Chapter 2 Structure

and Properties of
Organic Molecules
CHM 2210 Organic
Chemistry Broward
Community College
Assistant Professor Joseph
Lawry, Instructor
2003 All rights reserved. Use of this

Constructive interaction of two 1s orbitals results in

a bonding molecular orbital represented by the
bonding MO at the bottom right. Polarity (+ with +)
must match for this bonding interaction to occur.

When the polarity of the two 1s orbitals does not

match, an antibonding molecular orbital results. A
* antibonding orbital has a node directly between
the two nucleii, in contrast to a region of high edensity seen in the bonding

The bonding interaction exhibits a high e- density region

between the two nucleii resulting in a stable covalent bond. The
e-s here are close enough to the nucleii to lower the overall
energy and also mask the charges of the nucleii, decreasing the
natural electrostatic repulsion, so they dont push away from
each other as much, again, stabilizing the molecule

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
=>

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. (constructive

interference)

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.

=>

H2: s-s overlap: LCAO

forms Molecular
Orbital

=>

Cl2: p-p overlap forms a

type bond
Constructive overlap along the same
axis forms a sigma bond.

=>

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

=>

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.

=>

Molecular Shapes

Bond angles cannot be explained with simple s

and p orbitals (just the use of s and p gives ~90o)
Use VSEPR theory --> e-s repel to largest
seperable angle in 3-space
Hybridized orbitals (addition and subtraction of
orbitals on the same atom) are lower in energy
because electron pairs are farther apart in 3space.
Hybridization is LCAO within one atom, just prior
to bonding.

VSEPR- valence shell electron pair repulsion theory,

which states e-s around a central atom will repel
each other to the largest angle of separation in 3Dimensional space, accounts for the bond angles for
sp3, sp2 and sp1 hybrids

sp Hybrid Orbitals

2 VSEPR pairs
Linear electron
pair geometry
180 bond
angle

=>

sp2 Hybrid Orbitals

3 VSEPR pairs
Trigonal planar e- pair geometry
120 bond angle

=>

sp3 Hybrid Orbitals

4 VSEPR pairs
Tetrahedral e- pair geometry
109.5 bond angle

=>

Methane, the simplest alkane, shows the geometry

of the sp3 hybridization as pointing all four
hydrogen ligands to the corners of a regular
tetrahedron, bond angles 109.5o.

The wedge dashed-line representation

allows us to show a 3-D molecule in a 2-D
page or screen. Ball and stick
representations and space filling models
show 3D bond angles and ionic radius.

General rules of
hybridization and
geometry: sp2 (& sp)

1. # of hybrid orbitals = # bonds + # lone pr.s

2. geometry is driven by VSEPR- widest
separation in 3-D space possible
3. Triple bond = one + two bonds; The two
bonds lie in orthagonal planes

Triple bonds of an sp hybridized

ethyne lie in orthagonal planes

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-CC-CHO
O
CH3

_
CH2

=>

Rotation around
Bonds

Single bonds freely rotate.

Double bonds cannot rotate unless
the bond is broken.

=>

Ethane is composed of two methyl groups

appended to each other; these groups
rotate with respect to each other through
the higher energy eclipsed and lower
energy staggered

Isomers are compounds with the

same molecular formula,
different arrangement of atoms
in space
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.
=>

Constitutional isomers have the same molecular

formula, but a different sequence of connection.
The butane and pentane series illustrate how
compounds with the same formula can have
differing shapes and physical properties

Structural Isomers
CH3

O CH3
CH3

and

and

CH3

CH2

OH

CH3

=>

Stereoisomers
Br

Br
C

H3C

CH3

Cis - same side

and

Br
C
H3C

CH3
Br

Trans - across

Cis-trans isomers are also called geometric isomers.

There must be two different groups on the sp2 carbon.
H
H3C

H
C

C
H

No cis-trans isomers possible

=>

Stereoisomers differ only in how

their atoms are oriented in
space

Z or cis-2-butene and E or trans-2-butene have the same

connection sequence of bonds, so theyre not constitutional
isomers. They are stereoisomers because they differ only in
the spatial orientation of the groups attached to the double
bond. The cis isomer has the two methyl groups on the
same side of the double bond; the trans shows methyls on
opposite sides of the double bond. Again, different physical
properties is observed for stereoisomers: (cis & trans 1,2difluoroethene b.p.s)

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)

=>

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.

