CHEMICAL BONDING

CHM 101
 What is a Chemical Bond?
• Bonding is the force of attraction that holds atoms together in an element (N2)
or compound (CO2 or NaCl). A chemical bond links two atoms or groups of
atoms when the forces acting between them are sufficient to lead to the
formation of an aggregate (a molecule) with sufficient stability to make it
convenient for the chemist to consider it as an independent "molecular
species” Paraphrased from Linus Pauling (1967).
• The distances between bonded atoms are less than those between non-bonded
atoms.
• The forces between bonded atoms are greater than those between
non-bonded atoms.
• The principal types of bonding are ionic, covalent, and metallic.
Periodic Table
 Electronegativity
Electronegativity is a measure of the tendency of an atom to
attract a bonding pair of electrons. The Pauling scale is the
most commonly used. Fluorine (the most electronegative
element) is assigned a value of 4.0, and values range down
to caesium and francium which are the least electronegative
at 0.7. The greater the electronegativity of an atom in a
molecule, the more strongly it attracts electrons to itself.
Two properties that relate to electron attraction:
ionization energy e.g. Na → Na+ + e-
electron affinity e.g. S + 2 e- → S-2
Both apply to isolated atoms!
 The Octet Rule

In forming chemical bonds, atoms usually gain, lose

or share electrons until they have 8 in the outer shell

recall the electron configurations for group 8A

elements (ns2 np6)
 Lewis Dot Structures
• Developed by G. N. Lewis to serve as a way to
describe bonding in polyatomic systems. Lewis
structures represent molecules using element
symbols, lines for bonds, and dots for lone pairs.
• Central idea: the most stable arrangement of
electrons is one in which all atoms have a “noble”
gas configuration.

• Example: NaCl versus Na+Cl-

Na: [Ne]3s1 Cl: [Ne]3s23p5

Na+: [Ne] Cl-: [Ne]3s23p6 = [Ar]

Valence Electrons
- The electrons involved in bonding are called valence
electrons.
- Valence electrons are found in the incomplete,
outermost orbital shell of an atom.
- We can represent the electrons as dots around the
symbol for the element.
- These pictorial representations are called Lewis
Structures or Lewis Dot Structures.
Lewis Symbols and the Octet Rule
 LDS Mechanics
• Atoms are
represented by atomic
symbols surrounded
Lone Pair (6 x)
by valence electrons.

• Electron pairs
between atoms
indicate bond
formation.
Bonding Pair
 LDS Mechanics (cont.)
• Three steps for “basic” Lewis structures:

1. Sum the valence electrons for all atoms to determine

total number of electrons.

2. Use pairs of electrons to form a bond between each

pair of atoms (bonding pairs).

3. Arrange remaining electrons around atoms (lone pairs)

to satisfy the “octet rule” (“duet” rule for hydrogen).

- If you are “short” of electrons, form multiple bonds

- If you have “extra” electrons, one of the heavy atoms may be able to
hold more than eight electrons.
Drawing Lewis Structures
1) Draw a skeleton structure of the molecule or ion
showing the arrangement of the atoms and the
connect each atom to another with a single bond.
2) Determine the total number of valence electrons in
the molecule or ion.
3) Deduct 2 electrons for each single bond used in step 1.
4) Distribute the rest of the electrons so that each atom
(except H) has 8 electrons.
- If you are “short” electrons, form multiple bonds
- If you have “extra” electrons, one of the heavy atoms may be able to hold more
that eight electrons.

Chapter 9 11
Drawing Lewis Structures
PCl3

Element Number Electrons Total

P 1 5 5
Cl 3 7 21
Total Electrons 26
 LDS Mechanics (cont.)
• An example: Cl2O

20 e-

16 e- left
 LDS Mechanics (cont.)
• An example: CH4

8 e-

0 e- left

Done!
 LDS Mechanics (cont.)
• An example: CO2

16 e-

12 e- left

Octet Violation
0 e- left

CO double bond
 LDS Mechanics (cont.)
• An example: NO+
+ +

10 e-

8 e- left

+
 Types of Bonds

Polar Covalent
Bond

Covalent Ionic Bond

0 0.5 2.0 3.5

Electronegativity Difference
Chemical Bond Formation
- There are three types of chemical bonds
Ionic Bond - electrostatic attraction between ions of
opposite charge (NaCl).

Covalent Bond - sharing of electrons between two or

more atoms (Cl2).

