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Classification Tests for Hydroxyl- and Carbonyl-containing

Compounds
Sio, Camille; Sison, Gwen; Tolentino, Ana Lou; Tolentino, Rhodelyn; Uy, Kim;
Villanueva, Anna
Group 7, 2F-PH

ABSTRACT
Hydroxyl- and Carbonyl-containing compounds were classified through different tests.
Certain samples that were used in classifying compounds were ethanol, n-butyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, benzyl alcohol, n-butyraldehyde, benzaldehyde,
acetone, acetophenone, isopropyl alcohol and acetaldehyde. The tests performed were
the following: solubility test of alcohols in water, which was used to distinguish which
type of alcohol is miscible or immiscible with water and to determine the amount of
water needed for the solution to produce a homogenous dispersion; Lucas test, which
was used to differentiate primary, secondary, and tertiary alcohols; Chromic acid test to
determine if the sample undergoes oxidation and to classify ketones and aldehydes;
2,4-dinitrophenylhydrazone or 2,4-DNP test, which was also used to identify aldehydes
and ketones; Fehlings test and Tollens silver mirror test were used to find out which
among the tested samples are aldehydes; lastly, iodoform test for the determination of
methyl ketones.

INTRODUCTION
Alcohol is a class of organic
compounds bearing the functional group
OH (hydroxyl) group singly bonded to
a carbon atom, both atoms being sp3
hybridized. Two sp3 hybrid orbitals of
oxygen form sigma bonds to atoms of
carbon and hydrogen. The other two sp3
hybrid orbitals of oxygen each contain
an unshared pair of electrons. The most
important physical property of alcohols
is the polarity of the hydroxyl group,
with oxygen bearing a partial negative
charge and both the carbon and
hydrogen bonded to it bearing partial
positive charge. Alcohols interact with

water by hydrogen bonding and


therefore are more miscible in water
than are hydrocarbons of comparable
molecular weight.
Alcohols may be classified as 1,
2, 3 depending whether the OH
group is bonded to a primary,
secondary, or tertiary carbon.

Figure 1. Ball-and-stick model of the hydroxyl


functional group in an alcohol molecule (R3COH)

comparable molecular weight.


Organic compounds with a
carbonyl group constitute of carboxylic
acids, esters, anhydrides, acyl halides,
amids and quinines. They are composed
of an sp2 hybridized carbon and oxygen,
forming a double bond between the two
atoms. The carbonyl group is also the
characteristic functional group of
aldehydes and ketones.
The functional group of an
aldehyde, also known as an aldehyde
group is a carbonyl group bonded to a
hydrogen atom. Ketone, on the other
hand, contains a carbonyl group bonded
to two adjacent carbons. The carbonyl
group in ketones is placed in the middle
of the chain, between two carbon
atoms, instead of being placed in the
terminal part, which is a characteristic of
aldehydes. Both functional groups are
polar compounds and they interact in
the pure state by dipole-dipole
interactions. They have higher boiling
points and are more soluble in water
than are non-polar compounds or

The tests performed in the experiment


that were used to classify the organic
compounds were Solubility of Alcohols in
Water, Lucas Test, Chromic Acid Test
(Jones
Oxidation),
2,4Dinitrophenylhydrazon Test, finally, the
Iodoform Test.
The solubility of the alcohols in
water were tested to determine which
among the samples is the most miscible
and the least miscible. As mentioned
earlier, alcohols are polar molecules
hence, they are miscible in the presence
of water.
Lucas test is used to determine
the existence of the hydroxyl group in
the given samples. Tert-butyl alcohols
give a positive result because they easily
yield a carbocation as an intermediate
product.
Chromic acid test is the test for
oxidation of alcohols. The presence of a
hydroxyl substituent on a carbon
bonded to at least on hydrogen is
detected first to determine if it is
capable of being oxidized.
2,4-DNP test is a procedure used
to determine the presence of the ketone
or aldehyde functional group in a
compound.

