ALCOHOL

BOILING POINTS AND WATER SOLUBILITIES

Boling points for unbranched chain alcohols

with an –OH group on an end carbon increases as the
In alcohols, the hydroxyl group, -OH, is length of the carbon chain increases. This trend results
covalently held by a saturated carbon atom, a carbon from increasing London forces with increasing carbon
atom from which only single bond extend. Only when chain length. Alcohols with more than one hydroxyl
present in this form is the OH group called the alcohol group present have significantly higher boiling points
group. than their monohydroxy counterparts.
Alcohols with one OH per molecule as the sole Small monohydroxy alcohols are soluble in
functional group are called simple alcohol or water in all proportions. As carbon chain length
monohydric alcohol. Dihydric alcohol, sometimes called increases beyond three carbons, solubility in water
glycols have two OH groups. A trihydric alcohol is one rapidly decreases because of the increasing non-polar
whose molecules have three alcohol groups. character of the alcohol. Alcohols with two –OH groups
Alcohols are classified as primary, secondary or are more soluble in water than their counterparts with
tertiary depending on the number of carbon atoms only one –OH group. Increased hydrogen bonding is
bonded to the carbon atom that bears the hydroxyl responsible for this.
group. A primary alcohol is an alcohol in which the
hydroxyl-bearing carbon atom is bonded to only one ALCOHOLS AND HYDROGEN BONDING
other carbon atom. A secondary alcohol is an alcohol in
which the hydroxyl-bearing carbon atom is bonded to 1. Alcohols have higher boiling points than alkanes of
two other carbon atoms. A tertiary alcohol is an alcohol similar molecular mass.
in which the hydroxyl-bearing carbon atom is bonded to 2. Alcohols have much higher solubility in water than
three other carbon atoms. alkanes of similar molecular mass.

NOMENCLATURE The differences in physical properties between

alcohols and alkanes are related to hydrogen bonding.
1. Name the longest carbon chain to which the hydroxyl Because of their hydroxyl group, alcohols can
group is attached. The chain name is obtained by participate in hydrogen bonding, whereas alkanes
dropping the final –e from the alkane and adding the cannot. Hydrogen bonding between alcohol molecules
suffix –ol. is similar to that which occurs between water
2. Number the chain starting from the end nearest the molecules.
hydroxyl group, and use the appropriate number to Extra energy is needed to overcome alcohol-alcohol
indicate the position of the –OH group. (In numbering hydrogen bonds before alcohol molecules can enter the
the longest carbon chain, the hydroxyl group has vapor phase. Hence alcohol boiling points are higher
priority over double and triple bonds, as well as over than those for the corresponding alkanes (where no
alkyl, cycloalkyl, and halogen substituents.) hydrogen bonds are present).
3. Name and locate any other substituents present.
4. In alcohols where the –OH group is attached to a HYDROGEN BOND
carbon atom in a ring, the hydroxyl group is assumed
to be on carbon 1. An especially strong attraction exists between
molecules of water. The polarity of the O-H bond shifts
PHYSICAL PROPERTIES OF ALCOHOLS the electrons toward the oxygen within the molecule so
much that the hydrogen acquires a partial positive
Alcohol molecules have both polar and non- charge. Such a hydrogen is very strongly attracted
polar character. The hydroxyl groups present are polar toward the electron cloud of an oxygen in a neighboring
and the alkyl (R) group present is non-polar. water molecule.
The physical properties of an alcohol depend on Hydrogen bonds are not restricted to water.
whether the polar or the non-polar portion of its They form whenever two molecules, the same or
structure “dominates”. Factors that determine this different, come together, provided that
include the length of the non-polar carbon chain 1. One molecule has a hydrogen atom attached by a
present and the number of the polar hydroxyl group covalent bond to an atom of oxygen, nitrogen, or
present. fluorine.
 2. The other molecule has an oxygen, nitrogen, or At 140°C, 180°C with H2SO4:
fluorine atom. Secondary Alcohol alkene
Therefore, we expect hydrogen bonds to form here: At 140°C, 180°C with H2SO4:
Tertiary Alcohol alkene
H
O --- H – F
H
But not here: OXIDATION

H H 1. An organic oxidation is an oxidation that increases

O H–C–H the number of C-O bonds and/or decreases the
H H number of C-H bonds.
2. An organic reduction is a reduction that decreases
Although hydrogen bonds are among the the number of C-O bonds and/or increases the
strongest of the intermolecular forces, it must be kept number of C-H bonds.
in mind that they are still much weaker than the
covalent bonds within the molecules. Covalent bonds Some alcohols readily undergo oxidation with mild
are about ten times stronger than hydrogen bonds. oxidizing agents; others are resistant to oxidation with
these same oxidizing agents. Primary and secondary
PREPARATION OF ALCOHOLS alcohols, but not tertiary alcohols, readily undergo
oxidation in the presence of mild oxidizing agents to
A general method for preparing alcohols is the produce compounds that contain a carbon-oxygen
hydration of alkenes. Alkenes react with water in the double bond.
presence of sulfuric acid to form an alcohol.
Markovnikov’s rule is used to determine the HALOGENATION
predominant alcohol product.
Alcohols undergo halogenation reactions in
CHEMICAL REACTIONS OF ALCOHOL which a halogen atom is substituted for the hydroxyl
group, producing an alkyl halide. A single product is
COMBUSTION produced in which the halogen atom is found only
where the –OH group was originally located.
Alcohols are flammable as with hydrocarbons,
the combustion products are carbon dioxide and water. IMPORTANT COMMONLY ENCOUNTERED ALCOHOLS

