Chapter 3

Bonding:
General Concepts
 Types of Chemical Bonds
• Chemical bond: force that holds atoms together in a
compound
• Three types of chemical bonds:
─ Ionic
─ Covalent
─ Metallic
Covalent Bonds and Molecular Compounds
Interaction between nonmetals
• Covalent bond: sharing electrons between two atoms
• The covalently bound atoms compose a molecule.
─ The resulting compounds are called molecular compounds.
 Representing Molecular Compounds
• Chemical formula: shows Compounds Chemical Empirical
Formulas Formulas
type and number of each Water H2O H2O
element in the compound Hydrogen Peroxide H2O2 HO
• Empirical formula: shows Methane CH4 CH4
relative number of each Ethylene C2H4 CH2
element in the compound
• Structural formula: shows the way atoms
are bonded
• Space-filling model: Indicates the relative
sizes of the atoms as well as their relative
orientation in the molecule
• Ball and stick method: a three-
dimensional model using spheres and rods
 Ionic Bonds and Ionic Compounds
Interaction between e-
metal and nonmetal Metal atom Nonmetal atom
Na Cl
• Transfer of electron(s)
from metal to nonmetal Anion
Cation
• Ionic bond: electrostatic Na+ Cl-
attractive force between
oppositely charged ions
Ionic bond
• Ionic compounds: composed Ionic compound
of cations and anions bound NaCl
together by ionic bonds
• Coulomb’s law: used to calculate the
energy of interaction between ions
QQ 
E = (2.31 × 10 –19 J . nm)  1 2 
 r 
E - has units of joules
r - distance between
Q1 and Q2 - numerical ion charges
 Octet Rule

Octet Rule:

A chemical bond is the sharing or transfer of electrons

to attain a stable electron configuration for the bonding
atoms.
 Predicting Charges of Ions
For main group elements, the ions are formed in such a way
that both ions achieve noble gas electron configuration.
Atom Ion Formed
Ca [Ar]4s2 Ca2+ [Ar]
O2- [He]2s22p6 or [Ne]
O [He]2s 2p 2 4

For most main group elements:

charge of cation = group number
charge of anion = group number - 8
Predicting Formulas of Ionic Compounds
• Ions are charged particles, but ionic compounds are
electrically neutral.

Total number of Total number of

positive charges = negative charges

Examples: Na+ Cl- Ca2+ Br- K+ S2- Mg2+ N3-

↓ ↓ ↓ ↓
NaCl CaBr2 K2S Mg3N2

• The formula of an ionic compound reflects the smallest

whole-number ratio of ions.
 Sizes of Ions
• Ion size influences the structure and stability of ionic solids
• Size is determined by measuring the distance between ion
centers
• Factors that influence ionic size
‒ Size of the parent ion
‒ Position in the periodic table
• Cations are smaller than their parent atoms.
– The outermost electron is removed and
repulsions between electrons are reduced.
• Anions are larger than their parent atoms.
– Electrons are added and repulsions
between electrons are increased.
 Isoelectronic Ions
Na Mg Al O F
Z: 11 12 13 8 9
Na+ Mg2+ Al3+ O2- F- Isoelectronic ions
e: 10 10 10 10 10 – ions with same
number of electrons

• For a series of isoelectronic

ions, the size decreases with
an increasing nuclear charge.

increasing nuclear charge

O2- F- Na+ Mg2+ Al3+

140 136 95 65 50 pm

decreasing ionic radius

 Lattice Energy
• Lattice energy: energy change that takes place when
separated gaseous ions are packed together to form an
ionic solid
M + (g ) + X – (g )  MX(s)

QQ  k -constant
Lattice energy = k  1 2  Q1 and Q2 - charges on the ions
 r 
r - distance between two ions
• Compounds with smaller ions and higher charges have
higher lattice energies.

Question: Which one has the greater magnitude of

lattice energy, MgF2 or CaF2?
 Localized Electron (LE) Bonding Model
• A molecule is composed of atoms that are bound together
by sharing pairs of electrons using the atomic orbitals of
the bound atoms
‒ Pairs of electrons localized on a specific atom are called
lone pairs
‒ Electron pairs found in the space between the atoms
are called bonding pairs
• Three parts of LE Model
‒ Description of the valence electron arrangement in the
molecule using Lewis structures
‒ Prediction of the geometry of the molecule using the
valence shell electron-pair repulsion (VSEPR) model
‒ Description of the type of atomic orbitals used by the
atoms to share electrons or hold lone pairs
 Lewis Structures
• Lewis symbols of atoms
− Focuses on valence electrons
− Use dots surrounding the symbol
of the element to represent
valence electrons
− In writing Lewis symbols, the first four dots are placed singly
on each of the four sides of the chemical symbol. Dots are
paired as the next four are added.

