CHAPTER 8

Molecular Structure & Covalent Bonding Theories

Chapter Goals

Molecular Shapes and Bonding

Chapter Goals

Stereochemistry
 

Two Simple Theories of Covalent Bonding

Overview of Chapter

Overview of Chapter
electronic molecular

Overview of Chapter
 hybrid orbitals   molecular polarity

VSEPR Theory
  

VSEPR Theory

VSEPR Theory

VSEPR Theory

VSEPR Theory

VSEPR Theory

VSEPR Theory
 

Frequently, we will describe two geometries  for each molecule.  Electronic  geometry is determined by the  Electronic  geometry locations of regions of high electron density  around the central atom(s). Molecular geometry
Electron pairs are not used in the molecular geometry determination just the positions of the atoms in the molecule are used.

VSEPR Theory
 

VSEPR Theory
  

VSEPR Theory
 

VSEPR Theory

 

Polar Molecules: The Influence of Molecular Geometry

A

B A

A

B

linear molecule nonpolar

A angular molecule polar

Polar Molecules: The Influence of Molecular Geometry

or

Valence Bond (VB) Theory
 

overlap
hybridization

Valence Bond (VB) Theory
Regions of High Electron Density 2 3 4 5 6 Electronic Geometry Linear Trigonal planar Tetrahedral Trigonal bipyramidal Octahedral Hybridization

sp sp2 sp3 sp3d sp3d2

Molecular Shapes and Bonding

Linear Electronic Geometry:AB2 Species (No Lone Pairs of Electrons on A)
  

Linear Electronic Geometry:AB2 Species (No Lone Pairs of Electrons on A)
↑↓ ↑↓ ↑↓
Be

↑↓↑↓↑

Linear Electronic Geometry:AB2 Species (No Lone Pairs of Electrons on A)
Cl Be Cl

Cl Be Cl

Linear Electronic Geometry:AB2 Species (No Lone Pairs of Electrons on A)
Cl Be Cl
Cl - Be - Cl Cl - - - Be- - - Cl ← 1. Electronegativities 3.5   5→ 3.5  

2.0 2.0 bond dipoles are symmetric very polar bonds nonpolar molecule

Linear Electronic Geometry:AB2 Species (No Lone Pairs of Electrons on A)
↑↓ ↑↓
⇒ ↑↓↑↑

↑↓ ↑↓ ↑↓ ↑

Linear Electronic Geometry:AB2 Species (No Lone Pairs of Electrons on A)

Trigonal Planar Electronic Geometry: AB3 Species (No Lone Pairs of Electrons on A)
  

Trigonal Planar Electronic Geometry: AB3 Species (No Lone Pairs of Electrons on A)
↑↓ ↑↓ ↑
B

↑↓ ↑↓ ↑↓ ↑

Cl

Trigonal Planar Electronic Geometry: AB3 Species (No Lone Pairs of Electrons on A)
Cl B Cl Cl

B

Trigonal Planar Electronic Geometry: AB3 Species (No Lone Pairs of Electrons on A)
Cl

Cl

B Cl

Cl

Electronegativities 1.5  3.0   Cl
1.5

B

Cl B - Cl

very polar bonds

Trigonal Planar Electronic Geometry: AB3 Species (No Lone Pairs of Electrons on A)
↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑↓ ↑ ⇒ ↑↓ ↑ ↑ ↑

Trigonal Planar Electronic Geometry: AB3 Species (No Lone Pairs of Electrons on A)

Trigonal Planar Electronic Geometry: AB3 Species (No Lone Pairs of Electrons on A)

Tetrahedral Electronic Geometry: AB4 Species (No Lone Pairs of Electrons on A)
  

Tetrahedral Electronic Geometry: AB4 Species (No Lone Pairs of Electrons on A)

↑↓

↑ ↑

Tetrahedral Electronic Geometry: AB4 Species (No Lone Pairs of Electrons on A)

Tetrahedral Electronic Geometry: AB4 Species (No Lone Pairs of Electrons on A)
C - H Electronegativities 2.5  2.1  
0.4

slightly polar bonds

Tetrahedral Electronic Geometry: AB4 Species (No Lone Pairs of Electrons on A)
↑↓ ↑ ↑ ↑ ⇒ ↑ ↑ ↑ ↑

Tetrahedral Electronic Geometry: AB4 Species (No Lone Pairs of Electrons on A)

Tetrahedral Electronic Geometry: AB4 Species (No Lone Pairs of Electrons on A)

Example of Molecules with More Than One Central Atom
Alkanes CnH2n+2

 

Example of Molecules with More Than One Central Atom
Alkanes CnH2n+2

 

Tetrahedral Electronic Geometry: AB3U Species (One Lone Pair of Electrons on A)

polar

Tetrahedral Electronic Geometry: AB3U Species (One Lone Pair of Electrons on A)
↑↓ ↑↓ ↑ ↑ ↑

↑↓ ↑↓ ↑ ↑

Tetrahedral Electronic Geometry: AB3U Species (One Lone Pair of Electrons on A)

