Chapter 2

Functional Groups &

properties

Organic Molecules and Functional Groups

Functional Groups:
A functional group is an atom or a group of atoms
with characteristic chemical and physical properties.
It is the reactive part of a molecule.
Organic compounds having only CC and CH
bonds are called Hydrocarbons. There are four
classes of hydrocarbons: alkanes, alkenes, akynes
and aromatics. Alkanes are saturated structures and
the others contain unsaturations.
Many organic molecules contain Heteroatoms, these
are atoms other than carbon or hydrogen.

Organic Molecules and Functional Groups

Functional Groups:

Hydrocarbons

Hydrocarbons are compounds made up of only the elements

carbon and hydrogen. They may be aliphatic or aromatic.

Organic Molecules and Functional Groups

Functional Groups:

Heteroatoms

Functional Groups:

Carbonyl groups

Organic Molecules and Functional Groups

Functional Groups:

Heteroatoms and bonds confer reactivity on a particular

molecule.
Heteroatoms have lone pairs and create electrondeficient sites on carbon.
Bonds are easily broken in chemical reactions. A
bond makes a molecule a base and a nucleophile.

Dont think that the CC and CH bonds are unimportant.

They form the carbon backbone or skeleton to which the
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functional group is attached.

Organic Molecules and Functional Groups

Functional Groups:
Ethane: This molecule has only CC and CH bonds, so it has
no functional group. It has no polar bonds, no lone pairs, and
no bonds, so it has no reactive sites. It is very unreactive.
Ethanol: This molecule has an OH group attached to its
backbone. It is called a hydroxy functional group. Ethanol has
lone pairs and polar bonds that make it reactive with a variety
of reagents.
The hydroxy group makes the properties of ethanol very
different from the properties of ethane.

Organic Molecules and Functional Groups

Functional Groups:
Aromatic hydrocarbons are so named because many of the
earliest known aromatic compounds had strong characteristic
odors.
The simplest aromatic hydrocarbon is benzene. The sixmembered ring and three bonds of benzene comprise a
single functional group.
When a benzene ring is bonded to another group, it is called a
phenyl group.

Organic Molecules and Functional Groups

Functional Groups:
Examples of Molecules Containing C-Z Bonds
(where Z is a heteroatom).

Organic Molecules and Functional Groups

Functional Groups:
Compounds Containing the C=O Group:
This group is called a carbonyl group.
The polar CO bond makes the carbonyl carbon an
electrophile, while the lone pairs on O allow it to react
as a nucleophile and base.
The carbonyl group also contains a bond that is
more easily broken than a CO bond.

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Organic Molecules and Functional Groups

Functional Groups:
Molecules Containing the C=O Functional Group

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Organic Molecules and Functional Groups

Functional Groups:
It should be noted that the importance of a functional
group cannot be overstated.
A functional group determines all of the following
properties of a molecule:
Bonding and shape
Chemical reactivity
Type and strength of intermolecular forces
Physical properties
Nomenclature
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Organic Molecules and Functional Groups

Intermolecular Forces:
Intermolecular forces are interactions that exist
between molecules. Functional groups determine the
type and strength of these interactions.
There are several types of intermolecular interactions.
Ionic compounds contain
oppositely charged particles
held together by extremely
strong electrostatic interactions. These ionic interactions are much stronger
than the intermolecular forces
present between covalent
molecules.

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Organic Molecules and Functional Groups

Intermolecular Forces:
Covalent compounds are composed of discrete
molecules.
The nature of the forces between molecules depends
on the functional group present. There are three
different types of interactions, shown below in order
of increasing strength:
van der Waals forces (London forces)
dipole-dipole interactions
hydrogen bonding
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Organic Molecules and Functional Groups

Intermolecular Forces: van der Waals Forces
van der Waals forces are also known as London forces.
They are weak interactions caused by momentary changes in
electron density in a molecule.
They are the only attractive forces present in nonpolar
compounds.
Even though CH4 has no
net dipole, at any one
instant its electron density
may not be completely
symmetrical, resulting in a
temporary dipole. This can
induce a temporary dipole
in another molecule. The
weak interactions of this
type constitutes van der
Waals forces.

