Classification Tests for Hydroxyl- and Carbonyl- Containing Compounds

Ongchuan, C.F., Martinez, J.G., Ngo, M.C., Pangilinan, A.D., Pantig, P.P., Paulino, R.P.
Group 5, 2KMT, Faculty of Pharmacy

Abstract. Most of the time, organic compounds are insoluble in polar compounds such as, water except for low
molecular-weight amines and oxygen containing compound like: alcohols, carboxylic acids, aldehydes, and
ketones. The main objectives of this experiment is to distinguish whether a compound is hydroxyl- (OH) or
carbonyl- (C=O) containing; to see the distinction between the aldehydes and ketones; to differentiate the three
types of alcohols and to explain the mechanisms involved in the tests. In this conducted experiment hydroxyl
and carbonyl compounds were tested. The samples, ethanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl
alcohol, benzyl alchohol, n-butylraldehyde, benzaldehyde, acetone, acetophenone, isopropyl alcohol and
acetaldehyde, were analyzed by performing several differentiating tests involving their solubility in water such
as: Lucas test, Chromic Acid test, 2,4-Dinitrophenylhydrazone, Fehlings test, Tollens Silver Mirror test, and
Iodoform test. The Lucas test is done to differentiate primary, secondary and tertiary alcohols and gave a visible
turbity in the solution. The chromic acid is performed to see the dissimilarities of ketones and aldehydes in
which the ketones yields a result of s blue-green suspension. The 2-4 dinitrophenylhydrazone test is done as a
collateral for carbonyl groups and therefore gives a visible result of red-orange precipitate or yellow precipitate
for aldehydes and ketones. The Fehlings and Tollens tests are done to pinpoint different positive results of
aldehydes and lastly, the Iodoform test is conducted to to be used as a confirmatory for methyl carboynyl groups
which gives a positive results of yellow crystals or precipitate. Finally, it is proven that the samples used that are
classified as ketones, n-butyraldehyde, benzaldehyde and acetaldehyde are aldehydeswhile acetone and
acetophenone, contain carbonyl groups in their structures. Alcohols that are classified under the hydroxyl
groups are: Ethanol, n-butylalcohol, sec-butyl alcohol, tert -butyl alcohol and benzyl alcohol. The tertiary
alchohols are more stable while the primary alcohols are most polar among the three.
Introduction.
Alcohols are organic molecules containing
the hydroxyl functional group, OH- directly bonded
to a saturated, sp hybridized carbon atom (see
figure 1). Alcohols can be classified as primary (1),
secondary (2), or tertiary (3) depending on the
number of carbon substituents bonded to the
hydroxyl-bearing carbon. Primary alcohols have
the hydroxyl group on a primary (1) carbon atom
(see figure 2), which is bonded to only one other
carbon atom while a secondary alcohol has the
hydroxyl group on a secondary (2) carbon atom,
which is bonded to two other carbon atoms (see
figure 3). Similarly, a tertiary alcohol has the
hydroxyl group on a tertiary (3) carbon atom,
which is bonded to three other carbons (see figure
4). The most important physical property of

alcohols are the polarity of their OH groups.

Because of the large difference in electronegativity
between oxygen and carbon and between oxygen
and hydrogen, both the C-O and O-H bonds of an
alcohol are polar covalent, and alcohols are polar
molecules (Brown & Poon, 2011). The high
electronegativity of the oxygen compared to carbon
leads to the shortening and strengthening of the -OH
bond. The presence of the -OH groups allows for
hydrogen bonding with other -OH groups, hydrogen
atoms, and other molecules. Alcohols usually have
much higher boiling points than might be expected
from their molar masses. This difference can be
understood if we consider the types of
intermolecular attractions that occur in these liquids

carbonyl's polarity increases the melting and boiling

points, and influences the compound's solubility.

Figure 1. structure of an alcohol

Figure 2. Primary alcohol 1,

2-methylpropan-1-ol

The simplest carbonyl groups are aldehydes and

ketones, they are usually attached to another carbon
compound. It is important to understand that
aldehydesare organic compounds containing a
terminal carbonyl group. The functional group of an
aldehyde is a carbonyl group bonded to a hydrogen
atom. Thus the chemical formula for an aldehyde
functional group is -CH=O, and the general
formula for an aldehyde is R-CH=O (see figure 5).
On the other hand, the functional group of a ketone
is a carbonyl group bonded to two other carbon
atoms (see figure 6). They differ from aldehydes in
a way that the carbonyl is placed between two
carbons rather than at the end of the molecule.
Because of the polarity of the carbonyl
group, aldehydes and ketones are polar compounds
and interact in the liquid state by dipole-dipole
interactions. Therefore, aldehydes and ketones have
higher boiling points compared to nonpolar
compounds.

