Chem 5

Chapter 11
Chemical Bonding I:
Basic Concepts
Part 1
November 13, 2002

New Concepts
The octet rule
Ionic bond
Covalent bond
Electronegativity
Dipole moment
Molecular shapes - VESPR
Bond order
Bond length
Bond energy

MODELS OF CHEMICAL BONDING

The octet rule is the simplest model of bonding.

Atoms combine to form compounds in an attempt

to obtain a stable noble gas electron configuration
with an octet of electrons in the valence shell.
A stable electronic configuration can be attained
in two ways
ELECTRON TRANSFER
ELECTRON SHARING

IONIC BONDING
COVALENT BONDING

Gilbert Newton Lewis (1875 1946)

Born in Massachusetts, in 1875, Lewis earned his B.S. in
Chemistry in 1896 and his Ph.D. in 1899 at Harvard University.
Here he worked with Professor T. W. Richard, the first
American Nobel Prize winner in Chemistry.
From 1900 to 1901, he studied in Germany under Walther
Nernst and Wilhelm Ostwald. He taught briefly at Harvard. In
1905, he was appointed as a Professor of Chemistry and
Physics at M.I.T.

Chemical Achievers, 2000, The

Chemical Heritage Foundation.

In 1912, he accepted the Chairmanship of the Department of Chemistry at U.C.

Berkeley. He turned it into one of the leading programs in the nation. He
remained at its head until his death in 1946.
Lewis research was wide-ranging. He confirmed the Third Law of
Thermodynamics; introduced the Lewis dot symbol to valence theory;
produced heavy water, invaluable to later research in atomic energy; worked
with isotopes; and studied photochemistry, coining the term photon. Though
he mentored 20 Nobel Prize recipients, and was nominated 30 times, he never
received the honor himself.

IONIC BONDING
electron transfer
The formation of ionic bonds is represented in terms
of Lewis symbols

Na

Cl

Na+
1s22s22p6

Cl
1s22s22p63s23p6

The loss or gain of electrons (dots) until

both species have reached an octet of electrons.
Columbic attraction between the positive and
negative ions pull the ions together.

E=0

Na+(g) + Cl(g) + e-

Ionization
Energy of Na

Electron
Affinity of Cl
Na+(g) + Cl-(g)

Na(g) + Cl(g)

Formation of ionic
crystal
NaCl(s)

Columbic attraction between the positive and

negative ions pull the ions together.
Ionic solids typically
have high melting
and boiling points
and form electrolyte
solutions if they
dissolve in water.

COVALENT BONDING
electron sharing
Atoms complete their octets by sharing electron pairs.
The shared electrons between the two nuclei pull the
nuclei together.

F 1s22s22p5 +

F 1s22s22p5

F
bonding
pair of
electrons

or

non-bonding, or
lone pair of
electrons

IONIC OR COVALENT?

HF
+

This is a polar covalent bond.

Bonds are usually neither completely ionic nor covalent,
but somewhere in between...
The type of bond that forms depends on the
electronegativity difference between the two
atoms involved in the bond

ELECTRONEGATIVITY
is the tendency of an atom in a bond to attract shared
electrons to itself
Electronegativity increases
F is the highest.

Fr is the
lowest.

Same trend as I.E. and E.A.

Distinction between electron affinity and electronegativity?

IONIC vs COVALENT BONDS

Compounds composed of elements with a small difference in electronegativity
tend to have significant covalent character in their bonding:

A and B have equal share.

A

Compounds composed of elements with a large difference in electronegativity

tend to have significant ionic character in their bonding:

B has a greater share.

A

Variation of bond character with electronegativity

between the two atoms

Dipole Moment
A pair of opposite charges separated by a distance

+
d
H

+
direction
Dipole moment, = d

Unit: Debye, 3.34x10-30 coulomb meter

more polar

Polar Molecules in an electric field

Randomly Oriented

Oriented

How does a microwave oven work?

