Chem 31.

1 Laboratory Manual

EXPERIMENT 7
ORGANIC DERIVATIVES OF WATER

I. Prelab Preparation:
1. Review the principles you’ve learned about alcohols. The structure, bonding, physical properties
and the general features of its reaction.

II. Objectives:
At the end of the experiment, you should be able to:
1. identify the chemical properties of organic derivatives of water; and
2. observe the differences in chemical reactivity of primary, secondary, and tertiary alcohols,
phenols, and ethers towards selected chemical reagents.

III. Introduction:
In addition to carbon and hydrogen, the element oxygen is found in many important organic
compounds. Among the classes of oxygen – containing are alcohols, phenols, and ethers, also known as
organic derivatives of water because they may be seen to arise from the replacement of one or both of
the hydrogen atoms of water by an organic group. In alcohols, one hydrogen is replaced by an aliphatic
group, in phenols it is replaced by an aromatic group and in ether, both hydrogen atoms are replaced.

The hydroxyl group (-OH) is the functional group of alcohols and phenols. The O–H bond is polar
with the greater electron density around the oxygen atom. Under the proper conditions, the O–H bond
can be made to split heterolytically to release a proton:

Equation 7.1. Heterolytic splitting of the O–H bond.

At the same time, the oxygen atom acts as the Lewis base because of its unshared pair of
electrons. Hence, the oxygen atom is a site for attack by Lewis acids or electrophiles:

Equation 7.2. Reactivity of an alcohol in the presence of an electrophile.

The nature of the substituent bonded to the hydroxyl group greatly affects the reactivity of
alcohols and phenols. Thus, alcohols are classified as primary (1°), secondary (2°) or tertiary (3°), based

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 Chem 31.1 Laboratory Manual

on the type of carbon bearing the hydroxyl group. In phenols, the hydroxyl group is directly bonded to
an aromatic system. The aromatic ring makes the hydroxyl group more acidic than it is in alcohols.
Ethers are relatively inert molecules. The ether linkage C–O–C, is quite stable and can be cleaved
only under drastic conditions. The unshared pairs of electrons on the oxygen atom, however, make the
ethers susceptible to electrophilic attack.

Alcohols of the type undergo a unique reaction with halogens in the presence of
a base. This is called haloform reaction. The mixture of halogen and base produces a hypohalite which is
an oxidizing agent:

Equation 7.3. Formation of hypohalite.

The hypohalite first oxidizes the alcohol to a methyl carbonyl form which
subsequently undergoes the haloform reaction:

Equation 7.4. Oxidation of alcohol and formation of trihalomethane or haloform.

The compound classes considered in this exercise can be further differentiated via their
reactions with oxidizing and reducing agents. Below is a summary of the functional group
transformation for the oxidizable compounds:

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 Chem 31.1 Laboratory Manual

Figure 7.1 Transformation of functional group for oxidizable compounds.

Potassium permanganate is a powerful oxidizing agent with a characteristic purple color due to
the permanganate ion. When it reacts with oxidizable compound, the purple color is discharged and a
brown to black precipitate of MnO2 is formed together with the hydroxide ions.

In this exercise, a small amount of acid is added to the reagent to neutralize any hydroxide ions
produced from the reaction with oxidizable impurities.

Tollen’s reagent is a mild oxidizing agent which consists of ammoniacal silver nitrate prepared by
dissolving silver nitrate in excess ammonium hydroxide. The oxidizing agent here is the silver ion which,
exists as a stable complex Ag(NH3)+. Upon reaction, the silver ion is reduced to elemental silver (Ag)
which adheres to the clean glass walls of the container to form a mirror complex. Easily oxidizable
compounds give positive test with Tollen’s reagent.

Whether an alcohol is primary, secondary, or tertiary is determined using the Lucas test which is
based on the difference in reactivity of the alcohol toward hydrogen halides. Alcohols of no more than
six carbon atoms are soluble in the Lucas reagent, a mixture of concentrated hydrochloric acid and zinc
chloride. The alkyl chlorides formed are insoluble. The appearance of cloudiness thus indicates the
formation of a chloride from the alcohol. The reactions for 3° and 2° alcohols are shown below:

Figure 7.2. Reaction of 2° and 3° alcohol with hydrogen halide.

