ALCOHOL
BOILING POINTS AND WATER SOLUBILITIES
In alcohols, the hydroxyl group, -OH, is
covalently held by a saturated carbon atom, a carbon
atom from which only single bond extend. Only when
present in this form is the OH group called the alcohol
group.
Alcohols with one OH per molecule as the sole
functional group are called simple alcohol or
monohydric alcohol. Dihydric alcohol, sometimes called
glycols have two OH groups. A trihydric alcohol is one
whose molecules have three alcohol groups.
Alcohols are classified as primary, secondary or
tertiary depending on the number of carbon atoms
bonded to the carbon atom that bears the hydroxyl
group. A primary alcohol is an alcohol in which the
hydroxyl-bearing carbon atom is bonded to only one
other carbon atom. A secondary alcohol is an alcohol in
which the hydroxyl-bearing carbon atom is bonded to
two other carbon atoms. A tertiary alcohol is an alcohol
in which the hydroxyl-bearing carbon atom is bonded to
three other carbon atoms.
NOMENCLATURE
1. Name the longest carbon chain to which the hydroxyl
group is attached. The chain name is obtained by
dropping the final –e from the alkane and adding the
suffix –ol.
2. Number the chain starting from the end nearest the
hydroxyl group, and use the appropriate number to
indicate the position of the –OH group. (In numbering
the longest carbon chain, the hydroxyl group has
priority over double and triple bonds, as well as over
alkyl, cycloalkyl, and halogen substituents.)
3. Name and locate any other substituents present.
4. In alcohols where the –OH group is attached to a
carbon atom in a ring, the hydroxyl group is assumed
to be on carbon 1.
PHYSICAL PROPERTIES OF ALCOHOLS
Alcohol molecules have both polar and non-
polar character. The hydroxyl groups present are polar
and the alkyl (R) group present is non-polar.
The physical properties of an alcohol depend on
whether the polar or the non-polar portion of its
structure “dominates”. Factors that determine this
include the length of the non-polar carbon chain
present and the number of the polar hydroxyl group
present.
Boling points for unbranched chain alcohols
with an –OH group on an end carbon increases as the
length of the carbon chain increases. This trend results
from increasing London forces with increasing carbon
chain length. Alcohols with more than one hydroxyl
group present have significantly higher boiling points
than their monohydroxy counterparts.
Small monohydroxy alcohols are soluble in
water in all proportions. As carbon chain length
increases beyond three carbons, solubility in water
rapidly decreases because of the increasing non-polar
character of the alcohol. Alcohols with two –OH groups
are more soluble in water than their counterparts with
only one –OH group. Increased hydrogen bonding is
responsible for this.
ALCOHOLS AND HYDROGEN BONDING
1. Alcohols have higher boiling points than alkanes of
similar molecular mass.
2. Alcohols have much higher solubility in water than
alkanes of similar molecular mass.
The differences in physical properties between
alcohols and alkanes are related to hydrogen bonding.
Because of their hydroxyl group, alcohols can
participate in hydrogen bonding, whereas alkanes
cannot. Hydrogen bonding between alcohol molecules
is similar to that which occurs between water
molecules.
Extra energy is needed to overcome alcohol-alcohol
hydrogen bonds before alcohol molecules can enter the
vapor phase. Hence alcohol boiling points are higher
than those for the corresponding alkanes (where no
hydrogen bonds are present).
HYDROGEN BOND
An especially strong attraction exists between
molecules of water. The polarity of the O-H bond shifts
the electrons toward the oxygen within the molecule so
much that the hydrogen acquires a partial positive
charge. Such a hydrogen is very strongly attracted
toward the electron cloud of an oxygen in a neighboring
water molecule.
Hydrogen bonds are not restricted to water.
They form whenever two molecules, the same or
different, come together, provided that
1. One molecule has a hydrogen atom attached by a
covalent bond to an atom of oxygen, nitrogen, or
fluorine.
 2. The other molecule has an oxygen, nitrogen, or
fluorine atom.
Therefore, we expect hydrogen bonds to form here:
H
O --- H – F
H
But not here:
H H
O H–C–H
H H
Although hydrogen bonds are among the
strongest of the intermolecular forces, it must be kept
in mind that they are still much weaker than the
covalent bonds within the molecules. Covalent bonds
are about ten times stronger than hydrogen bonds.
PREPARATION OF ALCOHOLS
A general method for preparing alcohols is the
hydration of alkenes. Alkenes react with water in the
presence of sulfuric acid to form an alcohol.
