ALCOHOLS & PHENOLS

An important portion of this course is the recognition of organic chemistry functional groups.
These are parts of a molecule, with a specific structure that functions in a certain way. Not only
are you to learn to recognize the functional groups (a listing can be found in your textbook or on
the back cover of this laboratory manual), but you are also to learn the physical and chemical
properties of each of the functional groups studied in the course. This laboratory exercise will
introduce you to two of these functional groups, alcohols and phenols, as well as some of their
physical and chemical properties.

Alcohols

Although you may be familiar with "alcohol” as a beverage, the word actually represents an
entire classification of organic molecules and not just one substance. Alcohols contain the
−OH (hydroxyl) functional group attached to a saturated carbon. Notice that we did not call this
the hydroxide ion, because this group does not act as an ionic substance.

Alcohols are classified into three categories: primary (1°), secondary (2°) and tertiary (3°). This
classification is based on the number of carbon-containing groups (R− for an alkyl or an
aromatic group) attached to the carbon bearing the hydroxyl group. If the carbon bearing the
−OH has one R− group, the molecule is a primary alcohol. If two R− groups are attached, it is a
secondary alcohol. If three R− groups are attached, the alcohol is tertiary.

CH3
CH3
CH3 C OH
CH3 CH2 OH CH3 CH OH
CH3
ethanol 2-propanol 2-methyl-2-propanol
(primary) (secondary) (tertiary)

I. Physical Properties of Alcohols

R
The hydroxyl group present in all alcohols is a polar O
functional group. The polarity of this group allows H
alcohols to form hydrogen bonds. Small chain alcohols . Hydrogen bonding
.
are able to mix with water because of the hydrogen .
bonding interactions that will occur between the O
hydroxyl functional group and the water. If the R-group H
of the alcohol becomes too large however, the solubility H
of the alcohol will decrease.
 Procedure:

1. Place 10 drops of each alcohol (ethanol, 1-butanol, 2-butanol, 2-methyl-2-propanol

and 1-octanol) into its own test tube. Add 1-2 ml of water to each tube. Record your
observations on the data sheet.

2. Place another 10 drops of each of the above alcohols into its own test tube. Add 1-2
ml of dichloromethane. Record your observations on the data sheet.

!!CAUTION!! DICHLOROMETHANE IS FLAMMABLE. KEEP ALL FLAMES

AWAY. AVOID BREATHING FUMES. WORK IN THE HOOD AS
MUCH AS POSSIBLE. WEAR SAFETY GLASSES IN THE
LABORATORY AT ALL TIMES!

II. Chemical Properties of Alcohols

The classification of an alcohol as primary, secondary or tertiary (see above) affects the chemical
properties of the alcohols. This difference in chemical properties can be used as a means of
identification. The Lucas test and the chromic acid test are two common methods used to
distinguish among primary, secondary and tertiary alcohols.

A. Lucas Test:

The Lucas reagent contains zinc chloride and hydrochloric acid. When the Lucas reagent is
allowed to react with an alcohol, an alkyl halide is formed. This alkyl halide will not be
soluble in water, thus cloudiness or a second layer of droplets will form if the test is positive.
With this reagent, tertiary alcohols react immediately, secondary alcohols in 3 to 10 minutes,
and primary alcohols may take an hour or longer, or may never react.

ZnCl2
R-OH + HCl R-Cl + H2O
(insoluble)

Procedure:

3. Place 2 mL of the Lucas reagent in a test tube. Add 4 drops of ethanol. Shake the tube
to mix the materials and note the time required for the mixture to become cloudy or to
separate into two layers. Record your observations. Repeat this procedure for 1-
butanol, 2-butanol, and 2-methyl-2-propanol.
!!CAUTION!! Hydrochloric acid is very corrosive. Any spill should be immediately
flushed with water. Wear safety glasses in the laboratory at all times.

B. Chromic Acid Test:

Chromic acid (acidified dichromate, an oxidizing agent) can also be used to distinguish
between types of alcohols by oxidizing the alcohol. Primary alcohols are oxidized to
carboxylic acids; secondary alcohols are oxidized to ketones; and tertiary alcohols are not
oxidized. During the oxidation, the orange-red color of the chromic acid changes to a blue-
green solution.
O

R CH2 OH + H2CrO4 → R C OH + Cr2(SO4)3 + H2O

(primary) (red-orange) (carboxylic acid) (blue-green)

OH O

R CH R + H2CrO4 → R C R + Cr2(SO4)3 + H2O

(secondary) (red-orange) (ketone) (blue-green)

OH

R C R + H2CrO4 → No Reaction

R
(tertiary)

Procedure:

4. Place 10 drops of acetone in a test tube. Add 5 drops of ethanol and 2 drops of
chromic acid to the tube. Note and record the color of the solution on the data sheet.
Repeat this procedure for 1-butanol, 2-butanol, and 2-methyl-2-propanol.

!!CAUTION!! Chromic acid is very corrosive. Any spill should be immediately

flushed with water. Wear safety glasses in the laboratory at all times.
 Phenols

Phenols are closely related to alcohols because of the presence of the hydroxyl (−OH) group. In
phenols, however, the hydroxyl group is directly bonded to an aromatic group, such as benzene.
Phenol compounds often have curious but useful properties. Some are found in preservatives or
medications. The chemistry of phenols is different than that of alcohols. Concentrated solutions
of the compound phenol are quite toxic and can cause severe burns. In this experiment, we are
using an aqueous solution of phenol.