IV. Materials:

1-butanol concentrated H2SO4 Test tubes

2-butanol potassium permanganate Test tube rack
t-butyl alcohol Tollen’s reagent Test tube holder
diisopropyl ether Lucas reagent Water bath
phenol 2.5% aqueous ferric chloride Cork/rubber stopper
10% NaOH I2/KI soln Hot plate

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Department of Chemistry, College of Arts and Sciences, University of the Philippines Visayas, Miagao, Iloilo
 Chem 31.1 Laboratory Manual

V. Procedure:

The following representative compounds will be used in this experiment:

Figure 7.3. Chemical structure of the test samples.

CAUTION:
Phenol crystals slowly liquefy in hot humid air. The yellow color of the sample
is due to phenol oxidation products. The sample is suitable for the chemical tests,
except where anhydrous samples are required. HANDLE PHENOL WITH CARE AS IT
CAN CAUSE PAINFUL BURNS. IF SPILLED ON THE SKIN, WASH FREELY WITH 95% ETHANOL, THEN WITH
SOAP AND WATER.

Diisopropyl ether is highly volatile and flammable. Its vapor has a high tendency to form
explosive hydroxides. Fire is therefore a hazard to be guarded against. STAY AWAY FROM OPEN FLAME
WHEN WORKING WITH ETHER AND MINIMIZE EXPOSURE TO AIR.

A. Solubility behavior
Place 2 mL of water in a test tube then add 10 drops of the sample. Cover the tube with cork
stopper and shake to mix. Observe the mixture and record your observations. Repeat the process using
1 mL of 10% NaOH as solvent. If the compound is insoluble in base, repeat the steps using 1 mL
concentrated H2SO4 as solvent. Follow the same process for the remaining samples.

B. Chemical Reactivity

1. Reaction with potassium permanganate

Place 3 mL dilute, slightly acidic potassium permanganate in a clean test tube then add 5 drops
of the sample. Warm the tube gently in a water bath and observe the mixture after 5 minutes. Record
your observations.

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 Chem 31.1 Laboratory Manual

2. Reaction with Tollen’s reagent (ammoniacal silver nitrate)

Place 3 mL Tollen’s reagent in a test tube then add 5 drops of sample. Shake the tube then heat
gently in a water bath. Observe the mixture and record your observations.

NOTE: This test should be done using a test tube with smooth walls and is scrupulously clean.
Otherwise, the mirror will not deposit on the tube.

3. Lucas Test: reaction with HCl – ZnCl2 mixture

Place 2 mL of the HCl – ZnCl2 reagent in a test tube and add 5 drops of the sample. Stopper the
tube and shake. Allow the mixture to stand and note the time for the appearance of an insoluble layer
or emulsion.

4. Reaction with ferric chloride (FeCl3)

Place 2 drops of sample in 2 mL water then add several drops of 2.5% aqueous FeCl3. Observe
the mixture and compare the results with a blank using water.

5. Iodoform test: reaction with I2, NaOH

Place about 1 mL of the sample in a test tube, then add 2 mL water. Add about 1 mL I2/KI
solution followed by dropwise addition of 10% NaOH solution with shaking until the iodine color
disappears and the solution is faintly yellow. Observe the contents of the tube and note the odor. If the
test seems negative, shake the tube then heat gently in a water bath for 1 – 2 minutes. Observe the
mixture formed.

NOTE: Note the odor of the sample by wafting. DO NOT smell by holding the test tube to your nose.

VI. Questions:

1. Explain the solubility behavior of the representative compounds in water as a function of: a)
branching in the molecule and b) relative proportions of hydrophilic bonds to hydrophobic
bonds.

2. Explain the acidity differences observed for the compounds used in this exercise in terms of the
stability of the corresponding conjugate bases.

3. Based on the results of the oxidation test, classify the compounds tested according to the
following categories: easily oxidizable, oxidizable, and resistant to oxidation.

4. Discuss the reactivity differences of alcohols towards the Lucas reagent.

5. Suggest a simple chemical test that will differentiate between the following pairs of compounds.
Write the equations for the reactions involved.
a. phenol and isopentyl alcohol
b. tert-butyl alcohol and isobutyl alcohol
c. neopentyl alcohol and ether
d. sec-butyl alcohol and neopentyl alcohol
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 Chem 31.1 Laboratory Manual

e. propene and butanol

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Department of Chemistry, College of Arts and Sciences, University of the Philippines Visayas, Miagao, Iloilo