonance
• Some molecules cannot be adequately represented by a single
Lewis structure.
• These structures are called resonance structures or resonance

forms. A double-headed arrow is used to separate the two
resonance structures.
• Resonance structures are two Lewis structures having the same
placement of atoms but a different arrangement of electrons.
69
üDraw the resonance structures of
¤ SO2
¤ NO3-
SO2
S S
O O O O
NO3-
O O O
N N N
O O O O O O
For ozone, O3
# of e-’s A B C
Valence 6 6 6
Lone 4 2 6
pair
Shared 2 3 1
(x1/2)
F.C. 0 +1 -1
NCO- has 3 possible Lewis structures:
To choose the most plausible Lewis
structure:
ØThe sum of the FC’s of all atoms must equal
the overall charge on that species.
ØAtoms in molecules try to achieve FC’s as
close to zero as possible.
ØAny negative FC’s are expected to reside on
the most electronegative atoms.
Electronegativity
üElectronegativity is a measure of an atom’s attraction for electrons in a bond.
76
Which of the following structures is the most plausible?
Structure C is the most plausible

Electron sharing in Covalent Bonding
1. Equal sharing
a. Identical atoms sharing a pair of e-’s
H – H
b. Identical atoms with identical neighbors
H H
H C C H
H H
2. Unequal sharing
a. Dissimilar atoms
H – Cl stronger pull of e-’s by Cl
b. Identical atoms with dissimilar neighbors
H Cl
H C C Cl
H Cl
Polar bond – unequal sharing of
e-’s between 2 atoms
Geometry and Polarity
of Molecules
Limitation of Lewis Structures
Æ Tells us how atoms are bonded in a molecule

or ion
Æ Does not give the actual shape of the

molecule
VSEPR Theory
Valence Shell Electron Pair Repulsion

Predicts the overall geometry of molecules
from the electrostatic repulsions between
electrons (bonding and nonbonding) pairs
[Nevil Sidgwick and Herbert Powell, 1940]
Ø Geometry/Shape of Molecule
3D arrangement of atoms in a molecule
VSEPR Theory
Æ each set of valence electrons on the central

atom is significant
Æ these valence e-s repel one another
Æ they are arranged such that repulsions among

them are as minimal as possible
VSEPR Theory

Distinguish between:
• electron pair geometry – overall arrangement of e-
pairs (both bonding and lone pairs) around a central
atom
• molecular geometry (molecule or ion) – the

arrangement of the atoms in space; can be
predicted from the electron pair geometry
For 2 e- pairs:
0 lone pairs on central atom
Cl Be Cl
2 atoms bonded to central atom

For 3 e- pairs:
For 4 e- pairs:
For 5 e- pairs:
For 6 e- pairs:
Steps for using the
VSEPR Model:
vDraw the Lewis structure for the molecule/ion.
vCount the number of e- pairs around the central atom and
arrange them in the way that minimizes repulsions.
vDetermine the positions of the atoms from the ways the e-
pairs are shared.
v Name the molecule structure from the positions of the
atoms.
Molecular Geometries
# of e- pairs bonding pairs lone pairs
2 2 0
Type: AX2
Geometry: Linear
Example : BeH2
3 3 0
Type: AX3
Geometry: Trigonal planar
Example : BF3
3 2 1
Type: AX2E
Geometry: bent/V-shape
Example : SO2
# of e- pairs bonding pairs l one pairs
4 4 0
Type: AX4
Geometry: tetrahedral
Example : CCl4
4 3 1
Type: AX3 E
Geometry: trigonal pyramidal
Example : NH3
4 2 2
Type: AX2E2
Geometry: bent / V-shape
Example : H2O
5 5 0
Type: AX5
Geometry: trigonal bipyramidal
Example : PCl5
5 4 1
Type: AX4E
Geometry: See-saw shape
Example : SF4
5 3 2
Type: AX3E2
Geometry: T-shape
Example : BrF3
5 2 3
Type: AX2E3
Geometry: Linear
Example : ICl2-
6 6 0
Type: AX6
Geometry: Octahedral
Example : SF6
6 5 1
Type: AX5E
Geometry: Square pyramidal
Example : BrF5
6 4 2
Type: AX4E2
Geometry: Square planar
Example : ICl4-
VSEPR Theory
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
AX2 2 0 linear linear

trigonal trigonal
AX3 3 0
planar planar
AX4 4 0 tetrahedral tetrahedral
trigonal trigonal
AX5 5 0
bipyramidal bipyramidal
AX6 6 0 octahedral octahedral
VSEPR Theory
# of atoms # lone
trigonal trigonal
AX3 3 0
planar planar
trigonal
AX2E 2 1 bent
planar
VSEPR Theory
# of atoms # lone