=>

Intermolecular Forces
Strength of attractions between
molecules influence m.p., b.p., and
solubility; especially for solids and
liquids.
Classification depends on structure.
Hydrogen bonding

Dipole-dipole interactions
London dispersion forces

covalent bonds have a

dipole, , measured in
Debyes
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.

Dipole-Dipole

=>

London Dispersion Forces

aka Van Der Waals Forces
Between nonpolar molecules
Temporary dipole-dipole
interactions
Larger atoms are more polarizable.
Branching lowers b.p. because of
decreased surface contact CH
CH
H C C CH
molecules.
CH between
CH
CH
CH
CH
CH CH CH CH
3

n-pentane, b.p. = 36C

isopentane, b.p. = 28C

CH3

neopentane, b.p. = 10C

=>

London Dispersion Forces

or Van Der Waals Forces

=>

Hydrogen Bonding: a
particularly strong dipole-dipole
interaction
Just below covalent in strength
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

Hydrogen Bonds; a
particularly strong dipoledipole interaction

=>

Boiling Points and

Intermolecular Forces
CH3

CH2

ethanol, b.p. = 78C

H3C N CH3

O CH3

dimethyl ether, b.p. = -25C

CH3CH2

CH3CH2CH2

N CH3

N H

H
ethylmethylamine, b.p. 37C propylamine, b.p. 49C
H

CH3
trimethylamine, b.p. 3.5C

CH3

CH3

OH

CH2

OH

ethanol, b.p. = 78C

CH3

CH2

NH2

ethyl amine, b.p. 17C

=>

Three Isomers of Pentane; same

molecular formula, different 3-D
structure = different properties

Can you rationalize the difference in boiling point on

the basis that the more stackable the higher the
boiling point? Yes. Since Van Der Waals or London
Forces drop off as a function of: F = 1/r6 k, where r is
distance between molecules. Closer = stronger IMF

Polarity Effects on solubility:

like dissolves like
Polar solutes dissolve in polar
solvents.
Nonpolar solutes dissolve in
nonpolar solvents.
Molecules with similar
intermolecular forces will mix freely.

Ionic Solute with

Polar Solvent

Hydration releases energy.

Entropy increases.

=>

Ionic Solute with

Nonpolar Solvent

=>

Nonpolar Solute with

Nonpolar Solvent

=>

Nonpolar Solute
with Polar Solvent

=>

Classes of Compounds:
Functional Groups
Classification based on
functional group
Three broad classes

Hydrocarbons
Compounds containing oxygen
Compounds containing nitrogen

Hydrocarbons contain carbon

and hydrogen, combust to give
CO2, H2O
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

Correspondence of prefixes and

numbers of carbons atoms

methyl CH3- when used as a substituent

ethyl CH3CH2- again, as a branch-point

propyl CH3CH2CH2-a 3 carbon chain branch

butane CH3CH2CH2CH2- ..4 C branchs are rare

isobutane (CH3)3CH- a cross-shaped branch

Alkyl groups are named like the

alkanes they are derived from

An alkyl group can be thought of as a

substituent or branch-point named from
the parent hydrocarbon + yl. For
example, below is an ethyl-substituted
cyclohexane or ethylcyclohexane

Alkenes are hydrocarbons that

contain at least one double bond

Alkenes come in cis (z)* or trans (E). Cis geometric

isomers show both substituents either on the
topside or on the bottom side of the double
bond. Trans shows one top, one bottom. * Z =
zuzamen Ger. on the same side ; E = Entgagen Ger.
across from

Compounds
Containing Oxygen
Alcohol: R-OH
Ether: R-O-R'
Aldehyde: RCHO
CH CH

Ketone: RCOR'

O
C H

O
CH3

C CH3

=>

alcohols: miscible in water in all proportions up to ~four carbons

hydrophobic tail exceeds OHs
hydrogen bonding

Carboxylic Acids
and Their Derivatives
Carboxylic Acid: RCOOH
Acid Chloride: RCOCl
Ester: RCOOR'
Amide: RCONH2

O
C OH
O
C

C NH
2

Cl

OCH3

=>

Compounds
Containing Nitrogen

Amines: RNH2, RNHR', or R3N

Amides: RCONH2, RCONHR,

RCONR2

O
Nitrile:
RCN

CH3

C N

N CH3

=>

End of Chapter 2