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Organic Molecules and Functional Groups

Intermolecular Forces: van der Waals Forces
All compounds exhibit van der Waals forces.
The surface area of a molecule determines the strength of the
van der Waals interactions between molecules. The larger the
surface area, the larger the attractive force between two
molecules, and the stronger the intermolecular forces.
Figure 3.1 Surface area and van der Waals forces

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Organic Molecules and Functional Groups

Intermolecular Forces: van der Waals Forces
van der Waals forces are also affected by polarizability.
Polarizability is a measure of how the electron cloud around an
atom responds to changes in its electronic environment.
Larger atoms, like iodine,
which have more loosely
held valence electrons,
are more polarizable than
smaller atoms like
fluorine, which have more
tightly held electrons.
Thus, two F2 molecules
have little attractive force
between them since the
electrons are tightly held
and temporary dipoles
are difficult to induce.

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Organic Molecules and Functional Groups

Intermolecular Forces: Dipole-Dipole Interactions
Dipoledipole interactions are the attractive forces between
the permanent dipoles of two polar molecules.
Consider acetone (below). The dipoles in adjacent molecules
align so that the partial positive and partial negative charges
are in close proximity. These attractive forces caused by
permanent dipoles are much stronger than weak van der Waals
forces.

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Organic Molecules and Functional Groups

Intermolecular Forces: Hydrogen Bonding
Hydrogen bonding typically occurs when a hydrogen
atom bonded to O, N, or F, is electrostatically attracted
to a lone pair of electrons on an O, N, or F atom in
another molecule.

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Organic Molecules and Functional Groups

Intermolecular Forces: Summary
Note: as the polarity of an organic molecule increases,
so does the strength of its intermolecular forces.

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Organic Molecules and Functional Groups

Physical Properties: Boiling Point
The boiling point of a compound is the temperature at
which liquid molecules are converted into gas.
In boiling, energy is needed to overcome the attractive
forces in the more ordered liquid state.
The stronger the intermolecular forces, the higher the
boiling point. For compounds with approximately the
same molecular weight:

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Organic Molecules and Functional Groups

Physical Properties: Boiling Point
Consider the example below. Note that the relative
strength of the intermolecular forces increases from
pentane to butanal to 1-butanol. The boiling points of
these compounds increase in the same order.

For two compounds with similar functional groups:

The larger the surface area, the higher the boiling point.
The more polarizable the atoms, the higher the boiling
point.
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Organic Molecules and Functional Groups

Physical Properties: Boiling Point
Liquids having different boiling points can be separated in
the laboratory using a distillation apparatus, shown below.

Figure 3.3 Schematic

of
a distillation apparatus
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Organic Molecules and Functional Groups

Physical Properties: Melting Point
The melting point is the temperature at which a solid
is converted to its liquid phase.
In melting, energy is needed to overcome the
attractive forces in the more ordered crystalline solid.
The stronger the intermolecular forces, the higher the
melting point.
Given the same functional group, the more
symmetrical the compound, the higher the melting
point.
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Organic Molecules and Functional Groups

Physical Properties: Melting Point
Because ionic compounds are held together by
extremely strong interactions, they have very high
melting points.
With covalent molecules, the melting point depends
upon the identity of the functional group. For
compounds of approximately the same molecular
weight:

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Organic Molecules and Functional Groups

Physical Properties: Melting Point
The trend in melting points of pentane, butanal, and
1-butanol parallels the trend observed in their boiling
points.

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Organic Molecules and Functional Groups

Physical Properties: Melting Point
Symmetry also plays a role in determining the melting
points of compounds having the same functional group
and similar molecular weights, but very different shapes.
A compact symmetrical molecule like neopentane packs
well into a crystalline lattice whereas isopentane, which
has a CH3 group dangling from a four-carbon chain, does
not. Thus, neopentane has a much higher melting point.