Tetrahedral Electronic Geometry: AB3U Species (One Lone Pair of Electrons on A)
N - H Electronegativities 3.0 2.1 
0.9
µ

very polar bonds

N - F Electronegativities 3.0 4.0  
1.0
µ

very polar bonds

Tetrahedral Electronic Geometry: AB3U Species (One Lone Pair of Electrons on A)
↑↓ ↑ ↑ ↑ ⇒ ↑↓ ↑ ↑ ↑

Tetrahedral Electronic Geometry: AB2U2 Species (Two Lone Pairs of Electrons on A)
 

polar

Tetrahedral Electronic Geometry: AB2U2 Species (Two Lone Pairs of Electrons on A)
↑↓ ↑ ↑↓ ↑ ↑

Tetrahedral Electronic Geometry: AB2U2 Species (Two Lone Pairs of Electrons on A)
O - H Electronegativities 3.5  2.1   
1.4

very polar bonds

µ≈

Tetrahedral Electronic Geometry: AB2U2 Species (Two Lone Pairs of Electrons on A)
↑↓ ↑↓ ↑ ↑ ⇒ ↑↓ ↑↓ ↑ ↑

Tetrahedral Electronic Geometry: ABU3 Species (Three Lone Pairs of Electrons on A)
  

nonpolar

Tetrahedral Electronic Geometry: ABU3 Species (Three Lone Pairs of Electrons on A)

Tetrahedral Electronic Geometry: ABU3 Species (Three Lone Pairs of Electrons on A)

Tetrahedral Electronic Geometry: ABU3 Species (Three Lone Pairs of Electrons on A)
↑↓ ↑↓ ↑↓ ↑ ⇒ ↑↓ ↑↓ ↑↓ ↑

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3

 

polar

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3
↑↓ ↑ ↑ ↑

↑↓ ↑↓ ↑↓ ↑

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3
As - F Electronegativities 2.1  4.0   
1.9

very polar bonds

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3
↑↓ ↑ ↑ ↑ ⇓ ↑ ↑ ↑ ↑ ↑ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3
1. 2. 3.

If lone pairs are incorporated into the trigonal  bipyramidal structure, there are three possible  new shapes. 
One lone pair ­ Seesaw shape Two lone pairs ­ T­shape Three lone pairs – linear

The lone pairs occupy equatorial positions  because they are 120o from two bonding pairs  and 90o from the other two bonding pairs.

Results in decreased repulsions compared to lone pair  in axial position.

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3

trigonal bipyramid electronic geometry seesaw shaped molecular geometry polar

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3

trigonal bipyramid electronic geometry T-shaped molecular geometry polar

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3
Molecular  Geometry

 

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3
trigonal bipyramid electronic geometry linear molecular geometry nonpolar

XeF2

Trigonal Bipyramidal Electronic Geometry: AB5, AB4U, AB3U2, and AB2U3

Octahedral Electronic Geometry: AB6, AB5U, and AB4U2
  

octahedralnonpolar
polar

Octahedral Electronic Geometry: AB6, AB5U, and AB4U2

↑↓ ↑↓ ↑ ↑ ↑↓ ↑↓ ↑↓ ↑

Octahedral Electronic Geometry: AB6, AB5U, and AB4U2
Se - F Electronegativities 2.4  4.0  
1.6

very polar bonds

Octahedral Electronic Geometry: AB6, AB5U, and AB4U2

↑↓ ↑↓ ↑ ↑ ⇓

__ __ __ __ __

↑ ↑ ↑ ↑ ↑ ↑ __ __ __ __

Octahedral Electronic Geometry: AB6, AB5U, and AB4U2

If lone pairs are incorporated into the octahedral  structure, there are two possible new shapes. 
1. One lone pair ­ square pyramidal 2. Two lone pairs ­ square planar

The lone pairs occupy axial positions because  they are 90o from four bonding pairs.
– Results in decreased repulsions compared to lone  pairs in equatorial positions.

Octahedral Electronic Geometry: AB6, AB5U, and AB4U2

octahedral electronic geometry Square pyramidal molecular geometry polar

Octahedral Electronic Geometry: AB6, AB5U, and AB4U2

Octahedral Electronic Geometry: AB6, AB5U, and AB4U2

octahedral electronic geometry square planar molecular geometry nonpolar

Octahedral Electronic Geometry: AB6, AB5U, and AB4U2

Compounds Containing Double Bonds

Compounds Containing Double Bonds

Compounds Containing Double Bonds

Compounds Containing Double Bonds

H C H C

H

H

Compounds Containing Double Bonds

↑↓ ↑ ↑ ⇒

↑↑↑

Compounds Containing Double Bonds

Compounds Containing Double Bonds

Compounds Containing Double Bonds

Compounds Containing Double Bonds

σ

Compounds Containing Double Bonds

π

Compounds Containing Double Bonds

σπ

Compounds Containing Triple Bonds

Compounds Containing Triple Bonds

Compounds Containing Triple Bonds

↑↓ ↑ ↑ ⇒ ↑ ↑

↑↑

Compounds Containing Triple Bonds
σ

Compounds Containing Triple Bonds

π

σπ

Compounds Containing Triple Bonds

Summary of Electronic & Molecular Geometries

Synthesis Question

Synthesis Question

Group Question

End of Chapter 8
 

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