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 IONIC BONDING

ELECTRON SHARING 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 Chemical Achievers, © 2000, The

Physics at M.I.T. 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+ Cl
1s22s22p6 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.
 Na+(g) + Cl(g) + e-
E=0

Electron
Ionization Affinity of Cl
Energy of Na
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 + F F F F F
or
non-bonding, or
bonding lone pair of
pair of electrons
electrons
 IONIC OR COVALENT?
HF
+

H + F H F

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 B
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 B
Variation of bond character with electronegativity

between the two atoms

 Dipole Moment
A pair of opposite charges separated by a distance

d
H + F H F
δ+ δ–
direction
Dipole moment, µ = δd µ, more polar
Unit: Debye, 3.34x10-30 coulomb • meter
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 C N 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 C N

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 C N

No! The carbon and nitrogen have to share

more than one pair of electrons.
 Building Lewis Structures of Molecules

H C N

H C N
Still no octet on C Do it again!

H C N
a triple bond…

LEWIS STRUCTURE OF HCN

Also written H C N
Another Example: H2CO Formaldehyde

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

H H
C O Give C an octet C O
12 used H H
not yet octet on C a double bond...

We can write this…. H

C O

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

H C N

µ Linear molecule

CO2
.. ..
O C O

Net µ = 0
Linear molecule
3 electron groups Formaldehyde

H
C O

H
µ

Trigonal-planar
4 electron groups Water

.. ..
O
O H H H

H
µ

Tetrahedral H2O is a planar molecule.

NH3 H N H There are four electron
H groups around the
nitrogen atom.

N
H
H
µ
H

The shape of NH3 is trigonal pyramidal.

 Cl
Carbon Tetrachloride CCl4 Cl- C- Cl
Cl
Cl
109.5° Net µ =0

C Tetrahedral
Cl
Cl
Cl

Widely used organic solvent

Carcinogenic
Environmental pollutant
 CCl2F2 Freon - Chlorofluocarbon

Cl
Quasi-Tetrahedral
> 109.5° µ nonzero
but small
C
F
Cl
F < 109.5°
Chemically inert, low boiling point
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)

~ ΣBE (reactants) - ΣBE (products)
Comparison between Single, Double and Triple Bonds

Molecule C-C Bond C-C Bond C-C Bond

Formula Order Length Energy

1 145 pm 347kJ/mol

2 134 pm 611 kJ/mol

3 120 pm 837 kJ/mol

 EXPLOSIVES • Highly exothermic

Demo: • Gas products

• No O2 required

4 .. .. .. ..
6 N=N (g) + 12 O=C=O
.. .. (g)
.. .. ..
+ 10 H-O-H
.. (g) + O=O (g)
.. ..
Nitroglycerin Products have many double
and triple bonds with high
Liquid
bond energies.
Alfred Nobel discovered “dynamite”
- nitroglycerin explosive made more
stable when absorbed by cellulose.