DEHYDRATION Methyl Alcohol (Methanol)

Methyl alcohol, with one carbon atom and one
A chemical reaction in which the components of –OH group, is the simplest alcohol. This colorless liquid
water, (H and OH), are removed from a reactant. is a good fuel for internal combustion engines. Since
Reaction conditions are temperature of 180˚C and the 1965 all racing cars at the Indianapolis Speedway have
presence of sulfuric acid as catalyst. The dehydration been fueled with methyl alcohol. Methyl alcohol fires
product is an alkene. are easier to put out than gasoline fires because water
Ease of alcohol dehydration depends on alcohol mixes with and dilutes methyl alcohol.
classification. Primary alcohols are the most difficult to Methyl alcohol is sometimes called wood
dehydrate requiring temperature of 180°C. If the alcohol, terminology that draws attention to an early
temperature is not set correctly, a different pathway for method for its preparation – the heating of wood to a
dehydration can occur. Water can split out between high temperature in the absence of air. Today nearly all
two alcohol molecules, rather than from within one methyl alcohol is produced via the reaction between H2
alcohol molecule and produces an ether. and CO.
CO + 2H2 CH3OH
At 180°C with H2SO4:
Primary Alcohol alkene Drinking methyl alcohol is very dangerous.
At 140°C with H2SO4: Within the human body, methyl alcohol is oxidized by
Primary Alcohol ether the liver enzyme alcohol dehydrogenase to the toxic
metabolites formaldehyde and formic acid. interfere with its use, the mixture is treated with a
Formaldehyde can cause blindness (temporary or dehydrating agent to produce 100% ethyl alcohol. Such
permanent). Formic acid causes acidosis. Ingesting as alcohol, with all traces of water removed, is called
little as 1 oz (30mL) of methyl alcohol can cause optic absolute alcohol.
nerve damage.
Denatured alcohol is ethyl alcohol that has been
*Methyl alcohol poisoning is treated with ethyl alcohol, rendered unfit to drink by the addition of small
which ties up the enzyme that oxidizes methyl alcohol amounts of toxic substances (denaturing agents).
to its toxic metabolites. Almost all of ethyl alcohol used for industrial purposes
is denatured alcohol.
Ethyl Alcohol (Ethanol)
Ethyl alcohol, the two-carbon monohydroxy *The alcohol content of strong alcoholic beverages is
alcohol is the alcohol present in alcoholic beverages and often stated in terms of proof. Proof is twice the
is commonly referred to simply as alcohol or drinking percentage of alcohol. This system dates back to the
alcohol. Like methyl alcohol, ethyl alcohol is oxidized in seventeenth century and is based on the fact that a 50%
the human body by the liver enzyme alcohol (v/v) alcohol -water mixture will burn. Its flammability
hydrogenase. was proof that a liquor had not been watered down.

CH3CH2OH CH3COH CH3COOH Isopropyl Alcohol (2-propanol)

A 70% isopropyl alcohol – 30% water solution is
Acetaldehyde, the first oxidation product, is marketed as rubbing alcohol. Isopropyl alcohol’s rapid
largely responsible for the symptoms of hangover. The evaporation rate creates a dramatic cooling effect when
odors of both acetaldehyde and acetic acid are detected it is applied to the skin, hence its use for alcohol rubs to
on the breath of someone who has consumed a large combat high body temperature. It also finds use in
amount of alcohol. Ethyl alcohol oxidation products are cosmetics formulations such as after-shave lotion and
less toxic than those of methyl alcohol. hand lotions.
Long-term excessive use of ethyl alcohol may The “medicinal” odor associated with doctors’
cause undesirable effects such as cirrhosis of the liver, offices is usually that of isopropyl alcohol.
loss of memory, and strong physiological addiction. Isopropyl alcohol has a bitter taste. Its toxicity is
Ethyl alcohol can be produced by yeast twice that of ethyl alcohol, but it causes few fatalities
fermentation of sugars found in plant extracts. The because it often induces vomiting and thus doesn’t stay
synthesis of ethyl alcohol in this manner, from grains down long enough to be fatal. In the body it is oxidized
such as corn, rice, and barley is the reason why ethyl to acetone.
alcohol is often called grain alcohol.
Ethylene Glycol (1,2-Ethanediol) and Propylene Glycol
C6H12O6 2CH3CH2OH + 2CO2 (1,2-Propanediol)
Ethylene glycol and propylene glycol are the
Fermentation is the process by which ethyl two simplest alcohols possessing two –OH groups.
alcohol for alcoholic beverages is produced. The Besides being diols, they are also classified as glycols. A
maximum concentration of ethyl alcohol obtainable by glycol is a diol in which the two –OH groups are an
fermentation is about 18% (v/v) because yeast enzymes adjacent carbon atoms.
cannot function in stronger alcohol solutions. Alcoholic The ethylene glycol and propylene glycol used
beverages with a higher concentration of alcohol than in antifreeze formulations are colorless and odorless;
this are prepared by either distillation or fortification the color and odor of antifreeze come from additives
with alcohol obtained by the distillation of another for rust protection and the like.
fermentation product. Both of these glycols are colorless, odorless,
Most ethyl alcohol used in industry is prepared high-boiling liquids that are completely miscible with
from ethane via hydration reaction. water. Their major uses are as the main ingredients in
automobile “year-round” antifreeze and airplane “de-
CH2=CH2 + H2O CH3CH2OH icers” and as a starting material for the manufacture of
polyester fibers.
The reaction produces a product that is 95% Ethylene glycol is extremely toxic when
alcohol and 5% water. In application where water does 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.