Chapter 8

Basic Concepts of
Chemical Bonding

Compounds
• Types of compounds
– Ionic (ex. NaCl)
– Molecular (CH4)

• Bonding only involves valance electrons

Lewis Symbols
• Definition - representations of molecules that show all
electrons, bonding and nonbonding.
• The structures show the valence electrons as dots
arranged around the atomic symbol.

H hydrogen

Na sodium

Cl chlorine

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 Lewis Symbols
• Formation of Lewis Symbols of many elements

The Octet Rule

• Definition - atoms tend to gain, lose, or share electrons
until they have eight valence electrons.

• This forms a noble gas electron configuration.

Chemical Bonds
• Definition – attraction between two atoms or ions
• Types
– Ionic bond – electrostatic forces between two ions with
opposite charge (ex. NaCl)

– Covalent bond – bond formed between two atoms that

share electrons (ex. CH4)

– Metallic bond – bond formed only with metals in which

each atom in the metal is bonded to several neighboring
atoms (Fe)

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 Ionic Bonds
Formation of cations
Na  Na+ + 1e- (495 kJ/mol)

Formation of anions
Cl + 1e-  Cl- (-349 kJ/mol)

Ionic Energies

ionization energy,
electron affinity, and
lattice energy

Polyatomic Ions
• Polyatomic ions carry a net charge which is
used for ionic bonding.

• The atoms within polyatomic ions are bound

predominantly by covalent bonds.

NH4+ CO32-

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 Covalent Bonding
• Atoms share electrons.

• Electrostatic interactions in
these bonds:
– Attractions between electrons
and nuclei
attractive forces > repulsive forces
– Repulsions between electrons
– Repulsions between nuclei
H2

Covalent Bonding
The simplest covalent molecule is H2:

- Increased electron density

draws nuclei together
- So, the share the electrons

Lewis Symbols
• The formation of covalent bonds can be
represented using Lewis symbols.
H H
H H

H H

H H

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 Representing Covalent Bonding

• Each Lewis structure should have an octet for each

atom except hydrogen.

H2: H + H H H or H H

Cl2: Cl + Cl Cl Cl
Bonding
Electrons (line)

or Cl Cl
Nonbonding electrons (dot)

Bond Polarity
Shared equally F has more pull

• Fluorine pulls harder on the electrons it shares

with hydrogen than hydrogen does.
• Therefore, the fluorine end of the molecule has
more electron density than the hydrogen end.

Electronegativity
• Definition - Ability of atoms in a molecule to
attract electrons to itself.

• Periodic table
trend?

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 Polar Covalent Bonds
• When two atoms share
electrons unequally, a bond
dipole results.

• The dipole moment, ,

produced by two equal but
opposite charges separated
by a distance, r, is
calculated:
= Qr

• It is measured in debyes (D).

Polar Covalent Bonds

The greater the
difference in
electronegativity,
the more polar is
the bond.

Bond Polarities
+

H Cl = 0.9
2.1 3.0
Electronegativity
Difference Bond Type
0 - 0.5 Nonpolar
0.5 - 2.0 Polar
2.0 Ionic

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 Drawing Lewis Structures
1. Find the sum of valence electrons of all atoms in the
polyatomic ion or molecule.

PCl3 5 + 3(7) = 26

2. The central atom is the least electronegative element

that isn’t hydrogen. Connect the outer atoms to it by
single bonds.

26 6 = 20

3. Fill the octets of the outer atoms.

26 6 = 20 18 = 2

Drawing Lewis Structures

4. Fill the octet of the central atom.
26 6 = 20 18 = 2 2=0

5. If you run out of electrons before the central atom has an

octet, form multiple bonds until it does.

Covalent Bond Orders

• Single covalent bond - sharing a pair of electrons (ex.
Cl2)

• Double covalent bond – sharing two electron pairs

(ex. O2 )

• Triple covalent bond – sharing three electron pairs

(ex. N2)

• How many electrons are in each bond type?

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 Bond Distance & Order
• The distance between bonded atoms
decreases as the number of shared electron
pairs increases.