Figure 3. Secondary alcohol 2,

2-butanol

Figure 5. Structure of an
aldehyde
Figure 4. Tertiary alcohol 3,
2-methylpropan-2-ol / Tert-butyl
alcohol
A carbonyl group is a functional group
where a carbon atom is double bonded to an oxygen
atom. Because of a difference in the electron
affinities of the carbon and oxygen atoms, the
electron pairs that constitute the double bond are
held closer to the oxygen atom than to the carbon
atom; the electron-rich oxygen atom acquires a
negative charge and the electron-deficient carbon
atom a positive charge. Thus, molecules containing
the carbonyl group are polar. Furthermore, a

Figure 5. Structure of a ketone

Several tests can be used to determine and
differentiate alcohols, ketones and aldehydes. the
commonly used tests are Solubility test, Lucas test,
Chromic Acid test (Jones Oxidation), 2,4dinitrophenylhydrazine (2,4-DNP) test, Fehlings
test, and Tollens Silver Mirror test and Iodoform
tests.

Lucas test in alcohols is a test which is used

to distinguish between primary, secondary and
tertiary alcohols. It is based on the difference in
reactivity of the three classes of alcohols with
hydrogen halides. This test is carried out with the
help of Lucas reagent, which is a solution of
anhydrous zinc chloride and concentrated
hydrochloric acid (ZnCl2 + HCl).

Figure 6. SN1 mechanism of Lucas test

Chromic acid is a strong oxidizing agent,
used to oxidize many classes of organic compounds,
the most common of which is alcohols.
Any alcohol containing at least one alpha hydrogen
is oxidized by chromic acid, so tertiary alcohols are
not oxidized by chromic acid. Chromic acid test or
commonly known as Jones oxidation is done to
distinguish primary (1) and secondary (2) alcohols
and aldehydes from tertiary (3).

2,4-Dinitrophenylhydrazone test is used to

detect the carbonyl functionality of a ketone or
aldehyde functional group. If the carbonyl
compound is aromatic, then the precipitate will be
red; if aliphatic, then the precipitate will have a
more yellow color.

Figure 7. Mechanism for Chromic Acid test

both

A specific test that constitutes the reaction of

aldehydes
and
ketones
is
2,4

dinitrophenylhydrazine (DNP). It functions as a

derivative formation which shows whether the
carbonyl group in the unknown is conjugated or
unconjugated. If the solid 2,4- DNP shows a yellow
color, it means that the carbonyl group is
unconjugated; whereas the reddish-orange color
means that the carbonyl group in the unknown is
unconjugated.

Fehling's solution is used as a chemical

test used
to
differentiate
between
water
soluble aldehyde and ketone functional
groups.
However, Fehling's solution can only be used to test
for aliphatic aldehydes. Aldehydes are oxidized,
giving a positive result but ketones do not react,
unless they are alpha-hydroxy-ketones.

Figure 8. Mechanism for Fehlings test

Silver mirror test is a qualitative laboratory
test used to distinguish between an aldehyde and a
ketone. The procedure considers that aldehydes are
oxidized by silver (I) to generate a carboxylic acid
and silver metal, which coats the surface of the
glass vessel. Tollens' reagent is also used to test for
both aliphatic and aromatic aldehydes.

Methods.
A.

Sample Compounds
n-butyl alcohol, sec-butyl alcohol,
tert-butyl alcohol, Acetaldehyde, nbutylraldehyde, Benzaldehyde, Acetone,
Acetophenone, Isopropyl alcohol

B.

Procedure
1. Solubility of Alcohols in Water
Five test tubes were labeled from A
to E. With the aid of a Pasteur pipette,
10 drops each of ethanol, n-butyl
alcohol, sec-butyl alcohol, tert-butyl
alcohol, benzyl alcohol were added
into the appropriate test tube. 1 mL of
water was then added dropwise to the
tube containing alcohol, and the
mixture was shaken thoroughly after
each addition. For the results of
cloudiness, 0.25 mL of water was
added at a time with vigorous shaking
until a homogeneous dispersion
resulted. The total volume of water
added was noted. The alcohol was
soluble to water to those results with
no cloudiness obtained after the
addition of 2.0 mL. The results were
noted.