!!CAUTION!! Phenol is toxic and will cause burns to skin. Even though we are using
an aqueous solution of phenol, any contact should be thoroughly washed
with large quantities of water. Wear safety glasses at all times in the
laboratory. Report all accidents to the instructor.

III. Physical Properties of Phenols

Procedure:

5. Place 10 drops of phenol solution into a test tube. Add 1-2 ml of dichloromethane.
Record the observations for solubility on the data sheet.

IV. Chemical Properties of Phenols

Phenols react differently than alcohols. This is why they are given their own functional group
and are not technically “alcohols.” We will see this difference in the chromic acid test and the
ferric chloride test.

A. Chromic Acid Test

Phenols can be oxidized with chromic acid, but they give different types of products than
those formed from alcohols. The chromic acid test is described above, and the same results
are expected for a positive test (a blue-green solution is formed).

Procedure:

6. Place 10 drops of acetone in a test tube. Add 5 drops of phenol and 2 drops of
chromic acid to the tube. Note and record the color of the solution on the data sheet.
 Note: In the interest of time, this phenol experiment can be carried out at the same
time as the alcohol experiments. Consult instructor if there is a problem.

!!CAUTION!! Chromic acid is very corrosive. Any spill should be immediately

flushed with water. Wear safety glasses in the laboratory at all times.

B. Ferric Chloride test

Addition of aqueous ferric chloride to a phenol creates a colored solution. Depending upon
the structure of the phenol, the color can vary from green to purple.

Procedure:

7. Place 20 drops of the ferric chloride solution into a test tube. Add 5 drops of phenol
solution. Note and record any observations on the data sheet.

It is clear that some of the procedures will require some time to observe the results. The well-
prepared student, who has read the laboratory exercise in advance, may realize that the phenol
tests can be carried out at the same time some of the other tests are being done. These items
need not be tested sequentially. Ask the instructor if you need help.

UNKNOWN

Obtain an unknown sample which is one of the following: 1-butanol, 2-butanol, 2-methyl-2-
propanol or aqueous phenol. Using the information and knowledge gained during this
laboratory, and by utilizing your critical thinking skills, determine the identity of this unknown.
You can assume that if a test was not performed on a substance, the substance did not react with
the reagent.

Your report must include completion of the second data sheet which outlines the procedure for
determining the unknown. You should make a hypothesis and then design or select an
experiment which will support or invalidate your hypothesis. To verify the conclusion of your
unknown, you must have at least three experiments designed to check and/or verify your
hypotheses. Please be brief but clear and complete with your hypotheses, planned investigations,
and conclusion. For the conclusion, use complete sentences, proper grammar, etc.
 DATA SHEET I

Date Name
Alcohols & Phenols Partners

Solubility:

2-methyl-2-
Experiment ethanol 1-butanol 2-butanol 1-octanol phenol
propanol

 Comp  Comp  Comp  Comp  Comp

letely letely letely letely letely
Soluble Soluble Soluble Soluble Soluble
Solubility in  Partia  Partia  Partia  Partia  Partia
H2O lly Soluble lly Soluble lly Soluble lly Soluble lly Soluble
 Insolu  Insolu  Insolu  Insolu  Insolu
ble ble ble ble ble
 Comp  Comp  Comp  Comp  Comp  Comp
letely letely letely letely letely letely
Soluble Soluble Soluble Soluble Soluble Soluble
Solubility in  Partia  Partia  Partia  Partia  Partia  Partia
CH2Cl2 lly Soluble lly Soluble lly Soluble lly Soluble lly Soluble lly Soluble
 Insolu  Insolu  Insolu  Insolu  Insolu  Insolu
ble ble ble ble ble ble

Chemical Properties:

2-methyl-
Experiment ethanol 1-butanol 2-butanol phenol
2-propanol

Lucas
Test

Chromic Acid
Test

Ferric
Chloride Test
 DATA SHEET II

Date__________________ Name_________________________
Alcohols & Phenols Partner________________________

UNKNOWN # __________  Be sure to record the number of your unknown here!

1. A. Hypothesis:

B. Planned Investigation:

C. Observations (data):

D. Conclusion:

2. A. Hypothesis:

B. Planned Investigation:

C. Observations (data):

D. Conclusion:

3. A. Hypothesis:

B. Planned Investigation:

C. Observations (data):

D. Conclusion:

4. A. Hypothesis:

B. Planned Investigation:

C. Observations (data):

D. Conclusion:
 REPORT SHEET

Date__________________ Name_________________________
Alcohols & Phenols Partner________________________

Answer the following questions:

1. My Unknown (#______) was: (circle all that apply)

1-BUTANOL 2-BUTANOL 2-METHYL-2-PROPANOL PHENOL

2. Salicylic acid, shown below, could be (but, it wasn’t) used as an unknown. Describe what
you would see/learn as you “analyzed” this substance if it were your unknown in the
following:
OH
Solubility in water:
O
C FeCl3 Test:
OH
salicylic acid

3. What results would you expect from the reaction of 1-propanol with each of the following?

Lucas reagent:

Chromic acid reagent:

4. Alcohols are more soluble in water than hydrocarbons are in water. Why?

5. Why does the rule for solubility for alcohols depend upon their molecular size?

6. Most people find, in this experiment, that the result for the solubility of phenol in
dichloromethane is that it is insoluble. This does not seem to make sense to us, as both are
organic and it should be soluble. (Review your results for alcohols in dichloromethane.)
Explain why it appears to be insoluble.