• Lewis structures of molecules

− Show how valence electrons are arranged among the atoms
in the molecule
− Guideline for Lewis structure: atoms achieve noble gas
electron configuration –octet rule and duet rule
 Simple Lewis Structures
Each atom obeys the
or octet rule or duet
rule for H!
or
. Single bond – 1 pair
:O:
.
+ 2H 
.
of electron shared
Double bond – 2 pairs
of electrons shared
Triple bond – 3 pairs
of electrons shared
. . .. .. .. ..
Multiple bond is
. +. :O:  :O::O: (or :O=O:)
:O:
shorter and stronger
than single bond.
 Bond Length and Bond Energy
• Bond length - distance between the nuclei of bonded atoms
• Bond energy - amount of energy needed to break a bond
Cl2 (g)  2 Cl (g) Bond energy = 243 kJ
HCl (g)  H (g) + Cl (g) Bond energy = 421 kJ

• The stronger bond is shorter and has larger bond energy.

• Bond length: triple bond < double bond < single bond
Bond strength: triple bond > double bond > single bond
 Polar Covalent Bond
• Nonpolar covalent
H—H F—F bond - electrons are
equally shared.

H—F • Polar covalent bond

- electrons are
unequally shared.
 Electronegativity
• Electronegativity
− ability of an atom in a molecule to attract bonding
electrons to itself
− quantified by Linus Pauling (American Chemist)

• Trend: electronegativity increases across a period (left

to right) and decreases down a group (top to bottom).
Electronegativity Difference & Bond Polarity
The larger the electronegativity difference in
the bonding atoms, the more polar the bond.
EN 2.1 EN 4.0
Electronegativity Difference & Bond Polarity
Example
Order the following bonds according to polarity:
H—H, O—H, Cl—H, S—H, and F—H

From EN trend: S < Cl < O < F

ΔEN: H—H < S—H < Cl—H < O—H < F—H
 Writing Lewis Structures
Steps:
1. Write the correct skeletal structure for the molecule.
a. Central atom is the least electronegative element
b. H is always terminal
2. Determine the total number of valence electrons each atom
is bringing in to form the molecule.
a. For anion – add electron(s)
b. For cation – subtract electron(s)
3. Distribute the electrons among the atoms in the molecule
giving octets (or duets in the case of hydrogen) to as many
atoms as possible.
a. Begin with bonding electrons
b. The lone pairs on terminal atoms
c. Finally lone pairs on central atoms
4. If any atoms lack an octet, form double or triple bonds as
necessary to give them octets.
 Lewis Structure of PCl3
Steps Example Electron Count
1. Draw skeletal structure
a. Central atom is the least Cl P Cl
electronegative element Cl
b. H is always terminal
2. Determine total # of valence electrons
a. For anion - add electron(s) 5 + 3 x 7 = 26
b. For cation – subtract electron(s) total
3. Distribute electrons among atoms to
make octet for every atom
a. Begin with bonding electrons 26 – 6 = 20 left
b. Complete the octets of the outer
atoms
20 – 18 = 2 left
c. Place any leftover electrons on the
central atom.

2–2=0
No e- left
 Lewis Structure of HCN
Steps Example Electron Count
1. Draw skeletal structure
H C N
2. Determine total # of valence electrons 1 + 4 + 5 = 10
total
3. Distribute electrons among atoms to
make octet for every atom H–C–N 10 – 4 = 6 left
a. Begin with bonding electrons
b. Complete the octets of the outer
atoms 6–6=0
No e- left

c. Place any leftover electrons on the

central atom.

4. If any atoms lack an octet, form multiple

bonds
 Lewis Structure of O3
Steps Example Electron Count
1. Draw skeletal structure
O O O
2. Determine total # of valence electrons 3 x 6 = 18 total

3. Distribute electrons among atoms to

make octet for every atom O–O–O 18 – 4 = 14 left
a. Begin with bonding electrons
b. Complete the octets of the outer .. ..
atoms : O – O – O: 14 – 12 = 2 left
.. ..
c. Place any leftover electrons on the .. .. ..
central atom. 2–2=0
: O – O – O: No e- left
.. ..
4. If any atoms lack an octet, form multiple
bonds
 Resonance Structures
• Lewis structure for ozone (O3):
on average
O – O single bond: 1.48 Å
O = O double bond: 1.21 Å
• Observed structure of ozone:
Both O-O bonds have same length,
1.278 Å
• We use multiple structures,
resonance structures, to
describe the molecule.

• The resulting structure is derived from the average of

the resonance structures.
 Lewis Structure of NO3-
Steps Example Electron Count
1. Draw skeletal structure

2. Determine total # of valence 5+3x6+1=

electrons 24 total
3. Distribute electrons among atoms
to make octet for every atom 24 – 6 = 18 left
a. Begin with bonding electrons
b. Complete the octets of the
outer atoms 18 – 18 = 0
c. Place any leftover electrons on No electron left
the central atom.
4. If any atoms lack an octet, form
multiple bonds or

Resonance structures
All three N-O bonds are equal in
length!
 Lewis Structure of CO2
Steps Example Electron Count

1. Draw skeletal structure

O C O
2. Determine total # of valence electrons 4 + 2 x 6 = 16
total
3. Distribute electrons among atoms to
make octet for every atom 16 – 4 = 12 left
a. Begin with bonding electrons

b. Complete the octets of the outer 12 – 12 = 0

atoms No e- left
c. Place any leftover electrons on the
central atom.
4. If any atoms lack an octet, form multiple
bonds
 Formal Charges
• The concept of formal charge helps us chose between alternative
Lewis structures.
• During bonding, atoms may end with more or fewer electrons than
the valence electrons they brought in order to fulfill octets.
─ This results in atoms having a formal charge.