Figure 2. An aldehyde

Figure 3. A ketone

Fehlings test and Tollens silver


mirror test are performed to prove the
presence of aldehyde functional group.
The former is employed when aliphatic
aldehydes are used whereas the latter
can be used for both aliphatic and
aromatic aldehydes.

Iodoform test is a test for the


presence of methyl ketones. Methyl
ketones are not the only compounds
that result in a positive iodoform test.
Secondary alcohols having an adjacent
methyl group are oxidized into methyl
ketones by the iodoform test reagent.
These methyl ketones then give a
positive iodoform test.
The objectives of the experiment were
to a) differentiate a hydroxyl- or
carbonyl-containing compound, b) to
make a distinction among primary,
secondary and tertiary alcohols and c)
to distinguish an aldehydes from
ketones.

EXPERIMENTAL
A. Samples used
The samples tested include ethanol, nbutyl alcohol, sec-butyl alcohol, tertbutyl alcohol, benzyl alcohol, nbutyraldehyde, benzaldehyde, acetone,
acetophenone, isopropyl alcohol and
acetaldehyde.
B. Procedure
1. Solubility of Alcohols in Water
Ten drops of each of the alcohol
samples were placed in five previously
labeled (A through E) test tubes with
the aid of a Pasteur pipette. The
alcohols are listed below into the
appropriate tube:
A - ethanol
B - n-butyl alcohol
C - sec-butyl alcohol

D - tert-butyl alcohol
E - benzyl alcohol
One mL of water was added dropwise to
the tube containing the alcohols. The
mixtures were shaken thoroughly after
each addition. When cloudiness resulted
from this, 0.25 mL of water was added
at a time and was vigorously shaken
until a homogenous dispersion resulted.
The total volume of water added was
noted. When no cloudiness resulted
after the addition of 2.0 mL water, it
meant the alcohol was soluble in water.
The results of this procedure were
noted.
2. Lucas Test
To prepare the reagent, 16 g of
anhydrous zinc chloride was dissolved in
10 mL of concentrated HCl. After the
mixture was cooled, about 50 mg (2-3
drops) of the sample was added to 1 mL
of the prepared reagent in a small vial.
The vial was capped and the mixture
was vigorously shaken for a few
seconds and was allowed to stand at
room temperature. This test was
performed on n-butyl alcohol, sec-butyl
alcohol and tert-butyl alcohol. The rate
of the formation of the cloudy
suspension or the formation of 2 layers
was observed.
3. Chromic Acid Test (Jones Oxidation)
The reagent was prepared by dissolving
20 g of chromium trioxide (CrO3) in 60
mL of cold water in a beaker. Twenty
mL of concentrated sulfuric acid was
added to the solution slowly and
carefully with stirring.

After the preparation of the reagent,


one drop of liquid or a small amount of
the solid sample was dissolved in 1 mL
of acetone in a vial. Five drops of
chromic acid reagent was added one
drop at a time, while the mixture was
shaken. Then, the test tubes were
placed in a 60C water bath for five
minutes. The color of each solution was
noted after heating the mixture. This
test was conducted on n-butyl alcohol,
acetaldehyde, acetone and isopropyl
alcohol.
4. 2,4-dinitrophenylhydrazone (or 2,4DNP) Test
To prepare the reagent, a solution of 3g
of 2,4-dinitrophenylhydrazine in 15 mL
of concentrated H2SO4 was added slowly
while stirring to a mixture of 20 mL of
water and 70 mL of 95% ethanol. The
mixture was stirred and filtered.
Once the reagent was prepared, a drop
of the liquid sample was placed in a
small test tube. Then, five drops of 95%
ethanol was added and the mixture was
shaken well. After shaking, three drops
of
2,4-dinitrophenylhydrazine
was
added. The solution was allowed to
stand when no yellow or orange-red
precipitate formed. Ths test was
performed on acetone, acetaldehyde, nbutyraldehyde,
benzaldehyde
and
acetophenone.
5. Fehlings test
Fehlings A: Seven grams of hydrated
copper (II) sulfate was dissolved in 100
mL of water

