Organic Chemistry, 6th Edition

L. G. Wade, Jr.

Chapter 2
Structure and Properties
of Organic Molecules

Jo Blackburn
Richland College, Dallas, TX
Dallas County Community College District
2006,Prentice Hall
 Wave Properties
of Electrons
• Standing wave vibrates in fixed location.
• Wave function, , mathematical
description of size, shape, orientation.
• Amplitude may be positive or negative.
• Node: amplitude is zero.

Chapter 2
=>
2
 Wave Interactions
• Linear combination of atomic orbitals
on different atoms produce molecular
orbitals
on the same atom give hybrid orbitals.
• Conservation of orbitals.
• Waves that are in phase add together.
Amplitude increases.
• Waves that are out of phase cancel out.
=>
Chapter 2 3
 Bonding Region
• Electrons are close to both nuclei.

=>
Chapter 2 4
 Sigma Bonding
• Electron density lies between the nuclei.
• A bond may be formed by s-s, p-p, s-p,
or hybridized orbital overlaps.
• The bonding MO is lower in energy than
the original atomic orbitals.
• The antibonding MO is higher in energy
than the atomic orbitals.
=>
Chapter 2 5
 Bonding
Molecular Orbital
Two hydrogens, 1s constructive overlap

=>

Chapter 2 6
 Anti-Bonding
Molecular Orbital
Two hydrogens, destructive overlap.

=>

Chapter 2 7
H2: s-s overlap

=>
Chapter 2 8
 Cl2: p-p overlap
Constructive overlap along the same
axis forms a sigma bond.

=>

Chapter 2 9
 HCl: s-p overlap

Question: What is the predicted shape for

the bonding MO and the antibonding MO
of the HCl molecule?

=>
Chapter 2 10
 Pi Bonding
• Pi bonds form after sigma bonds.
• Sideways overlap of parallel p orbitals.

=>
Chapter 2 11
 Multiple Bonds
• A double bond (2 pairs of shared electrons)
consists of a sigma bond and a pi bond.
• A triple bond (3 pairs of shared electrons)
consists of a sigma bond and two pi bonds.

=>
Chapter 2 12
 Molecular Shapes
• Bond angles cannot be explained with simple
s and p orbitals. Use VSEPR theory.
• Hybridized orbitals are lower in energy
because electron pairs are farther apart.
• Hybridization is LCAO within one atom, just
prior to bonding.
=>

Chapter 2 13
 sp Hybrid Orbitals

• 2 VSEPR pairs
• Linear electron
pair geometry
• 180° bond angle

Chapter 2
=>
14
 sp2 Hybrid Orbitals
• 3 VSEPR pairs
• Trigonal planar e- pair geometry
• 120° bond angle

=>
Chapter 2 15
 sp3 Hybrid Orbitals
• 4 VSEPR pairs
• Tetrahedral e- pair geometry
• 109.5° bond angle

=>
Chapter 2 16
 Sample Problems
• Predict the hybridization, geometry,
and bond angle for each atom in the
following molecules:
• Caution! You must start with a good
Lewis structure!
• NH2NH2
• CH3-CC-CHO
O _
CH3 C CH2 =>
Chapter 2 17
Rotation around Bonds
• Single bonds freely rotate.

• Double bonds cannot rotate unless the

bond is broken.

Chapter 2
=>
18
 Isomerism
• Same molecular formula, but different
arrangement of atoms: isomers.
• Constitutional (or structural) isomers
differ in their bonding sequence.
• Stereoisomers differ only in the
arrangement of the atoms in space. =>

Chapter 2 19
 Structural Isomers

CH3 O CH3 and CH3 CH2 OH

CH3
and
CH3

=>
Chapter 2 20
 Stereoisomers
Br Br Br CH3
C C and C C
H3C CH3 H3C Br

Cis - same side Trans - across

Cis-trans isomers are also called geometric isomers.

