Organic Chemistry, 6th Edition

L. G. Wade, Jr.

Chapter 2
Structure and Properties
of Organic Molecules
 Wave Properties of Electrons
Electrons exhibit properties of both
waves and particles.
Wave function, (x, y, z, t) is a
mathematical description of the state of
the system (size, shape, orientation).
Amplitude may be positive or negative.
Node: amplitude is zero.
||2 : Probability density

Chapter 2 2
 Wave Functions

||2

Chapter 2 3
 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 4
 Bonding Region
Electrons are close to both nuclei.

Chapter 2 5
 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 6
 Bonding
Molecular Orbital
Two hydrogens, 1s constructive overlap

=>

Chapter 2 7
 Anti-Bonding
Molecular Orbital
Two hydrogens, destructive overlap.

=>

Chapter 2 8
H2: s-s overlap

=>
Chapter 2 9
 Cl2: p-p overlap
Constructive overlap along the same
axis forms a sigma bond.

=>

Chapter 2 10
HCl: s-p overlap

Chapter 2 11
 Pi Bonding
Pi bonds form after sigma bonds.
Sideways overlap of parallel p orbitals.

Chapter 2 12
 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 13
 Molecular Shapes
Bond angles cannot be explained with simple
s and p orbitals.
Use VSEPR theory: the bonds and the lone
pairs on a central atom are separated by the
largest possible angles.
Hybridization: a formalism to explain bonding
geometries in molecules.
Hybridization is LCAO within one atom, just
prior to bonding.

Chapter 2 14
 sp Hybrid Orbitals

2 VSEPR pairs
Linear electron
pair geometry
180 bond angle

Chapter 2 15
 sp2 Hybrid Orbitals
3 VSEPR pairs
Trigonal planar e- pair geometry
120 bond angle

Chapter 2 16
 sp3 Hybrid Orbitals
4 VSEPR pairs
Tetrahedral e- pair geometry
109.5 bond angle

Chapter 2 17
 Molecular Geometry Rules

Sigma bonding electrons and lone pairs

occupy hybrid orbitals.
Use the geometry that gives the widest
possible separation.
For multiple bonds, form a sigma bond
first using hybrid orbitals. Then, form pi
bonds using remaining p orbitals.

Chapter 2 18
 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 O _
CH3-CC-CHO CH3 C CH2

Why bond angle in water is 104.5?

Chapter 2 19
 Rotation around Bonds
Single bonds freely rotate.

Double bonds cannot rotate unless the

bond is broken.

Chapter 2 20
 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 21
 Structural Isomers

CH3 O CH3 and CH3 CH2 OH

CH3
and
CH3

Draw isomers of pentane, C5H12

Chapter 2 22
 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 23
 Bond Dipole Moments
are due to differences in electronegativity.
depend on the amount of charge and
distance of separation.
In debyes,
= 4.8 x (electron charge) x d(angstroms)

Chapter 2 24
 Molecular Dipole Moments
Depend on bond polarity and bond angles.
Vector sum of the bond dipole moments.

Chapter 2 25
 Effect of Lone Pairs
Lone pairs of electrons contribute to the
dipole moment.

Problem: Why (NH3) > (NF3)?

Chapter 2 26
 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 27
 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 28
Dipole-Dipole

=>
Chapter 2 29
 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 30
Dispersions

Chapter 2 31
 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 32
Hydrogen Bonds

Chapter 2 33
 Boiling Points and
Intermolecular Forces
CH3 CH2 OH CH3 O CH3
ethanol, b.p. = 78C dimethyl ether, b.p. = -25C
H3C N CH3 CH3CH2 N CH3 CH3CH2CH2 N H
CH3 H H
trimethylamine, b.p. 3.5C ethylmethylamine, b.p. 37C propylamine, b.p. 49C

CH3 CH2 OH CH3 CH2 NH2

ethanol, b.p. = 78 C ethyl amine, b.p. = 17 C
Chapter 2 34
 Solubility
Like dissolves like.
Polar solutes dissolve in polar solvents.
Nonpolar solutes dissolve in nonpolar
solvents.
Molecules with similar intermolecular
forces will mix freely.
Water is a very special molecule!

Chapter 2 35
 Thermodynamics of Mixing

Gm = Hm TSm
where Hm = Ha-b Ha Hb

Hm depends on interaction energy between a and b

Sm is typically favorable (randomness is better!)

Chapter 2 36
 Ionic Solute in Polar Solvent

Hydration releases energy (Hm<0).

Entropy increases (Sm>0).
Chapter 2 37
Ionic Solute in Nonpolar Solvent

Interactions between solvent and solute are

very unfavorable, Hm>> 0
Chapter 2 38
 Nonpolar Solute in
Nonpolar Solvent

Intermolecular interactions are weak (Hm~ 0).

Entropy increases (Sm>0).
Chapter 2 39
 Nonpolar Solute in Water

Enthalpy of mixing can be positive or negative

(e.g. pentane-water Hm < 0).
Entropy decreases (Sm > 0)! Why?
Chapter 2 40
 Hydrophobic Effect
Conformation entropy of water molecules
decreases when they are in contact with a
hydrophobic (nonpolar) surface.
Liquid water: av. 2 H-bonds per molecule, 6
possible configurations in a tetrahedral lattice.
When near a hydrophobic surface, only 3
possible configurations.
The reason for immiscibility of hydrophobic
solutes with water is entropy, not enthalpy!

Chapter 2 41
 Classes of Compounds
Classification based on functional group.
Three broad classes
Hydrocarbons
Compounds containing oxygen
Compounds containing nitrogen.

=>

Chapter 2 42
 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 43
Compounds Containing
Oxygen
Alcohol: R-OH
Ether: R-O-R'
O
Aldehyde: RCHO
CH3CH2 C H
O
Ketone: RCOR'
CH3 C CH3

=>
Chapter 2 44
 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 O C H3
2

=>
Chapter 2 45
Compounds Containing
Nitrogen
Amines: RNH2, RNHR', or R3N
Amides: RCONH2, RCONHR, RCONR2
Nitrile: RCN
O
CH3 C N

N CH3

=>
Chapter 2 46