Lecture 22: Lewis Dot Structures

Reading: Zumdahl 13.9-13.12 Outline

Lewis Dot Structure Basics Resonance Those annoying exceptions

Localized Bond Models

Consider our energy diagram for H2 bonding:

Localized Model Limitations

It is important to keep in mind that the models we are discussing are just that..models. We are operating under the assumption that when forming bonds, atoms share electrons using atomic orbitals. Electrons involved in bonding: bonding pairs. Electrons not involved in bonding: lone pairs.

Lewis Dot Structures (cont.)

Developed by G. N. Lewis to serve as a way to describe bonding in polyatomic systems. Central idea: the most stable arrangement of electrons is one in which all atoms have a noble gas configuration. Example: NaCl versus Na+ClNa: [Ne]3s1 Na+: [Ne] Cl: [Ne]3s23p5 Cl-: [Ne]3s23p6 = [Ar]

LDS Mechanics
F
Lone Pair (6 x)

Atoms are represented by atomic symbols surrounded by valence electrons. Electron pairs between atoms indicate bond formation.

F
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).

LDS Mechanics (cont.)

An example: Cl2O

Cl

Cl

20 e-

Cl O Cl
Cl O Cl

16 e- left

LDS Mechanics (cont.)

An example: CH4

H H

H H
H H C H H
Done!

8 e-

0 e- left

LDS Mechanics (cont.)

An example: CO2
O O C

16 e12 e- left

O C O
Octet Violation CO double bond

O C O
O C O

0 e- left

LDS Mechanics (cont.)

An example: NO+
+ +

10 e-

N O
+

8 e- left

Resonance Structures
We have assumed up to this point that there is one correct Lewis structure. There are systems for which more than one Lewis structure is possible:
Different atomic linkages: Structural Isomers Same atomic linkages, different bonding: Resonance

Resonance Structures (cont.)

The classic example: O3.
O O O

O O

O
Both structures are correct!

Resonance Structures (cont.)

In this example, O3 has two resonance structures:
O O O

Conceptually, we think of the bonding being an average of these two structures. Electrons are delocalized between the oxygens such that on average the bond strength is equivalent to 1.5 O-O bonds.

Structural Isomers
What if different sets of atomic linkages can be used to construct correct LDSs:
Cl O Cl Cl O Cl Cl Cl O Cl Cl O

Both are correct, but which is more correct?

Formal Charge
Formal Charge: Compare the nuclear charge (+Z) to the number of electrons (dividing bonding electron pairs by 2). Difference is known as the formal charge.

Cl O Cl
#eZ+ Formal C. 7 7 0 6 6 0 7 7 0

Cl Cl O
7 6 7 7 7 6 0 +1 -1

Structure with less F. C. is more correct.

Formal Charge
Example: CO2
O
eZ+ FC 6 6 0

C
4 4 0

O
6 6 0

O
6 6

O C
4 6 6 4 -2

O
7 6

O C
4 6 5 4

0 +2

-1 +2 -1

More Correct

Beyond the Octet Rule

There are numerous exceptions to the octet rule. Well deal with three classes of violation here:
Sub-octet systems Valence shell expansion Odd-electron systems

Beyond the Octet Rule (cont.)

Some atoms (Be and B in particular) undergo bonding, but will form stable molecules that do not fulfill the octet rule.
F F B F F F B F

Experiments demonstrate that the B-F bond strength is consistent with single bonds only.

Beyond the Octet Rule (cont.)

For third-row elements (Period 3), the energetic proximity of the d orbitals allows for the participation of these orbitals in bonding. When this occurs, more than 8 electrons can surround a third-row element. Example: ClF3 (a 28 e- system)
F F Cl F
F obey octet rule Cl has 10e-

Beyond the Octet Rule (cont.)

Finally, one can encounter odd electron systems where full pairs will not exist. Example: Chlorine Dioxide.

O Cl O

Unpaired electron

Summary
Remember the following:
C, N, O, and F almost always obey the octet rule. B and Be are often sub-octet Second row (Period 2) elements never exceed the octet rule Third Row elements and beyond can use valence shell expansion to exceed the octet rule.

In the end, you have to practice..a lot!