Formal Charge (FC) = (valence e−) − (nonbonding e− + ½ bonding e−)

= (valence e−) − (nonbonding e−) − ( ½ bonding e−)

- Nonbonding electrons: - 4 0 -4 -6 0 -2
- ½ Bonding electrons: - 2 - 4 - 2 -1 -4 -3
Formal charge: 0 0 0 -1 0 +1
• The best Lewis structure is the one with the fewest charges.
 Formal Charge

• The best Lewis structure…

─ …is the one with the fewest charges.
─ …puts a negative charge on the most electronegative
atom.
 Formal Charge - Summary
The concept of formal charge is useful because it helps
distinguish between competing skeletal structures or
competing resonance structures. In general, these four
rules apply:
1. The sum of all formal charges in a neutral
molecule must be zero.
2. The sum of all formal charges in an ion must
equal the charge of the ion.
3. Small (or zero) formal charges on individual
atoms are better than large ones.
4. When formal charge cannot be avoided, negative
formal charge should reside on the most
electronegative atom.
 Writing Lewis Structures
• The Octet rule
• Two additional concepts to write the best possible
Lewis structures for a large number of compounds
─ Resonance, used when two or more valid Lewis
structures can be drawn for the same compound
─ Formal charge, an electron bookkeeping system
that allows us to discriminate between alternative
Lewis structures
• Exceptions to the octet rule
− Odd-electron species
− Incomplete octets
− Expanded octets
 Exceptions to the Octet Rule
• Odd-electron species:
─ Molecules or ions with an odd number of electrons
are called free radicals or radicals.
─ Example: NO has 11 valence electrons.
─ Free radicals tend to be unstable and reactive.

Molecule of the Year in 1992

D. E. Koshland, Jr (1992). "The Molecule

of the Year". Science 258 (5090): 1861
 Exceptions to the Octet Rule
• Incomplete octets:
─ Some molecules have less than an octet of electrons, particular
those with Be, B or Al.
─ Examples:

─ Why not make a double bond to satisfy the octet rule?

─ Octet rule vs. formal charge

 Exceptions to the Octet Rule
• Expanded octets:
─ Some compounds have expanded octet, which
means that the central atom has more than eight
electrons around it.
─ Examples:
─ The only way PCl5 can exist is if
phosphorus has 10 electrons
around it.
─ In general, the expand octets
occur in 3rd row (or below)
elements.
 Exceptions to the Octet Rule
• Expanded octets:
─ Lewis structures of SO4 2- :

Which Lewis
structure is better?

─ Octet rule vs. formal charge again

Naming Binary Ionic Compounds (Type I)
• Binary compounds – compounds with two elements
• Binary ionic compounds: cation + anion
• Rules in naming type I binary compounds
‒ cation is named first and anion second
‒ cation name: name of the element
‒ anion name: root of the element name + adding -ide
 Binary Ionic Compounds (Type I)
• Name each binary ionic compound
NaCl sodium chloride
CaBr2 calcium bromide
K2S potassium sulfide
Mg3N2 magnesium nitride

• Write the formula for the following compound

Potassium iodide
Calcium oxide
Gallium bromide
Naming Binary Ionic Compounds (Type II)
• Some metals form more than
one type of positive ion
‒ The charge on the metal ion is
specified using Roman numerals
• Alternative for metals that form
only two ions
‒ ions with higher charge end in -ic
‒ ions with lower charge end in -ous
• Examples:
Ionic compounds: You must
FeCl3 iron(III) chloride determine
or ferric chloride the charge
CuO copper (II) oxide on the
or cupric oxide
cation first.
 Naming
Binary Ionic
Compounds
 Polyatomic Ions
• Polyatomic ions consist of atoms joined as in a • Memorize
molecule, but they have charge. name,
formula, and
charge of the
following
polyatomic
ions:
Acetate
Carbonate
Hydroxide
Nitrate
Phosphate
Ammonium
Sulfate
Perchlorate
Ionic Compounds with Polyatomic Ions

• Naming:
Al(NO3)3 aluminum nitrate
Cu(ClO4)2 copper (II) perchlorate
or cupric perchlorate

• Writing formula:
Cobalt(II) phosphate
Naming Binary covalent Compounds (Type III)
• They are formed between two non-metals
• Rules in naming binary covalent compounds
‒ The 1st element in the formula is
named first, using the element name.
‒ The 2nd element is named as if it
were an anion.
‒ Prefixes are used to denote the
numbers of atoms present.
‒ The prefix mono- is never used for
naming the 1st element, eg. CO.
• Examples:
NI3 nitrogen triiodide
PCl5 phosphorus pentachloride
P4S10 tetraphosphorus decasulfide