Determination of and Unknown

Primary, Secondary, Tertiary

Alcohols

Abstract
Alcohols and Phenols contain the functional group, OH.  In a phenol, the OH group is
connected to a carbon on a benzene ring whereas in alcohols, the OH group is connected
to a sp3 hybridized carbon atom.  Alcohols are classified as 10, 20 and 30, depending on
the number of carbon atoms connected to the carbon bearing the OH group.  Alcohols as
well as phenols find a variety of industrial, pharmaceutical, and even household
applications.  Derivatives of alcohols and phenols are found in medicines, alcohols are
used as common industrial solvents etc. Lucas test, chromic acid test, and boiling points
can be used to differentiate primary, secondary and tertiary alcohols.  Phenols do not
react under the reaction conditions of Lucas test and/or chromic acid test. 
INTRODUCTION
The functional groups we will consider in this experiment are alcohols and phenols.

In alcohols, the -OH group is attached to a tetrahedral carbon atom. If the carbon atom
is bonded to three hydrogens in addition to the -OH, the alcohol is methanol. If the
carbon that is bonded to the -OH, is bonded to one carbon and two hydrogens, the
alcohol is primary (1). If the carbon that is bonded to two carbons and one hydrogen
the alcohol is a secondary (2) alcohol. If the carbon that is bonded to the -OH is bonded
to three carbons, the alcohol is a tertiary (3) alcohol. Although these four classes of
compounds contain the functional group OH, the unique differences in their reaction
chemistry allows one to easily differentiate one from the other etc. Representative
examples of a phenol, and three types of alcohols are shown below.
 In phenols the -OH group is directly attached to a carbon that is part of an
aromatic ring. Alcohols and phenols are similar in some ways, but there are enough
differences so that they are considered different functional groups. One major difference
is that phenols are typically about a million times more acidic than alcohols. Addition of
sufficient aqueous sodium hydroxide to a phenol will cause the -OH group of most of the
molecules present to be deprotonated; this will not happen to an alcohol.

Physical Properties
The larger an alcohol or phenol the higher the boiling point, usually. As the alcohol size
increases the probability that the alcohol will be a solid increase. Many phenols are
solids. Small alcohols are water soluble because the hydroxyl group can hydrogen bond
with water molecules. But as the size of the alkyl group increases the solubility in water
decreases. This is the result of the alkyl group disrupting hydrogen bonding among the
water molecules. If the disruption becomes large enough the water molecules, in effect,
expel the alcohol molecules to reestablish hydrogen bonding.
The situation is similar for phenols. If nonpolar groups (like alkyl groups) are attached
to the aromatic ring the water solubility of the phenol decreases. [This is why nonpolar
groups are sometimes called hydrophobic. In this experiment, we preformed several test
to distinguish alcohols from phenols and properly classify alcohols.
Lucas Test.
This test is used to distinguish among primary, secondary, and tertiary water- soluble
alcohols. Lucas reagent is a mixture of concentrated hydrochloric acid and zinc chloride.
Zinc chloride is a Lewis acid, which when added to hydrochloric acid makes it even more
acidic. Water soluble tertiary alcohols react with Lucas reagent almost immediately to
form an alkyl chloride which is insoluble in the aqueous solution.
The rate of reaction of an alcohol with HCl in presence of ZnCl2 is dependant on the
nature of the alcohol.  Tertiary alcohols react almost instantaneously to give water
insoluble alkyl chlorides as products (remember the fact that alcohols are water soluble
due to H-bonding). 
R—OH + HCl ⃗ ZnCl 2
R—Cl + H2O
So, if a cloudy dispersion or as a separate layer within the solution occurs immediately
upon mixing the alcohol with the reagents then that alcohol must be a tertiary one. 
Secondary alcohols will form cloudy products upon standing while primary alcohols
need to be heated with the reagents before the reaction can occur.  This qualitative test
can be used to identify a primary alcohol from secondary and tertiary alcohols.
Ferric Chloride test
Alcohols are readily differentiated from phenols using this test.  Addition of a drop or
two of ferric chloride solution to a sample of phenol (3-4 drops) will produce a distinct
violet/purple coloration.   Alcohols do not produce such deep coloration when treated
with ferric chloride solution.

Lucas test, chromic acid test, and boiling points can be used to differentiate primary,
secondary and tertiary alcohols.  Phenols do not react under the reaction conditions of
Lucas test and/or chromic acid test. 

Chromic Acid Test:

Potassium dichromate, K2Cr2O7 in aq. acid and Jones Reagent (CrO3 in acetone and
sulfuric acid) are two common oxidizing agents.  In both these reagents, Cr is present as
Cr (VI) which is red orange in color.   However, after the oxidation reaction, Cr (VI) gets
reduced to Cr(III) which is dark green in color.  This color change is exploited and used
for the detection of alcohol in breath of suspected intoxicated drivers using a Breath
analyzer.  Oxidation of alcohols using potassium dichromate and acid can be used as a
method to differentiate tertiary alcohols from primary and secondary alcohols. Both
primary as well as secondary alcohols are oxidized using these reagents, producing a
green Cr III precipitate.  Tertiary alcohols are not oxidized with these reagents.

Acidity of Phenols
Most phenols are weaker acids than carboxylic acids and stronger acids than alcohols.
When phenols react with a base the phenol is converted into a phenoxide anion (see
reactions below). The phenoxide anion is more soluble in water than the corresponding
phenol. Consequently, if a water-insoluble phenol is treated with an aqueous solution of
a base that is strong enough to convert most of the phenol to the phenoxide anion, that
phenol will dissolve in the aqueous base (as the phenoxide salt). Aqueous sodium
hydroxide and sodium carbonate are strong enough bases to dissolve most water-
insoluble phenols, while aqueous sodium bicarbonate is not. None of the above-
mentioned bases is strong enough to convert a substantial amount of a typical alcohol
into an alkoxide anion (which would cause a water-insoluble alcohol to dissolve as its
alkoxide anion).

The order of basicity of the bases appearing on the left in the above equations is, from
most basic to least basic: sodium hydroxide, NaOH > sodium carbonate, Na CO >
2 3
sodium bicarbonate, NaHCO .
3
Iron(III) Chloride Test.
Addition of iron(III) chloride dissolved in chloroform (trichloromethane) to a phenol
dissolved in chloroform, gives a colored solution upon addition of pyridine. Depending
on the structure of the phenol the color of the product can be most anything from red to
violet. Alcohols do not give this test.

Boiling Point Determination

After setting up the apparatus as shown in the
diagram. A piece of fire-resistant wire gauze with
a small hole is placed on a ring. A test tube
containing about 2 mL of the alcohol to be tested
and a boiling stone is supported by a clamp so
that the bottom of the test tube rests directly over
the hole. The gauze shields the outer wall of the
test tube from the heat of the burner, keeping it
cool enough to cause condensation of the alcohol
vapor created upon heating. Lower a
thermometer (measuring to at least 150C) until
the bulb is 0.5-1.0 cm above the surface of the
liquid by centering the thermometer clamp so
that the bulb does not contact the inner walls of
the test tube.
Lastly adjusting the burner to a very low flame
and manipulate it beneath the hole in the gauze
until a gentle boiling of the liquid takes place.
(Gentle boiling is essential for the success of this
determination. Violent boiling will result in a
rapid loss of the sample and possibly increase the
danger of its becoming ignited by the burner flame.