Figure 9. Mechanism for Silver mirror test

Triiodomethane (iodoform) reaction can be
used to identify the presence of an aldehyde or
ketone in which one of the groups directly attached
to the carbonyl carbon is a methyl group. The test
uses iodine and sodium hydroxide solution. Only
methyl ketones can undergo the iodoform reaction
because only methyl ketones have three H atoms on
the alpha carbon which are necessary to form the
iodoform product. Acetaldehyde has an -methyl
group which behaves the same as methyl ketones.
Alcohols that upon oxidation form methyl ketones
will also undergo this reaction. A positive result of
this test is the formation of a pale yellow precipitate
of triiodomethane.

2.

Lucas Test
Lucas reagent was prepared by
dissolving 16g of anhydrous zinc
chloride in 10 mL of concentrated
hydrochloric acid. The mixture was
then allowed to cool. About 50mg(2-3
drops) of the sample were added to
1mL of the reagent prepared in a small
vial. The vial was capped and shaken
vigorously for a few seconds. The
mixture 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
formation of the cloudy suspension or

the formation of two layers was

observed.

3.

Chromic Acid Test (Jones Oxidation)

The reagent was prepared by
dissolving
20g
of
chromium
trioxide(CrO3) in 60mL of cold water
in a beaker. While it was stirred, 20
mL of concentrated sulfuric acid was
added slowly and carefully to the
solution. The reagent should be
prepared fresh each time. A drop of of
liquid was mixed or a small amount of
solid was dissolved in 1mL of acetone
in a small vial. 5 drops of the reagent
were added, one drop at a time, while
the mixture was shaken. The test tubes
were placed in a 60C water bath for 5
minutes. The color of each solution
was noted. This test was performed on
n-butyl alcohol, isopropyl alcohol,
tert-butyl
alcohol,
acetaldehyde,
benzaldehyde, and acetone.

4.

6.

Fehlings Test

Tollens Silver Mirror Test

The reagent was prepared by adding
2 drops of 5% sodium hydroxide
solution to 2 mL of 5% silver nitrate
solution, it was then mixed
thoroughly.
Only
enough
2%
ammonium hydroxide was added drop
by drop while being stirred to dissolve
the precipitate. The will fail if excess
ammonia is added. Four test tubes
with 1mL of freshly prepared Tollens
reagent was prepared. 2 drops of each
of the samples were added separately:
acetaldehyde, benzaldehyde, acetone,
and acetophenone. The mixture was
shaken and was allowed to stand for
10 minutes. If no reaction had
occurered, the tube was placed in a
beaker of warm water(35-50C) for 5
minutes. The observation was
recorded.

2,4-dinitrophenylhydrazone (or 2,4DNP)

Test The reagent was prepared by
adding slowly a solution of 3g of 2,4dinitrophenylhydrazine in 15 mL of
concentrated H2SO4 while it was
stirred to a mixture of 20 mL of water
and 70mL of 95% ethanol. It was then
stirred and filtered. A drop of a liquid
sample was placed into a small test
tube. 5 drops of 95% ethanol were
added and shaken well. Afterwards, 3
drops of 2,4-dinitrophenylhydrazine
was added. The solution was allowed
to stand for at least 15 minutes if no
yellow or orange-red precipitate
formed. This test was performed on
acetone, acetaldehyde, benzaldehyde,
and acetophenone. The results were
described and noted.

5.

Fehlings A reagent was prepared by

dissolving 7g of hydrated copper(II)
sulfate in 100 mL of water. Fehlings
B reagent was prepared by adding 35g
of potassium sodium tartrate and 10g
of NaOH in 100 mL of water. 1mL of
freshly prepared Fehlings reagent was
placed into each test tube( made by
mixing equal amounts of Fehlings A
and Fehlings B). 3 drops of the
sample to be tested were added. The
tubes were placed in a beaker of
boiling water and the changes which
occurred within 10-15 minutes, were
observed. This test was performed on
acetaldehyde, acetone, benzaldehyde,
and acetophenone.

7.

Iodoform Test
2
drops
of
each
sample
(acetaldehyde, acetone, acetophenone,
butyraldehyde, benzaldehyde, and
isopropyl alcohol) were placed into its
own vial. 2O drops of 10% KI
solution was added as well.
Afterwards, 20 drops of fresh chlorine

bleach(5% sodium hypochlorite) was

added slowly while shaking to each
test tube and then mixed. The
formation of a yellow precipitate was
noted.

Results and Discussion.

