Chem 5

Chapter 11

Chemical Bonding I:
Basic Concepts

Part 2

November 18, 2002

We covered the following concepts last time:

Lewis structure - the octet rule

Ionic bond and covalent bond
Polar bond, electronegativity and dipole moment
Molecular shapes - VSEPR
Bond length and bond energy
4 (g) 6 N≡ N (g) + 12 O=C=O (g)

+ 10 H-O-H (g) + O=O (g)

∆H = ∆H (bond breakage) + ∆H (bond formation)

= ΣBE (reactants) - ΣBE (products)
= 4x(5xBEC-H +2BEC-C +3BEC-O+6BEN-O +3BEN=O)
- (6xBEN=N+24xBEC=O+20xBEO-H+BEO=O)
 To predict molecular shape with VSEPR

An example of a polyatomic molecule with no single

central atom:

ETHANOL CH3CH2OH

Apply VSEPR to each atom with more than

one electron pair.
H H

H C C O H

H H
ETHANOL C2H5OH

O H
H

The atoms around the carbons form a

C
tetrahedral arrangement.

C The atoms around the oxygen form a

H V-shaped structure.
H
H
 The shape matters!

Ethanol Dehydrogenase
Ethanol
An enzyme that catalyzes the hydrolysis
of ethanol. O
CH3CH2OH Æ CH3C-H

A close look at the active site

The structure of ethanol

dehydrogenase
 New concepts today

Formal charge
Resonance
Exceptions to the octet rule

Ozone destruction and polymers

Two possible Lewis structures for HCN

H C N Why not H N C

Two possible Lewis structures for formaldehyde

Why not
H H
C O O C
H H
 FORMAL CHARGE
gives an indication of the extent to which atoms
have gained or lost electrons in the process of covalent
bond formation.
Each atom is assigned all of its lone electrons and
half of the bonding electrons.
_
Formal #valence _
charge = electrons { #unshared
electrons
} { 1/2#shared
electrons }
Structures with the lowest formal charges are the most
stable.
 All possible Lewis structures with stable
electronic configurations for HCN and HNC.

H C N
_
Formal #valence _
charge = electrons { #unshared
electrons
} { 1/2#shared
electrons }
Calculate formal charge for H C N

..
FC on C =4 -0 - 8/2 =0
FC on N =5 -2 - 6/2 =0
FC on H =1 -0 - 2/2 =0
 All possible Lewis structures with stable
electronic configurations for HNC.

H N C
_
Formal #valence _
charge = electrons { #unshared
electrons
} { 1/2#shared
electrons }
Calculate formal charge for H N C

..
FC on C =4 -2 - 6/2 = -1
FC on N =5 -0 - 8/2 = +1
FC on H =1 -0 - 2/2 =0
 Four Rules for Formal Charge

• The sum of F.C. must be the net charge of the

molecule or ion.
• F.C. should be as small as possible.
• Negative F.C. usually occurs on the most
electronegative atoms.
• F.C. of the same sign on adjacent atoms is unlikely.
 All possible Lewis structures with stable
electronic configurations for HCN and HNC.

H C N H N C
0 0 0 0 +1 -1
FORMAL CHARGES
We choose the structure based on
F.C. of each atom being zero
The most electronegative atom (N) should not have
positive F.C.
It should be
H C N
 Another Example:

H2CO vs. H2OC

H H
C O O C
H H
FC on C =4 – 0 – 2x2/2 – 4/2 = 0 FC on O = 6 – 0 – 2x2/2 –4/2 = 2

FC on O = 6 – 4 – 4/2 = 0 FC on C = 4 – 4 – 4/2 = - 2

Not stable!
 Let’s look at the carbonate anion CO32-

Count up valence electrons

C has four 1s22s22p2

O has six 1s22s22p4

Plus two extra for negative charge

Valence electrons = 4 + 3 x 6 + 2 = 24
Carbonate anion CO32-
Put a pair between each atom
24
O
valence
electrons
O C O

18 left

Add remaining electrons to terminal atoms to

complete octets...
Carbonate anion CO3 2-
2-
24 DO NOT
O
valence FORGET
electrons CHARGE!!!!
O C O

The oxygen atoms have their octet but...

The carbon atom does not!

So we form a double bond by sharing a pair

from one of the oxygen atoms...
Carbonate ion CO3 2-

2-

24
O
valence
electrons
O C O

Form a double bond by sharing a pair from

one of the oxygen atoms...
2- -
2
O O

O O O C O
C
But…
 FORM A DOUBLE BOND BETWEEN O AND C
2-
Here is one
O

O C O
Here is another! Here is another!
2- 2-

O O

O C O O C O

All three are perfect! But, none alone is correct!