1.47 Å Single N2
1.24 Å Double N2
1.10 Å Triple N2

Formal Charges
• Definition -the charge that an atom in a molecule would have
if the bonding electron pairs were shared evenly.

– For each atom, count the electrons in lone pairs and half the electrons
it shares with other atoms.

– Subtract that from the number of valence electrons for that atom:
The difference is its formal charge.

Formal Charge
FC = # val. e- isolated atom - # e- Lewis structure of atom

-
C N

1. Atoms in Lewis structure

C: 2 (nonbonded) + 3 (bonded) = 5
N: has 2 (nonbonded) + 3 (bonded) = 5

2. Formal Charge
C: 4 val. e-: 4 – 5 = -1
N: 5 val. e-: 5 – 5 = 0

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 Which Structure is Best?
• The best structures are those that:
• have the fewest charges
• puts a negative charge on the most
electronegative atom.

Resonance Structures
• Two Lewis structures for a compound may be
equivalent

ozone

• Resonance structures illustrate the multiple

structures of the molecule

• Electron locations are different

More Resonance
• The electrons that form the second C—O bond in the
double bonds below do not always sit between that C
and that O, but rather can move among the two
oxygens and the carbon.

• They are not localized, but rather are delocalized.

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 Octet Rule Exceptions
– Ions or molecules with an odd number of
electrons. We can’t pair all e- in NO, and NO2

– Ions or molecules with less than an octet.

(transition metals)
Fe: [Ar]3d64s2  Fe2+: [Ar]3d6

– Ions or molecules with more than eight valence

electrons (an expanded octet).

Exceptions-Shortened Octet
• Ions or molecules with less than an octet, they are
surrounded by 2 or 3 pairs of electrons instead of 4
pairs
• Example: BF3

Exceptions – Expanded Octet

• Ions or molecules with more than eight valence electrons
(an expanded octet).
• The only way PCl5 can exist is if phosphorus has 10
electrons around it.
• It is allowed to expand the octet of atoms on the 3rd row
or below.
– Believed d orbitals participate in bonding.

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 Exceptions – Expanded Octet

Common Elements

Group 15 Group 16 Group 17 Group 18

3rd
P S Cl
period

4th
As Se Br Kr
period

5th
Sb Te I Xe
period

Covalent Bond Strength

• Most simply, the strength of a bond is measured by

determining how much energy is required to break
the bond.
• This is the bond enthalpy.
• The bond enthalpy for a Cl—Cl bond,
D(Cl—Cl), is measured to be 242 kJ/mol.

Average Bond Enthalpy

Average bond enthalpies
(not absolute) for many
• Average bond different bond types. kJ/mol
enthalpies are positive,
because bond breaking
is an endothermic
process.

• Energy is released
when bonds are
formed.

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 Enthalpies of Reaction
• Estimate H for a
reaction by comparing
the bond enthalpies of
bonds broken to the
bond enthalpies of the
new bonds formed.

Hrxn = (bond enthalpies broken bonds)

(bond enthalpies formed bonds)

Endothermic vs Exothermic
• A reaction is endothermic when ∆H > 0 (+) and
exothermic when ∆H < 0 (-).

Hproducts < H reactants exothermic

Hreactants < H products endothermic

Bond Lengths & Enthalpies

C C single bond 348 kJ/mol, double bond 614 kJ/mol,

triple bond 839 kJ/mol

• We can also measure an average bond

length for different bond types.
• As the number of bonds between two atoms
increases, the bond length decreases.

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 Enthalpies of Reaction
CH4(g) + Cl2(g) CH3Cl(g) + HCl(g)

C—H bond and Cl—Cl bond are broken

C—Cl and H—Cl bond are formed.

To find heat of reaction:

Hrxn = [D(C—H) + D(Cl—Cl) [D(C—Cl) + D(H—Cl)
= [(413 kJ) + (242 kJ)] [(328 kJ) + (431 kJ)]
= (655 kJ) (759 kJ)
= 104 kJ

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