Markovnikov’s rule is used to determine the
predominant alcohol product.
CHEMICAL REACTIONS OF ALCOHOL
COMBUSTION
Alcohols are flammable as with hydrocarbons,
the combustion products are carbon dioxide and water.
DEHYDRATION
A chemical reaction in which the components of
water, (H and OH), are removed from a reactant.
Reaction conditions are temperature of 180˚C and the
presence of sulfuric acid as catalyst. The dehydration
product is an alkene.
Ease of alcohol dehydration depends on alcohol
classification. Primary alcohols are the most difficult to
dehydrate requiring temperature of 180°C. If the
temperature is not set correctly, a different pathway for
dehydration can occur. Water can split out between
two alcohol molecules, rather than from within one
alcohol molecule and produces an ether.
At 180°C with H2SO4:
Primary Alcohol alkene
At 140°C with H2SO4:
Primary Alcohol ether
At 140°C, 180°C with H2SO4:
Secondary Alcohol alkene
At 140°C, 180°C with H2SO4:
Tertiary Alcohol alkene
OXIDATION
1. An organic oxidation is an oxidation that increases
the number of C-O bonds and/or decreases the
number of C-H bonds.
2. An organic reduction is a reduction that decreases
the number of C-O bonds and/or increases the
number of C-H bonds.
Some alcohols readily undergo oxidation with mild
oxidizing agents; others are resistant to oxidation with
these same oxidizing agents. Primary and secondary
alcohols, but not tertiary alcohols, readily undergo
oxidation in the presence of mild oxidizing agents to
produce compounds that contain a carbon-oxygen
double bond.
HALOGENATION
Alcohols undergo halogenation reactions in
which a halogen atom is substituted for the hydroxyl
group, producing an alkyl halide. A single product is
produced in which the halogen atom is found only
where the –OH group was originally located.
IMPORTANT COMMONLY ENCOUNTERED ALCOHOLS
Methyl Alcohol (Methanol)
Methyl alcohol, with one carbon atom and one
–OH group, is the simplest alcohol. This colorless liquid
is a good fuel for internal combustion engines. Since
1965 all racing cars at the Indianapolis Speedway have
been fueled with methyl alcohol. Methyl alcohol fires
are easier to put out than gasoline fires because water
mixes with and dilutes methyl alcohol.
Methyl alcohol is sometimes called wood
alcohol, terminology that draws attention to an early
method for its preparation – the heating of wood to a
high temperature in the absence of air. Today nearly all
methyl alcohol is produced via the reaction between H2
and CO.
CO + 2H2 CH3OH
Drinking methyl alcohol is very dangerous.
Within the human body, methyl alcohol is oxidized by
the liver enzyme alcohol dehydrogenase to the toxic
metabolites formaldehyde and formic acid.
Formaldehyde can cause blindness (temporary or
permanent). Formic acid causes acidosis. Ingesting as
little as 1 oz (30mL) of methyl alcohol can cause optic
nerve damage.
*Methyl alcohol poisoning is treated with ethyl alcohol,
which ties up the enzyme that oxidizes methyl alcohol
to its toxic metabolites.
Ethyl Alcohol (Ethanol)
Ethyl alcohol, the two-carbon monohydroxy
alcohol is the alcohol present in alcoholic beverages and
is commonly referred to simply as alcohol or drinking
alcohol. Like methyl alcohol, ethyl alcohol is oxidized in
the human body by the liver enzyme alcohol
hydrogenase.
CH3CH2OH CH3COH CH3COOH
Acetaldehyde, the first oxidation product, is
largely responsible for the symptoms of hangover. The
odors of both acetaldehyde and acetic acid are detected
on the breath of someone who has consumed a large
amount of alcohol. Ethyl alcohol oxidation products are
less toxic than those of methyl alcohol.
Long-term excessive use of ethyl alcohol may
cause undesirable effects such as cirrhosis of the liver,
loss of memory, and strong physiological addiction.
Ethyl alcohol can be produced by yeast
fermentation of sugars found in plant extracts. The
synthesis of ethyl alcohol in this manner, from grains
such as corn, rice, and barley is the reason why ethyl
alcohol is often called grain alcohol.
C6H12O6 2CH3CH2OH + 2CO2
Fermentation is the process by which ethyl
alcohol for alcoholic beverages is produced. The
maximum concentration of ethyl alcohol obtainable by
fermentation is about 18% (v/v) because yeast enzymes
cannot function in stronger alcohol solutions. Alcoholic
beverages with a higher concentration of alcohol than
this are prepared by either distillation or fortification
with alcohol obtained by the distillation of another
fermentation product.
