Analysis of Alcohols, Aldehydes and Ketones

Karl Wayne Mancao, Raphaell Mordeno, Andres Pastrana III*, and Shannen Peaverde
Department of Biology, University of Santo Tomas, Manila, Philippines

Abstract
The proponents have done several tests for identifying alcohols, aldehydes and ketones. These
tests are Dichromate test, Tollens test, Lucas test, DNPH test and Iodoform test. Three samples got
positive result in dichromate test and one in Tollens test. Lucas test got one sample that has a positive
result, DNPH test got two positive results and Iodoform test also got two. All unknowns are identified
from which of the samples are they. Alcohols, aldehydes and ketones are excellently recognized after
the experiment.
Introduction
Oxygen is a chemical element that most living things need. It surrounds the atmosphere and
sustains our life to the fullest. It has an atomic number of eight and with a symbol O. It is also the third
most abundant element in the universe and makes up the 21% in the earth atmosphere. The ozone layer
that protects earth the UV lights are made up of oxygen. It was discovered by Charles Fabry and Henri
Buisson on 1931. Oxygen isnt all about a need in earths atmosphere but it is also very important in
organic materials [12] [16].
Functional groups are specific atoms that are grouped to make up a molecule that constitutes a
chemical behavior. Similar functional groups will be observed with the same chemical behavior
regardless of the size of the molecule. These characteristics may be flammable, will have precipitation to
a certain chemical, an acid and etc. With functional groups, the researcher can identify the chemical
characteristics of an organic material. Since they are organic materials, functional groups have a
backbone of carbon with attached hydrogen. There are some functional groups that can exhibit a primary
(1
o
), secondary (2
o
), and tertiary (3
o
) ranking. These ranking is based on how many carbon are attached
to the functional group. There are a lot of functional groups that can be attached to a molecule. These
are alkene, alkyne, alkyl halide, alcohol, ether, thiol, sulfide, aromatic, ketone, aldehyde, carboxylic
acid, acyl hydride, anhydride, amine, amide, ester, and many more. The difference between those
functional groups is the kind of element that attached to them. Mostly, oxygen is common to be
attached. Nevertheless, sulfur, nitrogen, and halogens are also attached [2].
Functional groups that contain sulfur and nitrogen are called Hetero-containing functional
groups. These groups have different atoms that attached to a specific functional group. For sulfur, thiol,
sulfide, disulfide, sulfenic acid, sulfinic acid, sulfonic acid, sulfonate ester, sulfoxide, thiocyanate,
thione, thial, and sulfone are its functional groups. Sulfur has a valence number of six and a chemical
symbol which is S. For nitrogen, amine, amide, imine, imide, azide, azocompound, cyanate, nitrate,
nitrile, nitrite, nitro compound, nitroso compound, and pyridine derivative. Nitrogen has a valence
number of five and a chemical symbol which is N. Another functional groups are the hydrocarbons.
These functional groups only constitute carbon and hydrogen. These are alkanes, alkenes, alkynes and
aromatic [4] [17].
Oxygen-containing functional groups are most abundant in all functional groups. These can be
divided into two sub-group and these are singly bonded oxygen and double bonded oxygen. The
functional groups that are in the singly bonded oxygen are alcohols, ethers and phenols. Alcohols are
like derivatives of water because of the replacement of alkyl group into OH group. It can have hydrogen
bonds and very soluble to water. In the double bonded oxygen, they have a basic group that everybody
exhibits and it is called, carbonyl group or keto. Under this group are aldehydes, ketones, and carboxylic
acids. Aldehydes and ketones are polar but they cant have hydrogen bonds within themselves. Their
boiling and melting points are higher than alkanes or ether but lower than the alcohols. There are still
functional groups under carboxylic acids. They are collectively called the acid derivatives of the
carboxylic acid. These groups are acyl halides which has halogens attached to it, anhydride, esters, and
amides.
Several tests can be performed to identify what functional groups are present in an organic
material. These tests can be Dichromate test, Tollens test, Lucas test, DNPH test, and Iodoform test.
Dichromate test is for the identification of primary/secondary alcohols and aldehydes in an organic
material having a blue solution as a result. It uses a potassium dichromate (K
2
Cr
2
O
7
) and sulfuric acid
(H
2
SO
4
) as the reagent. Tollens test is for the presence of aldehyde only in an organic material having a
silver mirror coat result. It uses tollens reagent [Ag(NH
3
)
2
OH]. Lucas test is for the identification of
tertiary alcohols leading to a result of turbidity. It uses HCl/ZnCl
2
as the reagent. 2,4-
Dinitrophenylhydrazine (DNPH) test is for the manifestation of carbonyl groups in the material with a
result of yellow-orange precipitation. It uses DNPH reagent. Lastly is the Iodoform test that is for the
methylcarbonyl group having a result of yellow precipitation. It uses potassium iodide (KI) and chlorox
(NaOCl) as the reagent [3].
Precipitation is the formation of solid material in a solution. This may happen when two aqueous
solutions are both ionic compounds. Precipitation also results to a two-layer solution. The lower layer
which is often solid or sedentary material is called precipitate while the upper layer that is often liquid is
called the supernate [5]
Condensation reaction is an occurrence when two molecules join together and small atoms lose
in the reaction. This is usually observed in DNPH test [5].