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Organic Molecules and Functional Groups

Physical Properties: Solubility
Solubility is the extent to which a compound, called a
solute, dissolves in a liquid, called a solvent.
In dissolving a
compound, the
energy needed to
break up the
interactions
between the
molecules or ions
of the solute comes
from new
interactions
between the solute
and the solvent.

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Organic Molecules and Functional Groups

Physical Properties: Solubility
To dissolve an ionic compound, the strong ion-ion
interactions must be replaced by many weaker ion-dipole
interactions.
Figure 3.4
Dissolving a ionic
compound in H2O

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Organic Molecules and Functional Groups

Physical Properties: Solubility
Compounds dissolve in solvents having similar kinds
of intermolecular forces. Like dissolves like.
Polar compounds dissolve in polar solvents. Nonpolar
or weakly polar compounds dissolve in nonpolar or
weakly polar solvents.
Water and organic solvents are two different kinds of
solvents. Water is very polar and is capable of
hydrogen bonding with a solute. Many organic
solvents are either nonpolar, like carbon tetrachloride
(CCl4) and hexane [CH3(CH2)4CH3], or weakly polar, like
diethyl ether (CH3CH2OCH2CH3).
Most ionic compounds are soluble in water, but
insoluble in organic solvents.

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Organic Molecules and Functional Groups

Physical Properties: Solubility
An organic compound is water soluble only if it contains
one polar functional group capable of hydrogen bonding
with the solvent for every five C atoms it contains. For
example, compare the solubility of butane and acetone in
H2O and CCl4.

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Organic Molecules and Functional Groups

Physical Properties: Solubility
Since butane and acetone are both organic compounds
having a CC and CH backbone, they are soluble in
the organic solvent CCl4. Butane, which is nonpolar, is
insoluble in H2O. Acetone is soluble in H2O because it
contains only three C atoms and its O atom can
hydrogen bond with an H atom of H2O.

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Organic Molecules and Functional Groups

Physical Properties: Solubility
The size of an organic molecule with a polar functional
group determines its water solubility. A low molecular
weight alcohol like ethanol is water soluble since it has a
small carbon skeleton of five C atoms, compared to the
size of its polar OH group. Cholesterol has 27 carbon
atoms and only one OH group. Its carbon skeleton is too
large for the OH group to solubilize by hydrogen
bonding, so cholesterol is insoluble in water.

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Organic Molecules and Functional Groups

Physical Properties: Solubility
The nonpolar part of a molecule that is not attracted to
H2O is said to be hydrophobic.
The polar part of a molecule that can hydrogen bond to
H2O is said to be hydrophilic.
In cholesterol, for example, the hydroxy group is
hydrophilic, whereas the carbon skeleton is
hydrophobic.
Figure 3.5
Solubility
summary

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Organic Molecules and Functional Groups

Influence of Functional Groups on Reactivity:
Recall that:
Functional groups create reactive sites in molecules.
Electron-rich sites react with electron poor sites.
All functional groups contain a heteroatom, a bond
or both, and these features create electron-deficient
(or electrophilic) sites and electron-rich (or
nucleophilic) sites in a molecule. Molecules react at
these sites.

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Organic Molecules and Functional Groups

Influence of Functional Groups on Reactivity:

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Organic Molecules and Functional Groups

Influence of Functional Groups on Reactivity:
An electron-deficient carbon (electrophilic) reacts
with a nucleophile, symbolized as :Nu.
An electron-rich carbon (nucleophilic) reacts with an
electrophile, symbolized as E+.
Example 1: alkenes contain an electron rich double
bond, and so they react with electrophiles E+.

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Organic Molecules and Functional Groups

Influence of Functional Groups on Reactivity:
Example 2: alkyl halides possess an electrophilic
carbon atom due to the electron withdrawing effect of
the halogen atom, so they react with electron-rich
nucleophiles.

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