Functional Groups

(Gugus Fungsi)

Tutorial VIII

S Rusdi

Dept of Chemical Engineering

The Islamic University of Indonesia

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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Functional Groups:
A functional group is an atom or a group of atoms
with characteristic chemical & physical properties.
An atom or group of atoms that influences the way
the molecule functions, reacts or behaves.
The center of reactivity in an organic compound
It is the reactive part of a molecule.

Functioal Groups consists of:

Hydrocarbons (CH).
Heteroatoms (AX)
Carbonyl groups(=C=O)
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 Functional Groups:

Hydrocarbons Heteroatom Carbonyl

* Alkane * Alkyl Halide * Aldehyde

* Alkene * Alcohol * Keton

* Alkyne * Ether * Carbocyclic Acid

* Aromatic * Amine * Ester
* Thiol * Amide

* Sulfide * Acid Chloride

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Functional Groups: Hydrocarbons
Hydrocarbons are compounds made up of only the elements C
and H. They may be aliphatic or aromatic.

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Functional Groups: Hydrocarbons
Hydrocarbons are compounds made up of only the elements C
and H.
They may be aliphatic or aromatic.

Ethane: This molecule has only CC and CH bonds, so it has no

functional group, no polar bonds, no lone pairs, and no bonds, so
it has no reactive sites. It is very unreactive (STABLE)
Dont think that the CC and CH bonds are unimportant. They
form the carbon backbone or skeleton to which the functional
group is attached.
Bonds are easily broken in chemical reactions. A bond
makes a molecule a base and a nucleophile.

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Catergorization of Hydrocarbons (CH)
Hydrocarbon

Alifatic Alicyclic Aromatic

Saturated Unsaturated Saturated Unsaturated

Alkanes

Alkenes Alkynes Cycloalkanes Cycloalkenes

Functional Groups: Heteroatoms

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Functional Groups:
Heteroatoms and bonds confer reactivity on a particular
molecule.
Heteroatoms have lone pairs and create electron-
deficient sites on carbon (kurang elektron).
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 functional group is attached. 8
Note !!
Electron deficiency occurs when a compound has too few valence electrons for the
connections between atoms to be described as covalent bonds.

The term electron-deficient is also used in a more general way in organic chemistry, to
indicate a -system such as an alkene or arene that has electron-withdrawing groups
attached, as found in nitrobenzene or acrylonitrile.

Instead of showing the nucleated character common with simple C=C bonds, electron-
deficient -systems may be electrophilic and susceptible to nucleophilic attack, as is
seen in the Michael addition or in nucleophilic aromatic substitution.

Electron deficiency can also be used to describe molecules with highly polarized bonds
(due to highly electronegative ligands) such as boron trifluoride or silicon tetrafluoride
where the valence shell is not fully occupied and as such can act as Lewis acids.

As the most extreme form of highly localize electron deficiency one can consider the
metallic bond.

A carbon skeleton is the chain, branch and/or ring of carbon atoms that form the basis of
the structure of an organic molecule.

Lweis :Nucleophilicity= electron richness (base),

Electrophilicity= electron poorness (acid) 9
Functional Groups:

Ethane: This molecule has only CC and CH bonds, so it has

no functional group, no polar bonds, no lone pairs, and no
bonds, so it has no reactive sites. It is very unreactive (STABLE)
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.

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Functional Groups:

Aromatic hydrocarbons are so named because many of the

earliest known aromatic compounds had strong characteristic
odors( AROMA).
The simplest aromatic hydrocarbon is benzene. The six-
membered ring + three bonds of benzene comprise a single
functional group.
When a benzene ring is bonded to another group, it is called a
phenyl group.

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Functional Groups:

Examples of Molecules Containing C-Z Bonds

(where Z is a heteroatom).

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Functional Groups: Carbonyl groups

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Functional Groups:

Compounds Containing the C=O Group:

This group is called a carbonyl group.
The polar C=O bond makes the carbonyl carbon an
electrophile, while the lone pairs on O(Oxygen) 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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Functional Groups:

Molecules Containing the C=O Functional Group

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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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Influence of Functional Groups
on Reactivity:

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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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Influence of Functional Groups on Reactivity:

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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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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 (Nu).

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Functional Groups
&
Its Intermolecular Forces

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
22
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 inter-
actions. These ionic inter-actions are
much stronger than the
intermolecular forces present
between covalent molecules.
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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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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. 25
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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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. 27
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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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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Intermolecular Forces: Summary

Note: as the polarity of an organic molecule increases,

so does the strength of its intermolecular forces.

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Functional Groups
&
Its Physical Properties:
Boiling Point
Melting Point
Solubility

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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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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. 33
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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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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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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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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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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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
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and the solvent.
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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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. 41
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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Physical Properties: Solubility

Since butane and acetone are both organic compounds having a C

C 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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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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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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