Organic Chemistry

Chapter 2
Structure and Properties
of Organic Molecules
 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
between different atoms is bond formation
on the same atom is hybridization.
• Conservation of orbitals
• Waves that are in phase add together.
Amplitude increases.
• Waves that are out of phase cancel out.
=>
Chapter 2 3
 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 4
H2: s-s overlap

=>
Chapter 2 5
 Cl2: p-p overlap
Constructive overlap along the same
axis forms a sigma bond.

=>

Chapter 2 6
 HCl: s-p overlap
Question:
Draw the predicted shape for
the bonding molecular orbital and
the antibonding molecular orbital
of the HCl molecule.

Answer: See bottom of page 42 in your text.

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Chapter 2 7
 Pi Bonding
• Pi bonds form after sigma bonds.
• Sideways overlap of parallel p orbitals.

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Chapter 2 8
 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 9
 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 10
 sp Hybrid Orbitals

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

=>
Chapter 2 11
 sp2 Hybrid Orbitals
• 3 VSEPR pairs
• Trigonal planar e- pair geometry
• 120° bond angle

=>
Chapter 2 12
 sp3 Hybrid Orbitals
• 4 VSEPR pairs
• Tetrahedral e- pair geometry
• 109.5° bond angle

=>
Chapter 2 13
 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 14
Rotation around Bonds
• Single bonds freely rotate.
• Double bonds cannot rotate unless the
bond is broken.

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Chapter 2 15
 Isomerism
• Molecules which have the same
molecular formula, but differ in the
arrangement of their atoms, are called
isomers.
• Constitutional (or structural) isomers
differ in their bonding sequence.
• Stereoisomers differ only in the
arrangement of the atoms in space. =>

Chapter 2 16
 Structural Isomers

CH3 O CH3 and CH3 CH2 OH

CH3
and
CH3

=>
Chapter 2 17
 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 => 18
 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 => 19
Molecular Dipole Moments
• Depend on bond polarity and bond angles.
• Vector sum of the bond dipole moments.
• Lone pairs of electrons contribute to the
dipole moment.

=>
Chapter 2 20
 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 21
 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 22
Dipole-Dipole

=>
Chapter 2 23
 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. CH 3
CH3
H3C C CH3
CH3 CH2 CH2 CH2 CH3 CH3 CH CH2 CH3
n-pentane, b.p. = 36°C isopentane, b.p. = 28°C CH3
neopentane, b.p. = 10°C

Chapter 2 24 =>
Dispersions

=>

Chapter 2 25
 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 26
H Bonds

=>
Chapter 2 27
 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 28
 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 29
Ionic Solute with
Polar Solvent

Hydration releases energy.

Entropy increases. =>
Chapter 2 30
Ionic Solute with
Nonpolar Solvent

=>
Chapter 2 31
Nonpolar Solute with
Nonpolar Solvent

=>
Chapter 2 32
 Nonpolar Solute
with Polar Solvent

=>
Chapter 2 33
 Classes of Compounds
• Classification based on functional group
• Three broad classes
Hydrocarbons
Compounds containing oxygen
Compounds containing nitrogen

=>

Chapter 2 34
 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 35
Compounds Containing
Oxygen
• Alcohol: R-OH
• Ether: R-O-R'
O
• Aldehyde: RCHO
CH3CH2 C H
O
• Ketone: RCOR'
CH3 C CH3

=>
Chapter 2 36
 Carboxylic Acids
and Their Derivatives
O
• Carboxylic Acid: RCOOH C OH
• Acid Chloride: RCOCl
• Ester: RCOOR' O

• Amide: RCONH2 C Cl

O O
C NH C OCH3
2

=>
Chapter 2 37
Compounds Containing
Nitrogen
• Amines: RNH2, RNHR', or R3N
• Amides: RCONH2, RCONHR, RCONR2
• Nitrile: RCN
O
CH3 C N

N CH3

=>
Chapter 2 38
End of Chapter 2

Chapter 2 39