Metallic Bond - sharing of electrons between several

atoms (Ag).
 Ionic Compounds
They are formed from a metallic cation, and a
non-metallic anion.
• An ionic bond generally occurs when elements on the far left side of the periodic table
combine with elements on the far right side, ignoring noble gases.
• A positively charged cation formed from the element on the left side attracts a
negatively charged anion formed from the element on the right side. An example is
sodium chloride, NaCl.

20
 It almost always works...

-
group 1A → +1 ions (except H → H )
group 2A → +2 ions

d-block → +1 to +4 ions

group 6A → -2 ions
group 7A → -1 ions
 notable exceptions

Sn+2, Sn+4
Pb+2, Pb+4
Bi+3, Bi+5
Tl+, Tl+3

and many transition metals

 reason for exceptions
in metals
e.g. Fe forms Fe+2 and Fe+3 ions

Fe: [Ar] 4s2 3d6

Fe+2: [Ar] 3d6 (4s higher in energy!)
Fe+3: [Ar] 3d5
 reason for exceptions
e.g. Phosphorus (group 5A)
[Ne] 3s23p3

expect P to gain 3 electrons

can actually gain 3, 4 or 5!
since 3d orbitals can accept a few
= “expanded octet”
Ionic Bonding
Consider the reaction between sodium and chlorine:
Na(s) + ½Cl2(g) → NaCl(s)
Ionic Bonding
Na(s) + ½Cl2(g) → NaCl(s) ΔH°f = -410.9 kJ

- This reaction is very exothermic

- Sodium loses an electron to become Na+
- Chlorine gains an electron to become Cl−
- Na+ has an Ne electron configuration and Cl− has an Ar
configuration
 example 1

..
. .. ..
.. .. -
Na
. + Cl

..
Na+ + Cl

..
 example 2

.
. .. . .
.. ..
. .
Mg + O

..
Mg+2 + O

..
-2
 example 3

Li
.
+ O
.
. .. 2 Li+ + O
. .
.. .. -2

Li
. .. ..
Ionic Bonding
Energetics of Ionic Bond Formation
Lattice Energy (ΔHlattice) – The energy required to
completely separate one mole of a solid ionic compound
into its gaseous ions.
Lattice energy depends on
-the charge on the ions
-the size of the ions
Coulomb’s equation:

Q1, Q2 = charge on ions

k = 8.99 x 109 J-m/c2
d = distance between ions
 Properties of Ionic Compounds
• Hard and are solid at room temperature
• Form crystal lattices not molecules
• Good insulators
• High melting points/ Boiling Points
• Conduct electricity when dissolved in water or
as a liquid.
• They are brittle and break under stress
• Usually soluble in water
 Covalent Bonding
• A covalent bond is a chemical link between two
atoms in which electrons are shared between
them.

Examples: There is a covalent bond between the

oxygen and each hydrogen in a water molecules
(H2O). Each of the covalent bond contains two
electrons - one from a hydrogen atom and one
from the oxygen atom. Both atoms share the
electrons.
 Covalent bonds
• Nonmetals hold onto their valence electrons.
• They can’t give away electrons to bond.
• Still want noble gas configuration.
1s22s22p63s23p6…eight valence electrons (stable octet)
• Get it by sharing valence electrons with each other.
• By sharing both atoms get to count the electrons
toward noble gas configuration.
 Covalent bonding
• Fluorine has seven valence electrons
• A second atom also has seven
By sharing electrons
…both end with full orbitals

8 Valence
electrons
F F 8 Valence
electrons
 Single Covalent Bond
• A sharing of two valence electrons.
• Only nonmetals and Hydrogen.
• Different from an ionic bond because they
actually form molecules.
• Two specific atoms are joined.
• In an ionic solid you can’t tell which atom the
electrons moved from or to.
 How to show how they formed
• It’s like a jigsaw puzzle.
• I have to tell you what the final formula is.
• You put the pieces together to end up with
the right formula.
• For example- show how water is formed with
covalent bonds.
 Water
Each hydrogen has 1 valence

H electron
Each hydrogen wants 1 more
The oxygen has 6 valence
electrons
The oxygen wants 2 more

O They share to make each other

happy
 Water
• Put the pieces together
• The first hydrogen is happy
• The oxygen still wants one more

H O
 Water
• The second hydrogen attaches
• Every atom has full energy levels
• A pair of electrons is a single bond