By an alternating field at a microwave frequency.

LEWIS BONDING MODEL

Lewis structures are based on a
localized electron model
Electrons are always localized in one of two ways:
As lone pairs on a specific atom
OR
As bonding pairs between two specific atoms

Building Lewis Structures of Molecules

HCN as an example...
Step 1. Count the total number of VALENCE electrons
C has 4

N has 5

H has 1

Total of 10

Step 2. Place one e- pair between each BONDED atom

H

We have 6 e- left

Step 3. Add electrons to terminal atoms first

To get an octet or duet (for H).

Building Lewis Structures of Molecules

Add 6 electrons in pairs to give the N an octet.
H

Step 4. Add any electrons left over to central atom

We have none left!
Step 5. Check for an acceptable Lewis Structure
Do all atoms have an octet?
H

No! The carbon and nitrogen have to share

more than one pair of electrons.

Building Lewis Structures of Molecules

H

Still no octet on C

Do it again!
H

N
a triple bond

LEWIS STRUCTURE OF HCN

Also written

Another Example: H2CO

Formaldehyde

Total number of valence electrons = 1+1+4+6=12

H

H
C

Give C an octet

H
a double bond...

H
12 used
not yet octet on C
We can write this.

H
C
H

Shapes of Molecules
Valence-Shell Electron-pair Repulsion (VSEPR)
- works well for octets and 2nd and 3rd period elements, but not for transition metal

Step 1. Draw the Lewis dot structure of the molecule

Step 2. Assign a number of electron groups to the structure
= # of bonded atoms + # of lone pairs

Regardless of single, double, triple bonds

Step 3. Consider that electron pairs repel each other. Electron

pairs assume orientations about an atom to minimize repulsions.
Step 4. Remember that the lone pairs are fat.

2 electron groups
Hydrogen Cyanide

N
Linear molecule

CO2

..

..

Net = 0
Linear molecule

3 electron groups

Formaldehyde

H
O

C
H

Trigonal-planar

4 electron groups

Water

.. ..
O

H
H

Tetrahedral

H2O is a planar molecule.

NH3

There are four electron

groups around the
nitrogen atom.

The shape of NH3 is trigonal pyramidal.

Cl
Carbon Tetrachloride CCl4
Cl

Cl- C- Cl
Cl
Net =0

109.5
C

Cl

Cl
Cl

Widely used organic solvent

Carcinogenic
Environmental pollutant

Tetrahedral

CCl2F2

Freon - Chlorofluocarbon
Cl

Quasi-Tetrahedral
> 109.5

nonzero
but small

C
Cl
Chemically inert, low boiling point

F
F < 109.5

First introduced by General Electric

Used as coolant for refrigerators and cars, much better than ammonia
500 kTon/year production in 1987
Lifetime in atmosphere 122 yr.
Responsible for ozone reduction

BOND LENGTHS AND ENERGRY

Bond Lengths...

rtriple bond < rdouble bond < rsingle bond

The strength of a bond is measured by...

Bond Energy (BE).

BEtriple bond > BEdouble bond > BEsingle bond
H = H (bond breakage) + H (bond formation)
~ BE (reactants) - BE (products)

Comparison between Single, Double and Triple Bonds

Molecule
Formula

C-C Bond
Order

C-C Bond
Length

C-C Bond
Energy

145 pm

347kJ/mol

134 pm

611 kJ/mol

120 pm

837 kJ/mol

EXPLOSIVES
Demo:

Highly exothermic
Gas products
No O2 required

.. ..
..
..
6 N=N (g) + 12 O=C=O
..
.. (g)
..
.. ..
+ 10 H-O-H
(g) + O=O (g)
..
.. ..
Nitroglycerin
Liquid

Alfred Nobel discovered dynamite

- nitroglycerin explosive made more
stable when absorbed by cellulose.

Products have many double

and triple bonds with high
bond energies.