Fehlings B: 35 grams of potassium


sodium tartrate and 10 grams of NaOH
were placed in 100 mL water.
Into each test tube, 1 mL of freshly
prepared Fehlings reagent (made by
mixing equal amounts of Fehlings A and
B) was placed into a test tube. Then,
three drops of the sample to be tested
were added to the Fehlings reagent.
The tubes were placed in a beaker of
boiling water and changes which
occurred within 10-15 minutes were
observed. The test was performed on
aldehyde, n-butyraldehyde, acetone,
benzaldehyde and acetophenone as
well.
6. Tollens Silver Mirror Test
The reagent was prepared by adding
two drops of 5% NaOH solution to 2 mL
of 5% silver nitrate solution and the
mixture was mixed thoroughly. Then,
enough 2% ammonium hydroxide was
added drop by drop and with stirring to
dissolve the precipitate.
Four test tubes with 1 mL of the Tollens
reagent were prepared. Two drops each
of the samples were added separately:
acetaldehyde, acetone. The mixture was
shaken and allowed to stand for 10
minutes. It was placed in a beaker of
warm water (35-50C) when no reaction
had occurred.
7. Iodoform Test
Two drops of each sample (acetone,
benzaldehyde and isopropyl alcohol)
were placed into their own vial and 20
drops of 10% KI solution was added.
While shaking the mixture, 20 drops of

fresh chlorine bleach (5% sodium


hypochlorite) was added slowly to each
tube and the mixture was mixed. The
formation of a yellow precipitate was
noted, indicating a positive result.

RESULTS AND DISCUSSION


For the solubility test of alcohols
in water, the turbidity of the product
produced in the interaction of water
with alcohol indicated immiscibility of
the alcohol. The amount of water
needed to produce a homogenous
dispersion was also determined.
Table 1. Solubility of Alcohols in Water
Alcohol

Ethanol
n-butyl
alcohol
sec-butyl
alcohol
tert-butyl
alcohol
Benzyl
alcohol

Amount of
water
(in
mL) needed
to produce a
homogenous
dispersion
1 mL
1.75 mL

Solubility
to water

a polar compound. Based on the


amount of water needed to produce a
homogenous dispersion, the first, third
and fourth sample required only 1 mL of
water. This points out that the number
of carbon atoms and the number of
substituents or branches may affect the
solubility of alcohols. According to the
data gathered, the sample containing
the lower number of carbon atoms and
those with more branches are more
miscible in water. The latter is only
applicable for organic compounds
having the same number of carbon
atoms present.
The three types of alcohols may
be determined through the Lucas test.
Turbid or cloudy products indicate the
formation of alkyl chloride.
Table 2. Lucas Test
Alcohol

Result observed

miscible
miscible

n-butyl alcohol

Clear solution

sec-butyl alcohol

Clear solution

1 mL

miscible

tert-butyl alcohol

Cloudy suspension

1 mL

miscible

2 mL

immiscible

As presented in the table, all


alcohol samples except for benzyl
alcohol showed miscibility in water. The
principle of like dissolves like applies
to this test therefore, ethanol, n-butyl
alcohol, sec-butyl alcohol and tert-butyl
alcohol are said to be polar compounds
since they did not form a cloudy product
when reacted with water, which is also

The table above shows that tertbutyl alcohol readily formed a cloudy
suspension with the addition of the
Lucas reagent compared with n-butyl
and sec-butyl alcohol. This is because
the first sample is a 1 alcohol; the
second a 2; and the third a 3. The
reaction had undergone SN1 reaction,
where a carbocation is formed as an
intermediate product. The stability of
the carbocation is the main factor that
affects the reactivity of alcohols.
Therefore a tertiary alcohol forming the

tertiary carbocation is the most reactive


among the three samples. ZnCl2, a
compound present in the reagent is a
good Lewis acid, making the reaction
more acidic and consequently enhancing
the formation of carbocations.
The Chromic Acid test is the test
for oxidation of alcohols or compounds
with reducing properties. The formation
of a blue green solution indicates a
positive result.
Table 3. Chromic Acid Test
Sample
n-butyl alcohol
Acetaldehyde
Acetone
Isopropyl alcohol

