Identification of Organic compounds

Identification of Alcohols

UNKNOWN: 65
Ali Hussein Sabr, Noor Riyadh, Mustafa Abd Alsalaam
| Pharmaceutical Chemistry | 13/2/2024
Supervised by: Assist. Prof. Dr. Karima Fadhil Ali
 Introduction:-
Alcohol is any of a class of organic compounds characterized by one or more
hydroxyl (―OH) groups attached to a carbon atom of an alkyl group (hydrocarbon
chain). Alcohols may be considered as organic derivatives of water (H2O) in which
one of the hydrogen atoms has been replaced by an alkyl group, typically represented
by R in organic structures. For example, in ethanol (or ethyl alcohol) the alkyl group
is the ethyl group, ―CH2CH3.

Alcohols are among the most common organic compounds. They are used as
sweeteners and in making perfumes, are valuable intermediates in the synthesis of
other compounds, and are among the most abundantly produced organic chemicals
in industry. Perhaps the two best-known alcohols are ethanol and methanol (or
methyl alcohol). Ethanol is used in toiletries, pharmaceuticals, and fuels, and it is
used to sterilize hospital instruments. It is, moreover, the alcohol in alcoholic
beverages. The anesthetic ether is also made from ethanol. Methanol is used as a
solvent, as a raw material for the manufacture of formaldehyde and special resins, in
special fuels, in antifreeze, and for cleaning metals.
Alcohols may be classified as primary, secondary, or tertiary, according to which
carbon of the alkyl group is bonded to the hydroxyl group. Most alcohols are
colorless liquids or solids at room temperature. Alcohols of low molecular weight are
highly soluble in water; with increasing molecular weight, they become less soluble
in water, and their boiling points, vapor pressures, densities, and viscosities increase.

Physical properties of alcohols

Most of the common alcohols are colorless liquids at room temperature. Methyl
alcohol, ethyl alcohol, and isopropyl alcohol are free-flowing liquids with fruity
odors. The higher alcohols—those containing 4 to 10 carbon atoms—are somewhat
viscous, or oily, and they have heavier fruity odors. Some of the highly branched
alcohols and many alcohols containing more than 12 carbon atoms are solids at room
temperature. The boiling points of alcohols are much higher than those of alkanes
with similar molecular weights. For example, ethanol, with a molecular weight (MW)
of 46, has a boiling point of 78 °C (173 °F), whereas propane (MW 44) has a boiling
point of −42 °C (−44 °F). Such a large difference in boiling points indicates that

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molecules of ethanol are attracted to one another much more strongly than propane
molecules. Most of this difference results from the ability of ethanol and other
alcohols to form intermolecular hydrogen bonds.

The oxygen atom of the strongly polarized O―H bond of an alcohol pulls electron
density away from the hydrogen atom. This polarized hydrogen, which bears a
partial positive charge, can form a hydrogen bond with a pair of nonbonding
electrons on another oxygen atom. Hydrogen bonds, with a strength of about 5
kilocalories (21 kilojoules) per mole, are much weaker than normal covalent bonds,
with bond energies of about 70 to 110 kilocalories per mole. (The amount of energy
per mole that is required to break a given bond is called its bond energy.)

Water and alcohols have similar properties because water molecules contain
hydroxyl groups that can form hydrogen bonds with other water molecules and with
alcohol molecules, and likewise alcohol molecules can form hydrogen bonds with
other alcohol molecules as well as with water. Because alcohols form hydrogen bonds
with water, they tend to be relatively soluble in water. The hydroxyl group is referred
to as a hydrophilic (“water-loving”) group because it forms hydrogen bonds with
water and enhances the solubility of alcohol in water. Methanol, ethanol, n-propyl
alcohol, isopropyl alcohol, and t-butyl alcohol are all miscible with water. Alcohols
with higher molecular weights tend to be less water-soluble, because the
hydrocarbon part of the molecule, which is hydrophobic (“water-hating”), is larger
with increased molecular weight. Because they are strongly polar, alcohols are better
solvents than hydrocarbons for ionic compounds and other polar substances.

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 Solubility classification
Alcohols are polar compounds because of the presence of the hydroxyl group which
is also responsible for their ability to form hydrogen bonding. The degree of the
polarity depends on the size of the alkyl side chain; the polarity decreases as the size
of the alkyl side chain increases, or in other words, as the hydroxyl group
/hydrocarbon ratio of alcohols increases, their water solubility increases, and vice
versa. Besides, low molecular weight alcohols are soluble in water due to hydrogen
bonding ability with water molecules. Therefore, alcohols that are soluble in water
and ether are classified under class S1 such as ethanol and methanol. Alcohols that
are insoluble in water are related to class N such as benzyl alcohol, sec-butanol, and
cyclohexanol.