HO HO
H H
 Multiple Bonds
• Sometimes atoms share more than one pair of
valence electrons.
• A double bond is when atoms share two pair
(4) of electrons.
• A triple bond is when atoms share three pair
(6) of electrons.
 Carbon dioxide
• CO2 - Carbon is central atom (
I have to tell you)

C • Carbon has 4 valence

electrons
• Wants 4 more
• Oxygen has 6 valence
O electrons
• Wants 2 more
 Carbon dioxide
• Attaching 1 oxygen leaves the oxygen 1 short
and the carbon 3 short

C O
 Carbon dioxide
● Attaching the second oxygen leaves both
oxygen 1 short and the carbon 2 short

OC O
 Carbon dioxide
● The only solution is to share more
● Requires two double bonds
● Each atom gets to count all the atoms in
the bond
8 valence 8 valence
8 valence
electrons electrons
electrons

O C O
 How to draw them
• Add up all the valence electrons.
• Count up the total number of electrons to
make all atoms happy.
• Subtract.
• Divide by 2
• Tells you how many bonds - draw them.
• Fill in the rest of the valence electrons to fill
atoms up.
 Examples
• NH3

N • N - has 5 valence electrons wants

8
• H - has 1 valence electrons wants
2

H • NH3 has 5+3(1) = 8

• NH3 wants 8+3(2) = 14
• (14-8)/2= 3 bonds
• 4 atoms with 3 bonds
 Examples
• Draw in the bonds
• All 8 electrons are accounted for
• Everything is full

H
H NH
 Examples
• HCN C is central atom
• N - has 5 valence electrons wants 8
• C - has 4 valence electrons wants 8
• H - has 1 valence electrons wants 2
• HCN has 5+4+1 = 10
• HCN wants 8+8+2 = 18
• (18-10)/2= 4 bonds
• 3 atoms with 4 bonds -will require multiple bonds
- not to H
 HCN
• Put in single bonds
• Need 2 more bonds
• Must go between C and N

HC N
 HCN
● Put in single bonds
● Need 2 more bonds
● Must go between C and N
● Uses 8 electrons - 2 more to add

HC N
 HCN
● Put in single bonds
● Need 2 more bonds
● Must go between C and N
● Uses 8 electrons - 2 more to add
● Must go on N to fill octet

HC N
 Another way of indicating bonds

• Often use a line to indicate a bond

• Called a structural formula
• Each line is 2 valence electrons

H O H =H O H
 Coordinate Covalent Bond
• When one atom donates both electrons in a
covalent bond.
• Carbon monoxide
• CO

C O
 Coordinate Covalent Bond
● When one atom donates both electrons in
a covalent bond.
● Carbon monoxide
● CO

C O
 Coordinate Covalent Bond
● When one atom donates both electrons in
a covalent bond.
● Carbon monoxide
● CO

C O
Properties of Covalent compounds
• Most covalent compounds have relatively low melting
points and boiling points.
• Covalent compounds usually have lower enthalpies of
fusion and vaporization than ionic compounds.
• Covalent compounds tend to be soft and relatively flexible.
• Covalent compounds tend to be more flammable than ionic
compounds.
• When dissolved in water, covalent compounds don't
conduct electricity.
• Many covalent compounds don't dissolve well in water.
 Covalent Compounds
Ionic Compounds 1.Gases, liquids, or solids (made of
1.Crystalline solids (made of ions) molecules)

2. High melting and boiling points 2.Low melting and boiling points

3. Conduct electricity when melted 3.Poor electrical conductors in all

phases
4. Many soluble in water but not in
nonpolar liquid 4.Many soluble in nonpolar liquids but
not in water
 Polar Covalent Bonds

• When the atoms in a bond are the same, the

electrons are shared equally.
• This is a nonpolar covalent bond.
• When two different atoms are connected, the
atoms may not be shared equally.
• This is a polar covalent bond.
• How do we measure how strong the atoms
pull on electrons?
 Electronegativity
• A measure of how strongly the atoms attract
electrons in a bond.
• The bigger the electronegativity difference the
more polar the bond.
0.0 - 0.5 Covalent nonpolar
0.5 - 1.0 Covalent moderately polar
1.0 - 2.0 Covalent polar
> 2.0 Ionic
 How to show a bond is polar
• Isn’t a whole charge just a partial charge
• δ+ means a partially positive
• δ− means a partially negative