 Because experiment shows all three bonds are
the same.

All three bond lengths the same!

2
Longer than double bonds, O

Shorter than single bonds C

O O
And bond angles 120°
 RESONANCE
We use a double headed arrow between the
structures..
2 2 2
O O O

C C C
O O O O O O

The electrons involved are said to be

DELOCALIZED over the structure.
The blended structure is a RESONANCE HYBRID
We interpret the experimental structure with a partial
double bond. The bond order is (2+2x1)/3 =1.33.
 Another example of resonance structure:

O3 LEWIS STRUCTURE O
Make double bond... O O

O O
O O O O

Experiment shows that both O-O bonds are equivalent.

The O3 molecule is a hybrid of the two resonance forms.

Ozone is generated by Ozone absorption spectrum
photochemistry in the
stratosphere (15-60 Km),
forming a protective layer
for all life on earth.

hν
O2 (g) → 2 O (g)

O2 (g) + O (g) → O3 (g)

• O3 absorbs UV light 220-300 nm

• N2 and O2 do not absorb at those wavelengths
• O3 layer protects DNA from photodamage
Ozone Reduction
The ozone destruction is related to human activity!
hν
chloroflorocarbon (CFC) → Cl

Cl + O3 = ClO + O2

ClO + O = Cl + O2

O3 + O = 2 O2
The Heroes
The billion-dollar CFC industry and
some government agencies attacked
them viciously, even tried to get them
fired from their professor posts.
However, the scientific community
provided moral support and
overwhelming experimental evidence.
The truth prevailed! Rowland and
Molina were awarded the Nobel Prize
Sherwood Rowland Mario Molina in 1995.
 International Ban on CFC

CFC is replaced by fluorocarbon.

The ozone level is expected to recover
in 50 years.
Professor Jim Anderson
The flying Chem Lab
to teach Chem7
EXCEPTIONS TO THE OCTET RULE…

• Molecules with more than an octet around

the central atom

• Molecules with less than an octet around the

central atom

• Molecules with unpaired electrons

A CENTRAL ATOM WITH MORE THAN AN OCTET

Elements in the third or higher periods can exceed

the octet due to d or f orbitals

F
EXAMPLE : PF5 F F
P
F F
 Five electron pairs
PF5 around the
P phosphorus atom.

AXIAL
Bond angle F
900
F
F P
F
1200
EQUATORIAL F

The shape of PF5 is trigonal bipyramidal.

Other examples based on 5 pairs of electrons…
All with empty d orbitals
SF4 ClF3 XeF2

1 lone pair 2 lone pairs 3 lone pairs

F F F

F
S Cl Xe
F F F
F F F

See-saw T-shaped Linear

shaped
Lone pairs occupy the trigonal plane (the “equator”)
first to minimize the number of 90° repulsions
Another Example I3-
I I I
Number of valence electrons: 7+7+7+1=22
Add electrons... 4 used in two bonds

I
-
I I I I
F
I
trigonal bipyramidal
Linear shape with three lone pairs
in the equator
 Draw the Lewis structure for SF6

Total number of valence electrons = 6 + 6 x 7 = 48

Why? F has seven 1s22s22p5
S has six 1s22s22p63s22p4

Place S in middle of 6 fluorine atoms

F
F F
There are six electron pairs
S
around the sulfur atom.
F F
F
Shape of SF6

All bond angles 900

F

F F
S
F F

6 electron pairs octahedral

A CENTRAL ATOM WITH LESS THAN AN OCTET
..
.. F ..

B ..
.. .
.. F F.
.. ..
.. ..
.. F .. .. F ..
F.C. with two with two
-1 +
B ..
resonance B ..
resonance
.. structures .. _
. F ..
structures
.. F F .. .. F . ..
.. +1 F.C.
..
Not stable Ionic
 FREE RADICALS
Have unpaired electrons.

NO2 Is a free radical

Total number of valence electrons=5+6+6=17

O N O

Form double bond to get N close to octet

O N O O N O

RESONANCE
 Summary
Formal Charge:
apparent charges on certain atoms in a Lewis structure that arise
when atoms have not contributed equal numbers of electrons to
the covalent bonds joining them
- Four rules to select Lewis structures based on F.C.

Resonance Structure:
More than one plausible Lewis structure can be written for a
species. The true structure is a resonance hybrid of two or more
contributing structures.

Exceptions to the Octet Rule

At times, a molecule may have unpaired electrons or the valence
shell of the central atom must be expanded to 10 (trigonal
bipyramidal) or 12 electrons (octahedral).