Table 1. shows the test for the solubility in
water of the following alcohols: Ethanol, n-butyl
alcohol, sec-butyl alcohol, tert-butyl alcohol and
benzyl alcohol. Turbidity of the solution was to be
observed and cloudiness of the solution would
indicate the insolubility of that specific alcohol to
water. The amount of water needed to produce
homogenous dispersion was also observed and the
condensed structural formula of each compound
was noted.
Table 1. Solubility of Alcohols in water

Alcohol

Condensed
Structural
Formula

Amount of
water needed
Solubility
to
produce
in water
homogenous
dispersion

Ethanol

0.25mL

Soluble

n-butyl
alcohol

1.5mL

Soluble

2mL

Soluble

Secbutyl
alcohol
Tertbutyl
alcohol

1.25mL

Soluble

Benzyl
alcohol

2mL

Insoluble

Based from the results, ethanol, n-butyl alcohol,

sec-butyl alcohol and tert-butyl alcohol all proved to
be soluble with water compared with benzyl
alcohol, the only one that was insoluble. This
follows the principle like dissolves like since the
4 alcohols are soluble with water, a polar
compound, they are therefore, polar. Among the
alcohols that were soluble in water, ethanol, n-butyl
alcohol, sec-butyl alcohol, and tert-butyl alcohol,
they all required different amounts of water for it to
be considered soluble. This may be due to the
different factors that affect its solubility in water,
one of these factors is the number of carbon atoms
present in the molecule. The lower the number of
carbon atoms present, the more soluble or more
miscible a substance is. Branching of carbon chains
also affect solubility. The more branching present,
the more soluble a compound is. This is only true
for organic compounds that have the same number
of carbon atoms present.
Table 2. shows the reaction of the alcohols:
n-butyl alcohol, sec-butyl alcohol and tert-butyl
alcohol when subjected to the Lucas test. The lucas
test differentiates 1, 2, and 3 alcohols and a
positive result is given by the formation of a white
turbid or cloudy solution.
Table 2. Lucas test results

Alcohol
n-butyl alcohol

Lucas
test
reaction
Clear
colorless
solution

Sec-butyl alcohol

Cloudy solution

Tert-butyl alcohol

Cloudy solution

From the results we can deduce that of the

three samples, sec-butyl alcohol and tert-butyl

alcohol yielded a positive result with the lucas test

while n-butyl alcohol proved to be soluble. The
reaction mechanism involved in the Lucas test is
based on SN1 reaction, which depends on the
formation of stable carbocations. Reactivity of
alcohols in SN1 reaction is 3 > 2 > 1.
Table 3. shows the reaction of the following
alcohols: n-butyl alcohol, tert-butyl alcohol,
acetaldehyde, benzaldehyde, acetone, and isopropyl
alcohol under the Chromic Acid test. The Chromic
acid test shows a positive result for 1 and 2
alcohols and aldehydes indicated by a blue green
solution.

Table 3. Chromic acid test results

do not oxidize further and 3alcohols were

usually unreactive and aldehydes were oxidized to
carboxylic acids.
Table 4. shows the reaction of the alcohols:
acetaldehyde,
benzaldehyde,
acetone
and
acetophenone when subjected to the 2,4dinitrophenylhydrazone (or 2,4-DNP) test. This test
is done to detect the presence of carbonyl groups
and the test is positive for aldehydes and ketones
indicated by the formation of an orange precipitate.

Table 4. 2-4 DNP test results

Alcohol

Chromic Acid test

reaction

Alcohol

n-butyl alcohol

Blue green solution

Acetaldehyde

Tert-butyl alcohol

Blue green solution

Benzaldehyde

Acetaldehyde

No reaction

Benzaldehyde

No reaction

Acetone

Blue green solution

Isopropyl Alcohol

Blue green solution

From table 3. the alcohols, n-butyl

alcohol, tert-butyl alcohol, acetone and isopropyl
alcohol produced a positive result of a blue green
solution for the Chromic acid test. In Chromic Acid
test, aldehydes and primary alcohols are oxidized to
carboxylic acids while the Cr+6 ion in the chromic
acid is reduced to Cr+3, also secondary alcohols are
oxidized to ketones while the Cr+6 ion in the
chromic acid is reduced to Cr+3. 1 alcohols reacted
with chromic acid to yield aldehydes, which are
further oxidized to carboxylic acids, 2 alcohols
reacted with chromic acid to yield ketones, which

Acetone
Acetophenone

2-4
DNP
reaction
Formation
precipitate
Formation
precipitate
Formation
precipitate
Formation
precipitate

test

of orange
of orange
of orange
of orange

Based from the results, all samples produced

a positive result indicated by the formation of an
orange precipitate. Hence, 2,4-DNP test proved that
all the samples, acetaldehyde, benzaldehyde,
acetone, acetophenon are carbonyl-containing
compounds and are either aldehydes or ketones.
Table 5. shows the reaction of acetaldehyde,
benzaldehyde, acetone and acetophenone when
subjected to Fehlings test. This test is another
differentiating test for aldehydes and ketones.
Aldehydes will give a positive result in this test by
yielding a brick red precipitate while ketones would
have no reaction.