δ+harder onδ−
• The Cl pulls the electrons
H spendClmore time near the Cl
• The electrons
Polar Molecules

Molecules with ends

 Polar Molecules
• Molecules with a positive and a negative end
• Requires two things to be true
● The molecule must contain polar bonds
This can be determined from differences in
electronegativity.
● Symmetry can not cancel out the effects of the polar
bonds.
● Must determine geometry first.
 Is it polar?
HF

H2 O

NH3

CCl4

CO2
 Intermolecular Forces

What holds molecules to each other

 Intermolecular Forces
• Intermolecular forces are interactions that exist between
molecules. Functional groups determine the type and strength of
these interactions. They are what make solid and liquid molecular
compounds possible.
• There are three different types of interactions, shown below in
order of increasing strength:
▪ van der Waals forces ( London forces)
▪ dipole-dipole interactions
▪ hydrogen bonding
• The weakest are called van derWaal’s forces - there are two kinds
• Dispersion forces
• Dipole Interactions
van der Waals Forces

• van der Waals forces are also known as London forces.

• They are weak interactions caused by momentary changes in electron
density in a molecule.
• They are the only attractive forces present in nonpolar compounds.

Even though CH4 has no net

dipole, at any one instant its
electron density may not be
completely symmetrical,
resulting in a temporary dipole.
This can induce a temporary
dipole in another molecule. The
weak interaction of these
temporary dipoles
constitutes van der Waals
forces.
• All compounds exhibit van der Waals forces.
• The surface area of a molecule determines the strength of the van der
Waals interactions between molecules. The larger the surface area, the
larger the attractive force between two molecules, and the stronger the
intermolecular forces.

Surface area and

van der Waals
forces
• van der Waals forces are also affected by polarizability.
• Polarizability is a measure of how the electron cloud around an atom responds
to changes in its electronic environment.

Larger atoms, like iodine,

which have more loosely held
valence electrons, are more
polarizable than smaller atoms
like fluorine, which have more
tightly held electrons. Thus,
two F2 molecules have little
attractive force between them
since the electrons are tightly
held and temporary dipoles
are difficult to induce.
Dipole-Dipole Interactions

• Dipole—dipole interactions are the attractive forces between the

permanent dipoles of two polar molecules.
• Consider acetone (below). The dipoles in adjacent molecules align so that
the partial positive and partial negative charges are in close proximity.
These attractive forces caused by permanent dipoles are much stronger
than weak van der Waals forces.
 Dipole interactions
• Depends on the number of electrons
• More electrons stronger forces
• Bigger molecules more electrons
•Fluorine is a gas
•Bromine is a liquid
•Iodine is a solid
 Dipole interactions
• Occur when polar molecules are attracted to
each other.
• Slightly stronger than dispersion forces.
• Opposites attract but not completely hooked
like in ionic solids.
+ − + −
δ δ δ δ
HF HF
 Dipole Interactions
δ+

δ−

δ
δ−

+
δ+

δ
−
δ−

δ+
+
δ δ
+
δ

δ−
− δ+
δ +
δ δ−
 Hydrogen bonding
• Are the attractive force caused by hydrogen
bonded to F, O, or N.
• F, O, and N are very electronegative so it is a
very strong dipole.
• The hydrogen partially share with the lone
pair in the molecule next to it.
• The strongest of the intermolecular forces.
 Hydrogen Bonding

-
+ δ
δ O +
δ+
δ - H H δ
H O
+
H δ
 Hydrogen bonding

H
O

O
H O H
H

H
H

O
H O

H
H

H
H O
O

H
H
 Hydrogen Bonding
• Hydrogen bonding typically occurs when a hydrogen atom bonded to O, N, or F, is
electrostatically attracted to a lone pair of electrons on an O, N, or F atom in another
molecule.

76
Note: as the polarity of an organic molecule increases, so does the strength of its
intermolecular forces.

77
 Metallic Bonding
The chemical bond characteristic of metals, in which
mobile valence electrons are shared among atoms
in a usually stable crystalline structure.
Metals hold on to their valence electrons very
weakly. Think of them as positive ions (cations)
floating in a sea of electrons.
The combination of two phenomena gives rise to
metallic bonding: delocalization of electrons and the
availability of a far larger number of delocalized
energy states than of delocalized electrons. The
latter could be called electron deficiency.
 Sea of Electrons
• Electrons are free to move through the
solid.
• Metals conduct electricity.
+ + + +
+ + + +
+ + + +