Chemistry 162

Text: Chemical Principles, 6th Ed. - By Steven Zumdahl

Chapter #14 : Covalent Bonding: Orbitals Chapter #15 : Chemical Kinetics Chapter #16 : Liquids and Solids Chapter #17 : Properties of Solutions Chapters #18: Representative Elements Chapter #19: Transition Metals and Coordination Chemistry

Chapter #14 - Covalent Bonding: Orbitals

14.1) Hybridization and the Localized Electron Model 14.2) The Molecular Orbital Model 14.3) Bonding in Homonuclear Diatomic Molecules 14.4) Bonding in Heteronuclear Diatomic Molecules 14.5) Combining the Localized Electron and Molecular Orbital Models 14.6) Orbitals: Human Inventions 14.7) Molecular Spectroscopy

Hybridization and the Localized Electron Model

Chapter 12: Atomic orbitals, Properties of electrons, Wave functions, Electronic configurations, Aufbau principle, etc. Chapter 13: General Concepts of Bonding in Molecules - Types of bonds: ionic, covalent, etc. - Bond energies, lengths, polarities, etc. Localized Electron Model - Lewis dot structures - Resonance structures - The octet rule - VSEPR model Chapter 14: What types of orbitals are used to form bonds?

Central Themes of Valence Bond Theory (Localized Electron Model)

Basic Principle of Valence Bond Theory: A covalent bond forms when the orbitals from two atoms overlap and a pair of electrons occupies the region between the two nuclei. 1) Maximum overlap. The bond strength depends on the coulombic attraction between the shared electrons and the two nuclei. The greater the orbital overlap, the stronger the bond.

Central Themes of Valence Bond Theory (Localized Electron Model)

Basic Principle of Valence Bond Theory: A covalent bond forms when the orbitals from two atoms overlap and a pair of electrons occupies the region between the two nuclei. 1) Maximum overlap. The bond strength depends on the coulombic attraction between the shared electrons and the two nuclei. The greater the orbital overlap, the stronger the bond. 2) Spins pair. The two electrons in the overlap region occupy the same space and therefore must have opposite spins. (Pauli exclusion principle) 3) Hybridization. To explain experimental observations, Pauling proposed that the valence atomic orbitals in a molecule are different from those in the isolated atoms. We call this Hybridization!

Example: Methane

Lewis dot structure

VSEPR 3D shape

4 equivalent C-H covalent bonds VSEPR predicts a tetrahedral geometry

Recall, the method of generating Lewis dot structures

CH4
1. determine the total # of valence electrons total # valence electrons = 8 2. use pairs of e to connect terminal atoms to central atom, and then distribute the rest as lone pairs H
H H H H C
H C H H

0 e left

Recall, the method of determining 3D structure (VSEPR)

Valence Shell Electron Pair Repulsion (VSEPR): the!3-D geometric structure is determined by minimizing repulsion of electron pairs (both bond pairs and lone pairs).

H H C H H
Lewis Structure VSEPR Structure
9

(VSEPR)

AB2

AB3

AB4, AB3E, AB2E2

(VSEPR)

AB5

AB6

The Valence Orbitals of a Carbon Atom

Carbon: 2s22p2

So, how do we explain the formation of 4 equivalent C-H bonds?

Hybridization: Mixing of Atomic Orbitals to form New Orbitals for Bonding

4 atomic orbitals

4 new hybrid orbitals

Grouped together, the four sp3 hybrid orbitals have a tetrahedral shape

Other Representations of Hybridization:

!1 = 1/2[(2s) + (2px) + (2py) + (2pz)] !2 = 1/2[(2s) + (2px) - (2py) - (2pz)] !3 = 1/2[(2s) - (2px) + (2py) - (2pz)] !4 = 1/2[(2s) - (2px) - (2py) + (2pz)]

Hybridization is related to the number of electron pairs determined from VSEPR:

Methane VSEPR: AB4 tetrahedral sp3 hybridized Ammonia VSEPR: AB3E tetrahedral sp3 hybridized Water VSEPR : AB2E2 tetrahedral sp3 hybridized

Recall NH3 & H2O (chapter 13). Each has one or more lone pairs occupying space and thus repelling the other atoms resulting in a tetrahedral arrangement of electron clouds
VSEPR: AB3E

Ammonia

VSEPR : AB2E2

Water

Problem: Describe the hybridization and bonding of the carbon orbitals in ethylene (C2H4) step 1) Lewis dot structure

c)

b)

d)

H C C H

H H
carbon possesses 3 effective pairs of electrons

Problem: Describe the hybridization and bonding of the carbon orbitals in ethylene (C2H4) VSEPR: AB3 trigonal planar sp2 hybridized orbitals

H C C H

H H

sp2 hybridized orbitals used for # bonding remaining p orbital used for " bonding

The Formation of sp2 Hybrid Orbitals Involves the Combination of an sorbital with a px and pyorbital

three hybrid orbitals

three atomic orbitals

One of the porbitals, the pzorbital remains unhybridized

z

The unhybridized pzorbital will be used to form a !bond

The ! (sigma) bonds in C2H4

A carbon-carbon double bond consists of a ! bond and a " bond

H C C H

H H

# bonding vs " bonding

Read pages 665 of Zumdahl Two modes of bonding are important for 1st and 2nd row elements: # bonding and " bonding These two differ in their relationship to the internuclear axis: # bonds have electron density ON the internuclear axis " bonds have electron density ABOVE AND BELOW the internuclear axis

# bond

" bond

# bond

Bonding in ethylene (C2H4)

Problem: Describe the hybridization and bonding of the carbon orbitals in Carbon Dioxide (CO2) VSEPR: AB2 linear sp hybridized orbitals for # bonding

The ! (sigma) bonds in CO2

Two of the porbitals of CO2 remain unhybridized

The unhybridized orbitals will be used to form two !bonds

Bonding in Carbon Dioxide (CO2)

5- and 6-Coordinate Molecules: e.g. PCl5

VSEPR: AB5 trigonal bipyrimidal sp3d hybridized orbitals Expanded Octet for P (10 valence electrons)

Strategies used in forming Hybrid Orbitals

1. Molecular Formula 2. Lewis Structure 3. VSEPR- shape and arrangement 4. Hybrid orbitals

Summary:
hybrid combination

sp

sp2

sp3

Summary:
hybrid combination

dsp3

d2sp3