Chemical properties
Alcohols are neutral compounds that don’t change the color of litmus paper.
All reactions of alcohols are related to its active hydroxyl group and are of two types:
a) Removal of the hydroxyl itself as in the reaction with hydrogen halides to form
alkyl halides or in the dehydration reaction to form a double bond.
b) Removal of the proton only from the active hydroxyl as in the formation of
esters or the reaction with active metals such as sodium.

Purpose of the Experiment:-

Differentiate between primary, secondary, and tertiary alcohols.

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 Procedure:-
Oxidation of alcohol
1- Take a very small quantity of the given sample in a test tube.
2- Add 2 drops of K2Cr2O7 to the test tube containing the given sample and mix
them.
3- Record change in color.

Lucas test
1- Take a very small quantity of the given sample in a test tube.
2- Add 1 ml of the Lucas reagent in the test tube containing the given sample and
mix them.
3- Record the time until the solution becomes turbid or cloudy.

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Results:-
1- Add 2 drops of K2Cr2O7 to the unknown alcohol, the result was an
orange color.

So, the unknown is Tertiary alcohol.

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2- Add Lucas reagent to the unknown alcohol giving cloudiness (turbid
solution).

This means that it's confirmed Tertiary alcohol.

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 Discussion:-
Oxidation by K2Cr2O7
Alcohol oxidation is a chemical reaction in which an alcohol molecule
is converted into an aldehyde or ketone through the removal of one or
more hydroxyl groups. Alcohol oxidation typically follows a two-step
mechanism, involving the formation of an intermediate alkoxide ion
and the subsequent elimination of a hydroxyl group.
Alcohols can be oxidized by a warm solution of potassium dichromate
(VII) (K2Cr2O7) mixed with dilute sulfuric acid.
As the alcohol gets oxidized, the C2O7-2 ions in solution become
reduced to Cr3+ ions. This causes the solution to change color from
orange to green.
The products of oxidation depend on whether the alcohol is primary,
secondary, or tertiary.

Primary Alcohols
Primary alcohols can be oxidized to form an aldehyde. The aldehyde
will have a lower boiling point than the alcohol and can be distilled off.
If however the alcohol is heated under reflux, the aldehyde does not
evaporate off and stays in the reaction vessel, which causes it to
become further oxidized to form a carboxylic acid. The presence of a
carboxylic acid will cause the pH of the reaction mixture to become
acidic, which can be tested with a pH indicator.
Secondary Alcohols
Secondary alcohols are oxidized into ketones. Ketones do not undergo
further oxidation.
Tertiary Alcohols
Tertiary alcohols are resistant to oxidation by oxidizing agents.

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During the oxidation of primary and secondary alcohols the H atom in
the -OH group and a H atom on the C atom the -OH is bonded to, are
removed to form a C=O bond.
In tertiary alcohols, the C atom the -OH group is bonded to, has no H
atom attached to it. Therefore, the C=O cannot be formed.
Tertiary alcohols can only be oxidized by combustion.

The products of oxidation can be used to determine alcohol structure.

For starters, tertiary alcohols can be identified because no color change
will be seen when mixed with potassium dichromate (VII).
If potassium dichromate (VII) solution is mixed with primary or
secondary alcohols instead, the solution will change color from orange
to green.

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Lucas test
Lucas Reagent is the solution of concentrated hydrochloric acid with
zinc chloride is called Lucas reagent. Thus it can also be defined as a
solution of anhydrous zinc chloride present in the concentrated
Hydrochloric acid. It is used to classify the alcohols that have a lower
molecular weight. It is a substitution reaction where the chloride
finally replaces the hydroxyl group. The reaction results from the clear
and colorless solution to the turbid that indicates the formation of
chloroalkanes. In this reaction, the tertiary alcohols from their
respective halides are much faster than the primary or the secondary
alcohols because the intermediate tertiary carbocation is much more
stable in tertiary alcohol. Both concentrated HCl and ZnCl₂ are taken
in equi-molar quantities to make the reagent. The test became the
standard test for the identification of primary, secondary, and tertiary
alcohol. But with the development of new testing methods like
spectroscopy and various chromatography, Luca’s test is becoming less
popular. In the Lucas test, the Lucas reagent reacts with alcohols and
gives different results based on stability of the carbocation
intermediate formed during the reaction. The Chloride ion of
hydrochloric acid reacts with an alkyl group of alcohol and forms alkyl
chloride while zinc chloride is used as a catalyst. The rate of reaction of
primary, secondary, and tertiary alcohols with Lucas reagent differ
which forms the base of the Lucas Test. The simple reaction involved is
represented below

ROH + HCl → RCl + H₂O

The difference in the reactivity of the degrees of alcohol provides the

differing ease of formation of the corresponding carbocations. The
primary carbocation is the least stable followed by secondary
carbocation and the tertiary alcohols form the most stable tertiary
carbocations.

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