the chemical bond:

the force that holds atoms or ions

Chapter 9 ◆

together as an aggregate unit

bond energy (or bond dissociation enthalpy, ∆HBDE):

Ionic and Covalent ◆ energy required to break a chemical bond
Cl–Cl (g) ! 2 Cl (g); ∆H = bond
Bonding energy
◆ bond energy is always endothermic

generally 3 types of bonds - ionic, covalent, metallic

Lewis Symbols
The Octet Rule
developed by G.N. Lewis to represent an element and
its number of valence electrons atoms tend to lose, gain, or share e-’s in such a way
that they attain a noble gas configuration (ns2 np6)
◆ each side of element’s symbol may have
0, 1, or 2 dots ◆ ionic compounds:
typically metals with low ionization energy
◆ each dot represents a valence electron lose e-‘s
◆ for main group elements: nonmetals with favorable electron affinity
# valence e–’s = group # gain e-’s
 The Octet Rule Energy Considerations of Ionic Compounds
◆ molecular compounds: Lattice Energy, U: the energy required to
typically nonmetals will share e-’s to form separate an ionic solid into its gas phase
covalent bonds ions
MX (s) ! M+ (g) + X– (g); endothermic

Lattice Energy and Coulomb’s Law Electron Configurations of Ions

Coulomb’s Law: cations
◆ describes the energy of electrostatic
◆ formed by the loss of electrons
interaction between 2 charged particles
separated by some distance ◆ e–’s are lost from the highest energy,
populated atomic orbital
Q1●Q2
Ecoul ∝ ––––––
r anions
Q1 and Q2 = charges on ions ◆ formed by the gain of electrons
r = distance between ions
◆ e–’s are added to the lowest energy available
◆ this relationship is also true for lattice energy atomic orbital
How does the e– configuration of an atom change as an ion is formed?
U ∝ charges on ions
U ∝ 1/distance separating ions
 Electron Configurations of Ions Ionic Radii
◆ size of cation or anion relative to the parent atom
some examples of cations that do not have a noble
gas configuration:
cations are smaller than
◆ heavy main group metals: their parent, neutral atom
ex. Sn2+ rNa+ < rNa

◆ transition metals: anions are larger than their

ex. Fe3+ parent, neutral atom
rCl– > rCl

Periodic Trend in Ionic Radii

◆ Similar to atomic radii, ionic radii increase from
the top to the bottom of the periodic table.

◆ To understand the trend moving left to right across

the periodic table, consider isoelectric species.
isoelectric – same number of electrons
O2– F– Na+ Mg2+ Al3+
# e–’s 10 10 10 10 10
# p’s 8 9 11 12 13
ionic
140 pm 136 pm 95 pm 65 pm 50 pm
radius
 Molecular Compounds:
Covalent Bonds
In molecular compounds, atoms share electrons to
achieve a noble gas configuration
◆ covalent bonds result from shared pairs of
electrons between atoms
◆ electrons are shared in the region between
atoms where atomic orbitals overlap
◆ orbital overlap results in a concentration of
electron density between 2 nuclei

Nonpolar vs Polar Covalent Bonds:

How is the electron density distributed between
atoms in a bond?
Electronegativity, !: Some Introductory Thoughts About Structure and
the ability of an atom in a polyatomic species to Bonding in Molecular Compounds
attract electrons to itself
◆ How many covalent bonds is a central atom in a
molecule likely to form?
consider the element’s group # and # valence e–’s
use the octet rule as a guideline

◆ bonding vs. nonbonding pairs of electrons

◆ The greater the difference in electronegativity (∆ !)

between 2 atoms in a bond, the more polar the bond.

Some Introductory Thoughts About Structure and

Bonding in Molecular Compounds Drawing Lewis Structures
◆ single vs. multiple bonds
1 pair of e–’s shared between atoms (i.e. 2 shared e–’s)
a 1st step to understanding:
! single bond ◆ molecular structure
2 pairs of e–’s shared between atoms (i.e. 4 shared e–’s)
! double bond ◆ atom connectivity
3 pairs of e–’s shared between atoms (i.e. 6 shared e–’s) ◆ arrangement & distribution of valence e–’s
! triple bond ◆ numbers and types of bonds
◆ numbers of nonbonding pairs of e–’s
◆ 3-D shape
◆ bond angles
◆ molecular polarity
 Drawing Lewis Structures Drawing Lewis Structures

start by thinking about structures of molecules We will use the localized electron model to:
using the localized electron model: ◆ describe the atom arrangement and
distribution of valence e–’s in a molecule
◆ localized electron model assumes molecules
Lewis Dot Structures (now)
are collections of atoms bonded together by
covalent bonds ◆ predict molecular geometry, bond angles,
and polarity
◆ pairs of electrons are either localized on
VSEPR Theory (Ch. 10)
atoms (lone or nonbonding e– pairs), or
localized in the space between 2 atoms ◆ describe the types of atomic orbitals used
(bonding e– pairs) by atoms in bonding or to house lone pairs
Valence Bond Theory (Ch. 10)

Drawing Lewis Structures Drawing Lewis Structures

1. Determine the total number of valence electrons in
the molecule: 3. Complete the octets of atoms bonded to the
total # valence e–’s = ∑valence e–’s of atoms in central atom(s).
molecule
H, He, Li, and Be will only have a duplet of e–’s
◆ main group elements: # valence e–’s = group #
◆ add 1e– for each unit negative charge on anion 4. Place any left over electrons on the central
◆ subtract 1e– for each positive charge on cation atom, even if it results in greater than an octet.

