Miles Eckles April 7, 2011

Chem 101 A Chapter 9 (con’t)

Molecular Geometry and Bonding Theories (con’t)

Polarity of Molecules

 A molecule is said to be polar if its centers of negative and positive charge do not

coincide. One end of a polar molecule has a slight positive charge, the other end a slight

negative charge. Molecules that are not polar are called nonpolar.

o It is possible for a molecule to have polar bonds and be nonpolar.

o Treated like vector quantities

δ + δ-
H—F

Dipoles

 Whenever two electrical charges of equal magnitude but opposite sign are separated by

a distance, a dipole is established. The size of a dipole is established by its dipole

moment, denoted μ.

o In any given bond a dipole can be given caused by unequal sharing of electrons

μ = Qr

 Q is the charge magnitude

 r is the distance between charges

 Dipole moment comes from electrostatic strength and distance

  Measured in terms of strength

 This determines if molecule is polar or nonpolar

 Debye – a unit that equals 3..34 x 10-30 Coulomb-meters and is used to express dipole

moments.

o Do not need to memorize ↑

 For polyatomic molecules, we must consider each bond dipole and then the overall net

affect on the dipole of the entire molecule.

Net polarity of polyatomics

No net dipole

O ==C==O

Net dipole
Covalent Bonding and Orbital Overlap

 Valence—bond theory. Visualizes the build-up of electron density between two nuclei

as occurring when a valence atomic orbital of atom merges with a valence atomic orbital

of another atom. The orbitals are then said to share a region of space, or overlap.

Approach of two H atoms to form H2

H . . H

. .
Overlap region

Hybridization

 Hybrid orbitals are a useful way to envision the mixing of s, p, and d orbitals in

polyatomic molecules.

 The process of hybridization leads to hybrid orbitals that are directed along certain

definite directions.

Sp hybrid orbitals p orbital

. .
↓ hybridize
 . .
Two sp hybrid orbitals

 Electrons are “promoted” from s to p orbital then they hybridize to form sp hybrid

orbitals.

 Similar for sp2 and sp3

Hybridization involving d orbitals

 Atoms in the third period and beyond can also use d orbitals to form hybrid orbitals,

e.g., sp3d

To predict hybridization:

1. Draw Lewis Structure

2. Determine electron-pair geometry

3. Specify hybrid orbitals needed based on geometry (Table 9.4)

Hybridization

 Determine the hybridization of each atom in CO and BF3. Start with Lewis Structures.

:C:::O: C – sp

O – sp

F:B:F F – no hybridization
..
F B – sp2
Sigma Bonds (ơ)

 Electron density is concentrated symmetrically about the line connecting the nuclei.
Hybridization in Multiple bonds

 Multiple bonds involve electron overlap off the bonding axis between atoms.

H3 C CH3 H2 C CH2 HC CH

Ethane Ethylene Acetylene

Consider N2

What is the hybridization of N2?

:N≡N:

One sigma (ơ) bond plus two pi (π) bonds.

Pi – bonds (π)

H2 C CH2
Ethylene

C C

1-sigma bond

1-pi bond

Delocalized Bonding

 While many electrons can be said to be localized to specific atoms within molecules, this

description is often inadequate.

 Delocalized bonding in the case of multiple pi bonds in succession (the electrons are not

localized to individual atoms.

General conclusions

1. Every pair of bonded atoms shares one or more pairs of electrons. In every bond at least

one pair of electrons is localized in space between atoms to form ơ bonds.

2. Electrons in ơ bonds are localized in the region between two atoms and do not affect

bonding in any other atoms.

3. When atoms share more than one pair of electrons, the additional electrons are in π

bonds. The charge density of π bond lies above and below bond axis.

4. Molecules with two or more resonance structures have π bonds that extend over more

than two bonded atoms are said to be delocalized.

Molecular Orbitals

 Molecular orbital theory describes the electrons in molecules existing in allowed energy

states called molecular orbitals.

 Bonding molecular orbital – lower energy molecular orbital.

 Antibonding molecular orbital – higher energy molecular orbital.

 Molecula orbitals centered about the internuclear axis are called sigma molecular

orbitals.

 Energy level diagrams or molecular orbital diagrams are a way to represent the

interaction between molecular orbitals.

Bond Order

 Bond Order = ½ (# bonding electrons -- # anti-bonding electrons)

 Examples: For H2,

 Bond order = ½ (2-0) = 1

o For He,
  Bond order = ½ (2-2) = 0

Second Row Diatomics

 Rules for relate to formation of molecular orbitals

1. Number of molecular orbitals formed equals number of atomic orbitals.

2. Atomic orbitals combine most effectively with other atomic orbitals of similar

energy.

3. Effectiveness with which two atomic orbitals combine is proportional to their

overlap with one another.

4. Each molecular orbital can accommodate at most two electrons with their spins

paired.

5. When molecular orbitals have same energy, one electron enters each orbital (Hund’s

rule).

 No molecular orbitals can have more than two electrons

 If there are 2 spins they’re going in opposite directions

Molecular Orbitals for Li2

 Li2

o Inner-shell or “core: electrons do NOT contribute significantly to bonding.

o Add total valence electrons

o Fill into electron configuration

 Electron configuration (molecular)

*
o (ơ2s)2(ơ2s )0

Molecular Orbitals from 2p Atomic Orbitals

 2p orbitals will consist of :

 *
o Ơ2p and ơ2p orbitals along which electron density lies

o Everything else will be in pi (π) molecular orbitals

 Electron Configuration

* * *
(ơ2s)2(ơ2s )( π2p x,y)4(ơ2p z)2(π2p x, y )2(ơ2p z)0+

 2p can be involved in sigma or pi bonds

Magnetism

 Paramagnetism

o Unpaired electrons – oriented by a magnetic field

 Diamagnetism

o No unpaired electrons – slightly repelled by a magnetic field