trigonal
AX3E 3 1 tetrahedral
pyramidal
VSEPR Theory
# of atoms # lone

trigonal
AX3E 3 1 tetrahedral
pyramidal
AX2E2 2 2 tetrahedral bent

O
H H
VSEPR Theory
# of atoms # lone
trigonal trigonal
AX5 5 0
trigonal see-saw
AX4E 4 1
bipyramidal
VSEPR Theory
# of atoms # lone
trigonal trigonal
AX5 5 0
trigonal see-saw
AX4E 4 1
bipyramidal
trigonal
AX3E2 3 2 T-shaped
bipyramidal
F
F Cl
F
VSEPR Theory
# of atoms # lone
trigonal trigonal
AX5 5 0
trigonal see-saw
AX4E 4 1
bipyramidal
trigonal
AX3E2 3 2 T-shaped
bipyramidal
trigonal
AX2E3 2 3 linear
bipyramidal
I
I
VSEPR Theory
# of atoms # lone

square
AX5E 5 1 octahedral
pyramidal
F
F F
Br
F F
VSEPR Theory
# of atoms # lone

square
AX5E 5 1 octahedral
pyramidal
octahedral square
AX4E2 4 2
planar
F F
Xe
F F
Multiple Bonds
vFor the VSEPR model, multiple bonds count as one
effective e- pair.
vWhen a molecule exhibits resonance, any one of
the resonance structures can be used to predict the
geometry.
Examples:
VSEPR Theory
Implications of VSEPR
Bonding electrons are weaker because they are held by

attractive forces of 2 nuclei and have lesser “spatial
distribution” (can be compressed) than lone pairs.
According to VSEPR, volume occupied by e pairs show:

LP > triple bond > double bond > single bond
TYPES OF BONDS AND THEIR
PROPERTIES
1) Bond Order- number of bonds
between atoms
Bond Order
C-C 1
C=C 2
2) bond strength - measured in terms of the energy released
when a new bond is formed
- the same energy is needed to break the same

bond
Consider the following diatomic molecules:
H2 – the hydrogen molecule
H + H H H
1 1
1s 1s s bond
DH = 104 kcal/mol
bond length = 0.74 A°
DH - a measure of bond strength
3) bond length - the optimum distance between two nuclei
that leads to maximum stability
DE
equilibrium bond distance

(bond length)
internuclear distance
Bond type Bond Bond Bond
order length energy
(Å) (KJ/mol)
H3C-CH3 1 1.54 3339
H2C=CH2 2 1.33 5899
HCΞ CH 3 1.20 8117
↑ Bond order, ↓ Bond length,

↑ Bond energy
4) Bond Angle - angle between any two bonds in
a molecule
Molecular Geometry
Class Bond Angle
AX2 180o
AX3 120o
AX3 109.5o
Comparison of Bond angles of:
CH4 NH3 H2O
109.5o 107o 104.5o
5) Bond Polarity
- used in determining the net molecular

polarity, which is affected by the presence
of polar bonds and the overall geometry
of the molecule
RECALL: Electronegativity Trend:

Across a period: increasing up to
Group 17
Down a group: decreasing
Polar Covalent Bonds
E separation of charge creates a dipole
E polarity is indicated by the dipole moment, µ
µ = d ´q
where d = distance that separates the charges
q = magnitude of the charge
Polarity of Molecules
Dipole moment – represented by arrows pointing to
the more electronegative atom
A polar bond
Dipole moment
X:X X-Y+
symmetrical polar covalent ionic
covalent bond (non-polar) bond bond
Polar covalent bond
vWhen EN difference is
between 0.5 and 2, the
bond formed is a polar
covalent bond.
2 atoms of same element – same
EN – non-polar covalent bond
Atoms EN Type of
difference Bond
H-H none Non-polar
F-F
C-H 0.4 small Slightly
0.5 polar
N-O
H-Cl 0.9 polar
moderate
P-O
1.4
NaCl 2.1 high Ionic
KBr 2.0
Molecules may have polar bonds but are nonpolar
because they do not have a resultant dipole
moment.
A tetrahedral molecule is nonpolar only if all the
substituents are atoms of the same kind
Other examples
Generalizations on Polarity
Considering all substituents to be atoms of the
same kind:
üAll molecules containing lone pairs EXCEPT
AX2E3(linear) and AX4E2 (square planar) are
POLAR.
Practice:
Draw the Lewis Structure of
a. IF5 c. CH3I
b. BeF2 d. CH2S
Give the type of molecule (AXnEn).
Give the geometry.
Identify the polarity (polar or non-polar).
Bonding Theories:
Valence Bond Theory and
Molecular Orbital Theory
Valence Bond Theory
Ø Describes covalent bond formation in terms of
atomic orbitals
Key Ideas
ücovalent bonds are formed by overlap of atomic orbitals,
each of which contains one electron of opposite spin
üeach of the bonded atoms maintains its own atomic
orbitals, but the electron pair in the overlapping orbitals is
shared by both atoms
ü directional character to the bond when other than s orbitals
are involved
Valence Bond Theory
Overlap of two 1s orbitals