Result Observed
Blue green solution
Blue green solution
Brownish
yellow
solution
Blue green solution

Based on the results above, all


samples except for acetone yielded a
positive result. Chromic acid test
involves oxidation of primary and
secondary alcohols and aldehydes and
the reduction from Cr6+ to Cr3+. Primary
alcohols reacted with chromic acid to
synthesize aldehydes which are further
oxidized to carboxylic acids since the
oxidizing agent used was a strong one.
Secondary alcohols, on the other hand,
reacted with chromic acid to form
ketones, which do not undergo
oxidation.
2,4-dinitrophenylhydrazone
(or
2,4-DNP) test was used to determine
the presence of the ketone or aldehyde
functional group in a compound. The
formation of a yellow-orange precipitate
shows a positive result

Table 4. 2,4-dinitrophenylhydrazone
Test
Sample
Acetaldehyde
Benzaldehyde
Acetone
Acetophenone

Result Observed
yellow-orange
precipitate
yellow-orange
precipitate
yellow-orange
precipitate
orange precipitate

Based on the data presented in


the table, the first three samples yielded
a yellow orange precipitate except for
acetophenone which produced an
orange precipitate. The formation of the
latter indicated the existence of
conjugated carbonyl compounds and the
formation of yellow-orange precipitate
indicated the presence of uconjugated
carbonyl compounds.
Fehlings test was used to
distinguish an aldehyde from a ketone.
The formation of a brick-red precipitate
is the positive result produced by
aldehydes.
Table 5. Fehlings Test
Sample
Acetaldehyde
Benzaldehyde
Acetone
acetophenone

Result Observed
Brick red precipitate
Brick red precipitate
No precipitate
No precipitate

The table above shows that only


acetaldehyde
and
benzaldehyde
(aldehydes) produced a brick red
precipitate
and
acetone
and
acetophenone (ketones) did not react to
form the precipitate. The formation of

the brick red precipitate indicates the


oxidation of aldehydes into carboxylic
acids. To sum it up, Fehlings test
involves a redox reaction.
Similar with Fehlings test,
Tollens silver mirror test is also a test to
differentiate aldehydes from ketones. In
this test, aldehydes are to be oxidized.
Table 6. Tollens Silver Mirror Test
Sample
Acetaldehyde
acetone

Result Observed
Silver mirror
No reaction

As shown in the table, only


acetaldehyde formed a silver mirror and
acetone, which is a ketone did not form
this product. Silver diamine complex
was formed in preparing the reagent for
this test. This complex exhibits solubility
property in water in basic solutions. The
Tollens test, just like the previous tests
also involves redox reaction. Aldehydes
were once again oxidized into carboxylic
acids and silver gained an electron,
hence it is reduced from Ag1+ to Ag0.
The presence of methyl ketones
may be identified through the iodoform
test. The formation of a yellow
crystalline
precipitate
indicates
a
positive result.
Table 7. Iodoform Test
Sample
Benzaldehyde
Acetone
Isopropyl alcohol

Results Observed
Brown precipitate
Yellow crystalline
precipitate
Yellow crystalline
precipitate

As presented on the table above,


only acetone and isopropyl alcohol gave
a positive result of yellow crystalline
precipitate. Based on the structure of
acetone or 2-propanol, it is evident that
methyl ketone is present hence it
yielded a positive result. Isopropyl
alcohol, on the other hand, was oxidized
by iodoform (reagent and also an
oxidizing agent) to form an aldehyde or
a methyl ketone and also gave a
positive result.

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