Most ethyl alcohol used in industry is prepared
from ethane via hydration reaction.
CH2=CH2 + H2O CH3CH2OH
The reaction produces a product that is 95%
alcohol and 5% water. In application where water does
interfere with its use, the mixture is treated with a
dehydrating agent to produce 100% ethyl alcohol. Such
alcohol, with all traces of water removed, is called
absolute alcohol.
Denatured alcohol is ethyl alcohol that has been
rendered unfit to drink by the addition of small
amounts of toxic substances (denaturing agents).
Almost all of ethyl alcohol used for industrial purposes
is denatured alcohol.
*The alcohol content of strong alcoholic beverages is
often stated in terms of proof. Proof is twice the
percentage of alcohol. This system dates back to the
seventeenth century and is based on the fact that a 50%
(v/v) alcohol -water mixture will burn. Its flammability
was proof that a liquor had not been watered down.
Isopropyl Alcohol (2-propanol)
A 70% isopropyl alcohol – 30% water solution is
marketed as rubbing alcohol. Isopropyl alcohol’s rapid
evaporation rate creates a dramatic cooling effect when
it is applied to the skin, hence its use for alcohol rubs to
combat high body temperature. It also finds use in
cosmetics formulations such as after-shave lotion and
hand lotions.
The “medicinal” odor associated with doctors’
offices is usually that of isopropyl alcohol.
Isopropyl alcohol has a bitter taste. Its toxicity is
twice that of ethyl alcohol, but it causes few fatalities
because it often induces vomiting and thus doesn’t stay
down long enough to be fatal. In the body it is oxidized
to acetone.
Ethylene Glycol (1,2-Ethanediol) and Propylene Glycol
(1,2-Propanediol)
Ethylene glycol and propylene glycol are the
two simplest alcohols possessing two –OH groups.
Besides being diols, they are also classified as glycols. A
glycol is a diol in which the two –OH groups are an
adjacent carbon atoms.
The ethylene glycol and propylene glycol used
in antifreeze formulations are colorless and odorless;
the color and odor of antifreeze come from additives
for rust protection and the like.
Both of these glycols are colorless, odorless,
high-boiling liquids that are completely miscible with
water. Their major uses are as the main ingredients in
automobile “year-round” antifreeze and airplane “de-
icers” and as a starting material for the manufacture of
polyester fibers.
Ethylene glycol is extremely toxic when
ingested. In the body, liver enzymes oxidize it to oxalic
acid. Oxalic acid, as a calcium salt, crystallizes in the
kidneys, which leads to renal problems.
Propylene glycol, on the other hand, is
essentially nontoxic and has been used as a solvent for
drugs. Like ethylene glycol, it is oxidized by liver
enzymes.

Glycerol (1,2,3-Propanetriol)
Glycerol, which is often also called glycerin, is a
clear, thick liquid that has the consistency of honey. Its
molecular structure involves three –OH groups on three
different carbon atoms.
Glycerol is normally present in the human body
because it is a product of fat metabolism. It is present,
in combined form, in all animal fats and vegetable oils.
In some Arctic species glycerol functions as a “biological
antifreeze”.
Because glycerol has a great affinity for water
vapor (moisture), it is often added to pharmaceutical
preparations such as skin lotions and soap. Florists
sometimes use glycerol on cut flowers to help retain
water and maintain freshness. Its lubricative properties
also make it useful in shaving creams and in applications
such as glycerol suppositories for rectal administration
of medicines. It is used in candies and icings as a
retardant for preventing sugar crystallization.
In 1847 an Italian chemist, Ascanio Sobrero
(1812-1888) discovered that glycerol reacts with a
mixture of nitric and sulfuric acid to give a liquid called
nitroglycerine.
When Sobrero heated a small quantity of this
liquid, it exploded. This problem was essentially solved
by a Swedish chemist, Alfred Nobel (1833-1896) whose
brother had been killed when Nobel’s nitroglycerine
factory exploded in 1864.
In 1866 Nobel found that a clay-like substance,
diatomaceous earth would absorb liquid nitroglycerine
so it would not explode without a fuse. He called it
dynamite, still one of our most important explosives.
Nitroglycerine is also used to treat angina
pectoris, sharp chest pains caused by reduced flow of
blood. Nitroglycerine relaxes and smoothes muscles of
the blood vessels and dilates the arteries allowing more
blood to reach the heart.