Consider F2 – the fluorine molecule
– 2 possible orbital overlaps:
F F
direct head-on overlap s bond
OR
F F
p bond
sideways overlap
•Which overlap type will prevail?
PAULING’s principle of maximum overlap:
*The strongest bond will be formed when two orbitals
achieve maximum overlap.
üStrength of the covalent bond depends on the

amount of orbital overlap " #overlap, stronger
the bond
Key Ideas
üdescribes a region of space in a molecule where
electrons are most likely to be found
üformed by combining atomic orbitals on different atoms;
# of molecular orbitals formed = # of atomic orbitals
combined
üelectrons occupy the molecular orbitals beginning with
the lowest energy
üonly 2 e–s occupy each orbital, and their spins are paired
Molecular Orbitals of H2
ütwo ways of orbital interaction
üAdditive combination – denoted by s; lower
in energy than the two isolated 1s orbitals;
bonding molecular orbitals; electrons spend
most of their time in the region between the
two nuclei
üSubtractive combination – denoted by s*;
higher in energy than the two isolated 1s
orbitals; antibonding molecular orbitals;
electrons can’t occupy the central region
between the nuclei and can’t contribute to
bonding
H• •H
üBond order – the number of electrons shared
between two atoms
(No. of bonding e- s) - (No. of antibonding e- s)

Bond order =
2
Øfor the H2 molecule, the bond order = 1

üBO > 0 " no. of bonding e-’s > antibonding e-
’s; more stable than separate atoms
üfractional bond orders exist in species that

contain an odd number of electrons
ühigher bond order, greater bond strength

MO Diagram of H2
B.O. = ½ (2-0) = 1
MO Diagram of He2
B.O. = ½ (2-2) = 0
MO Diagram of H2+
B.O. = ½ (1-0) =1/2

Thus it is stable.
MO Diagram of He2+
B.O. = ½ (2-1) = ½
Thus it is stable.
field
B2 C2 N2
Magnetism Paramag- Diamag- Diamag-
netic netic netic
B.O. 1 2 3
Bond 290 620 942

dissociation
E (KJ/mol)
Bond length 159 131 110
(pm)
Explains the Band Theory (MOT for Metals)
Øcombination of 3s orbitals of two sodium atoms

Conductivity of Metals
Example:
Draw the MO diagram and compare

the B.O. of O2, O2+ and O2-.
Which has the strongest bond?
Practice!
Draw the MO diagram for F2.
Calculate bond order and determine

whether it is paramagnetic or
diamagnetic.

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CHEMICAL

• Describe the octet rule

• Write the Lewis structure of elements and compounds

• Describe the formation and nature of the metallic bond

• Determine molecular geometry and predict polarity of molecules

• Explain chemical bonding using the Valence Bond Theory / MOT

•Ionic bonds: result from the transfer of

•Covalent bonds: result from the sharing of

7N: [He]2s22p3 + 3e- 5N3- [Ne]

8O: [He]2s 22p4 + 2e- 8O 2- [Ne]

9F: [He] 2s 22p5 + 1e- 9F- [Ne]

Ionic bond: the electrostatic force that

Ca : [Ar] 4s2 ® Ca2+ : [Ar]

Ca2+ + O2- ® CaO

Al3+ + O2- ® Al2O3

Group 1: H-, Li+, Na+, K+, Rb+, Cs+

LATTICE ENERGY – the change in energy that

Na+ (g) + Cl- (g)

Na (g) + 2Cl (g)

Na (s) + ½ Cl2 (g) NaCl (s)

¤Hydrogen: follows DUET RULE

FORMAL CHARGE OF ATOMS IN A MOLECULE: apparent electronic

1. Know the covalencies of each atom in the

Draw the Lewis structure of:

Lewis Structure of BF3

have 3d orbitals that can be

• These structures are called resonance structures or resonance

Structure C is the most plausible

Æ Tells us how atoms are bonded in a molecule

Æ Does not give the actual shape of the

Valence Shell Electron Pair Repulsion

Æ each set of valence electrons on the central

Æ these valence e-s repel one another

Æ they are arranged such that repulsions among

Valence Shell Electron Pair Repulsion

• molecular geometry (molecule or ion) – the

0 lone pairs on central atom

2 atoms bonded to central atom

AX2 2 0 linear linear

AX4 4 0 tetrahedral tetrahedral

AX4 4 0 tetrahedral tetrahedral

AX2E2 2 2 tetrahedral bent

AX6 6 0 octahedral octahedral

AX6 6 0 octahedral octahedral

Bonding electrons are weaker because they are held by

According to VSEPR, volume occupied by e pairs show:

- the same energy is needed to break the same

equilibrium bond distance

H2C=CH2 2 1.33 5899

HCΞ CH 3 1.20 8117

↑ Bond order, ↓ Bond length,

- used in determining the net molecular

RECALL: Electronegativity Trend:

E polarity is indicated by the dipole moment, µ

Overlap of two 1s orbitals

direct head-on overlap s bond

üStrength of the covalent bond depends on the

(No. of bonding e- s) - (No. of antibonding e- s)

Øfor the H2 molecule, the bond order = 1

üfractional bond orders exist in species that

ühigher bond order, greater bond strength

B.O. = ½ (1-0) =1/2

Bond 290 620 942