There must be two different groups on the sp2 carbon.
H H
C C
H3C No cis-trans isomers possible
H
Chapter 2 => 21
 Bond Dipole Moments
• are due to differences in electronegativity.
• depend on the amount of charge and
distance of separation.
• In debyes,
x (electron charge) x d(angstroms)

=>
Chapter 2 22
Molecular Dipole Moments
• Depend on bond polarity and bond angles.
• Vector sum of the bond dipole moments.

Chapter 2
=>
23
 Effect of Lone Pairs
Lone pairs of electrons contribute to the
dipole moment.

=>
Chapter 2 24
 Intermolecular Forces
• Strength of attractions between
molecules influence m.p., b.p., and
solubility, esp. for solids and liquids.
• Classification depends on structure.
Dipole-dipole interactions
London dispersions
Hydrogen bonding
=>
Chapter 2 25
 Dipole-Dipole Forces
• Between polar molecules.
• Positive end of one molecule aligns with
negative end of another molecule.
• Lower energy than repulsions, so net force
is attractive.
• Larger dipoles cause higher boiling points
and higher heats of vaporization.
=>
Chapter 2 26
Dipole-Dipole

=>
Chapter 2 27
 London Dispersions
• Between nonpolar molecules
• Temporary dipole-dipole interactions
• Larger atoms are more polarizable.
• Branching lowers b.p. because of
decreased surface contact between
molecules.

Chapter 2 28 =>
Dispersions

=>

Chapter 2 29
 Hydrogen Bonding
• Strong dipole-dipole attraction.
• Organic molecule must have N-H or O-H.
• The hydrogen from one molecule is
strongly attracted to a lone pair of
electrons on the other molecule.
• O-H more polar than N-H, so stronger
hydrogen bonding. =>
Chapter 2 30
H Bonds

=>
Chapter 2 31
 Boiling Points and
Intermolecular Forces
CH3 CH2 OH CH3 O CH3
ethanol, b.p. = 78°C dimethyl ether, b.p. = -25°C
H3C N CH3 CH3CH2 N CH3 CH3CH2CH2 N H
CH3 H H
trimethylamine, b.p. 3.5°C ethylmethylamine, b.p. 37°C propylamine, b.p. 49°C

CH3 CH2 OH CH3 CH2 NH2

ethanol, b.p. = 78° C ethyl amine, b.p. = 17 ° C
Chapter 2 32
 Solubility
• Like dissolves like.
• Polar solutes dissolve in polar solvents.
• Nonpolar solutes dissolve in nonpolar
solvents.
• Molecules with similar intermolecular
forces will mix freely.
=>

Chapter 2 33
Ionic Solute with
Polar Solvent

Hydration releases energy.

Entropy increases. =>
Chapter 2 34
Ionic Solute with
Nonpolar Solvent

=>
Chapter 2 35
Nonpolar Solute with
Nonpolar Solvent

=>
Chapter 2 36
Nonpolar Solute
with Polar Solvent

=>
Chapter 2 37
 Classes of Compounds
• Classification based on functional group.
• Three broad classes
Hydrocarbons
Compounds containing oxygen
Compounds containing nitrogen.

=>

Chapter 2 38
 Hydrocarbons
• Alkane: single bonds, sp3 carbons
• Cycloalkane: carbons form a ring
• Alkene: double bond, sp2 carbons
• Cycloalkene: double bond in ring
• Alkyne: triple bond, sp carbons
• Aromatic: contains a benzene ring
=>
Chapter 2 39
Compounds Containing
Oxygen
• Alcohol: R-OH
• Ether: R-O-R'
O
• Aldehyde: RCHO
CH3CH2 C H
O
• Ketone: RCOR' CH3 C CH3

=>
Chapter 2 40
 Carboxylic Acids
and Their Derivatives
O
• Carboxylic Acid: RCOOH C OH
• Acid Chloride: RCOCl
• Ester: RCOOR' O
C
• Amide: RCONH2 Cl

O O
C NH C OCH3
2

=>
Chapter 2 41
Compounds Containing
Nitrogen
• Amines: RNH2, RNHR', or R3N
• Amides: RCONH2, RCONHR, RCONR2
• Nitrile: RCN
O
CH 3 C N

N CH3

=>
Chapter 2 42
End of Chapter 2

Chapter 2 43