! this is the total number of electrons you will 5. If there are not enough electrons to give the
need to have in your final structure central atom a full octet, try multiple bonds.
2. Write symbols for atoms in order of connectivity;
connect appropriate atoms with single bonds
 Drawing Lewis Structures What if you can draw more than one Lewis
examples: Structure that obeys the octet rule?
PCl3 CH2Cl2
Which one is the “right” one?

2 concepts to help interpret Lewis structures:

HCN ClO2– ◆ Formal Charge
same atom arrangement; different
e– arrangement
NH4+ N2H4
◆ Resonance Structures
same atom arrangement; same net e–
COBr2 arrangement; same formal charge
distribution

◆ Considering formal charges In general, the more stable Lewis structure is

considered to be the one in which:
to determine formal charges of elements in structure:
1. all unshared e–’s (lone pairs) are assigned to the atom ◆ atoms bear formal charges closest to 0
on which they are found ◆ any negative formal charge resides on more
2. bonding e–’s
are assumed to be shared evenly between electronegative element
the atoms participating in the bond;
◆ homolytic clevage of the bond ex: Consider 2 possible Lewis structures of CO2.
◆ ! of the bonding e–’s are assigned to each atom in the
bond
3. formal charge = # valence e–’s of isolated atom –
ex: Consider 3 possible Lewis structure of NCS–.
# e–‘s assigned by Lewis structure
 ◆ Considering resonance structures
The 2 resonance structures A and B are equivalent
sometimes one Lewis structure does not contributors to the overall resonance hybrid structure.
adequately describe e– arrangement
supported by experimental evidence
resonance hybrid
example: Consider 2 possible Lewis structures for
structure
ozone, O3:
example: carbonate ion, CO32–

experimental data:
◆ O3 is a bent molecule

◆ both O–O bond lengths equivalent

Exceptions to the Octet Rule Exceptions to the Octet Rule

1. odd number of electrons 3. central atom has more than an octet of e–’s

ex. NO ◆ expanded valence

◆ possible for larger central atoms in the
3rd period and below
ex. PCl5
2. central atom has less than an octet
ex. BF3

XeF4
 A Way to Think About Expanded Valence A Way to Think About Expanded Valence

for PCl5: for XeF4:

◆ central atom: P ◆ central atom: Xe
◆ valence e– configuration: 3s2 3p3 ◆ valence e– configuration: 5s2 5p6
◆ empty 3d orbitals sit at slightly higher energy ◆ empty 5d orbitals sit at slightly higher energy

◆ 2 5p e–’s absorb E and are promoted

◆ a 3s e– absorbs E and is promoted to a to higher E, empty 5d orbitals
higher E, empty 3d orbital

↑↓ ↑ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑↓
3s 3p 3d 5s 5p 5d

↑ ↑ ↑ ↑ ↑ ↑↓ ↑↓ ↑ ↑ ↑ ↑
3s 3p 3d 5s 5p 5d

Using Covalent Radii to Approximate Bond Length

A A A B

A–A bond length = rA + rA A–B bond length = rA + rB

◆ knowing periodic trend in atomic radii can help

you make predictions about relative lengths of
bonds
example: Would you predict that a N–Cl or
a P–Br bond would be longer?
 Bond Multiplicity (or Bond Order) and
Relationship to Bond Length and Bond Energy

bond bond # e– pairs # e–’s

type order shared shared

bond single 1 1 2 bond

length energy
decreases increases

double 2 2 4

triple 3 3 6

A Word About Tabulated Bond Energy Data Using Bond Energies to Approximate ∆Hrxn:
recall: ∆Hrxn = ∑ E of bonds broken " ∑ E of bonds formed
◆ bond energy (or bond enthalpy) is the energy
required to break a bond
◆ endothermic
◆ units kJ/mol

example:
What is the C–H bond energy?
if: CH4 (g) ! C (g) + 4 H (g); ∆H = 1660 kJ
then: we can approximate the average C–H
bond energy as 1660 ÷ 4 = 415 kJ
 Using Bond Energies to Approximate ∆Hrxn:
∆Hrxn = ∑ E of bonds broken " ∑ E of bonds formed

example:
Calculate ∆H for the following reaction using
bond energies:
C2H4 (g) + H2O (l) ! C2H5OH (l)