Table 5. Fehlings test results

Alcohol

Fehlings
reaction

test

Acetaldehyde

Brick red precipitate

Benzaldehyde

Brick red precipitate

Acetone

No reaction

Acetophenone

No reaction

From the results acetaldehyde and

benzaldehyde produced a positive result while
acetone and acetophenone had no reaction.
Fehlings test involves a redox reaction. The
bistartratocuprate(II) complex in Fehling's solution
is an oxidizing agent and the active reagent in the
test. Aldehydes are oxidized, giving a positive
result, but ketones do not react, unless they are
alpha-hydroxy-ketones. The bistartratocuprate(II)
complex oxidizes the aldehyde to a carboxylate
anion, and in the process the copper(II) ions of the
complex are reduced to copper(I) ions. Red
copper(I) oxide then precipitates out of the reaction
mixture, which indicates a positive result i.e.
that redox has taken place.
Table 6. shows the reaction of the following
alcohols when they undergo the Tollens silver
mirror test: acetaldehyde, benzaldehyde, acetone
and acetophenone. Tollens test is used primarily as
another test to differentiate aldehydes from ketones
where aldehydes are expected to be oxidized and
form a silver mirror.
Table 6. Tollens silver mirror test results

Alcohol

Tollens
mirror
reaction

Acetaldehyde

Silver mirror

Benzaldehyde

No reaction

silver
test

Acetone

No reaction

Acetophenone

No reaction

From the table, only acetaldehyde yielded a

positive result with the test while the rest had no
reaction. The Tollens Silver Mirror test involved
reduction-oxidation or redox reaction. Aldehydes
were oxidized to carboxylic acids while ketones did
not undergo oxidation except alpha-hydroxyketone.
Silver was reduced from Ag1+ to Ag0.
Table 7. shows the reaction of acetaldehyde,
benzaldehyde, n-butylraldehyde, acetone, isopropyl
alcohol and acetophenone when subjected to
Iodofrom test. Iodoform test is used to detect the
presence of a CH3CO group in aldehydes and
ketone. A positive result is the appearance of a very
pale yellow precipitate of triiodomethane, CHI3.
Table 7. Iodoform test results
Iodoform

Alcohol

reaction

Acetaldehyde

Formation
ppt

Benzaldehyde

No reaction

n-butylraldehyde

No reaction

Acetone
Acetophenone
Isopropyl alcohol

test

Formation
ppt
Formation
ppt
Formation
ppt

of

yellow

of

yellow

of

yellow

of

yellow

From the results, only benzaldehyde and nbutylraldehyde failed to give any reaction with the
iodoform test while acetaldehyde, acetone,
acetophenone, and isopropyl alcohol produced a
positive result indicated by the formation of a
yellow precipitate. An alkaline solution of sodium
hypoiodite, formed from sodium hydroxide and
iodine, converted acetaldehyde and aliphatic methyl
ketones into iodoform (haloform reaction). Since
the reagent was also an oxidizing agent, alcohols
which are readily oxidized to acetaldehydes or
methyl ketones also gave a positive reaction. The
mechanism of iodoform synthesis occurred through

a series of enolate anions, which are iodinated;

hydroxide displaced the Cl3- anion through an
addition/elimination pathway

ooks/boundless-chemistry-textbook/organicchemistry-23/functional-group-namesproperties-and-reactions-166/alcohols-6387231/

Conclusion.
Once all tests were performed in classifying
certain organic compounds, it can be concluded that
test compounds tested have similar intrinsic
physical properties such as appearance, color, and
physical state. However, in order to classify them
more accurately, they have very distinct odors from
each other. Classification by chemical properties
would be a more accurate basis in differentiating
hydrocarbons.

List of references.
Boundless. Alcohols. Boundless Chemistry.
Boundless, 08 Aug. 2016.
Retrieved
19
Nov.
2016
from
https://www.boundless.com/chemistry/textb

The Triiodomethane (iodoform) reaction with

aldehydes
and
ketones.
(n.d.).
Retrieved November 20, 2016,from
http://www.chemguide.co.uk/organicprops/c
arbonyls/iodoform.html
Fehlings test (n.d.) Randy Sullivan, University of
Oregon Chemistry Department and UO Libraries
Interactive Media Group
Retrieved November 20, 2016 from
http://chemdemos.uoregon.edu/demos/Fehli
ng-Test
McMurry, J. (2016). Organic chemistry (Philippine
edition). USA: Cengage
Learning
Asia
Pte.
Ltd