Results and Discussion
Dichromate
Test
Tollens Test

Lucas Test DNPH Test Iodoform Test
Methanol
(1
O
alcohol)
Blue liquid
mixture (+)
Clear colorless
liquid (-)
Clear colorless
liquid (-)
Orange liquid mixture
w/ no precipitation
(-)
Clear colorless liquid
(-)
2-Propanol (2
o

alcohol)
Blue liquid
mixture (+)
Clear colorless
liquid (-)
Clear colorless
liquid (-)
Smoke was
observed
Orange liquid mixture
w/ no precipitation
(-)
With precipitation (2
layers: upper layer-
colorless liquid; lower
layer- yellow ppt) (+)
3-Butanol
(3
o
alcohol)
Orange liquid
mixture (-)
Clear colorless
liquid (-)
Turbid (+)
Smoke was
observed
Orange liquid mixture
w/ no precipitation
(-)
Clear colorless liquid
(-)
Formalin
(Aldehyde)
Blue liquid
mixture (+)
Silver mirror
coat was seen (+)
Clear colorless
liquid (-)
With precipitation (2
layers: upper layer-
orange liquid; lower
layer- yellow ppt) (+)
Red liquid mixture (-)
Acetone
(Ketone)
Orange liquid
mixture (-)
Clear colorless
liquid (-)
Clear colorless
liquid (-)
With precipitation (2
layers: upper layer-
orange liquid; lower
layer- yellow ppt) (+)
With precipitation (2
layers: upper layer-
colorless liquid; lower
layer- yellow ppt) (+)
Unknown 1 Blue liquid
mixture (+)
Silver mirror
coat was seen (+)
Clear colorless
liquid (-)
Smoke was
observed
With precipitation (2
layers: upper layer-
orange liquid; lower
layer- yellow ppt) (+)
Red liquid mixture (-)
Unknown 2 Blue liquid
mixture (+)
Clear colorless
liquid (-)
Clear colorless
liquid (-)
Orange liquid mixture
w/ no precipitation
(-)
Clear colorless liquid
(-)
Unknown 3 Orange liquid
mixture (-)
Clear colorless
liquid (-)
Turbid (+)
Smoke was
observed
Orange liquid mixture
w/ no precipitation
(-)
Clear colorless liquid
(-)
Unknown 4 Orange liquid
mixture (-)
Clear colorless
liquid (-)
Clear colorless
liquid (-)
With precipitation (2
layers: upper layer-
orange liquid; lower
layer- yellow ppt) (+)
With precipitation (2
layers: upper layer-
colorless liquid; lower
layer- yellow ppt) (+)

Based from the results written above, the unknowns are identified as methanol, 2-propanol, 3-
butanol, formalin or acetone. Unknown 1 is a formalin, unknown 2 is methanol, unknown 3 is 3-butanol,
and unknown 4 is acetone. Methanol is only positive in dichromate test while 2-propanol got positives in
dichromate test and iodoform test. 3-butanol got Lucas test as the only positive while formalin got
positives in dichromate test, tollens test and DNPH test. Acetone got DNPH and iodoform test.
Dichromate test uses a reagent called the potassium dichromate (K
2
Cr
2
O
7
) and sulfuric acid
(H
2
SO
4)
. The dichromate oxidizes the primary/secondary alcohols and aldehydes into ketones or
carboxylic acids by using chromic acid or acidic dichromate. These reagents that are being used are
oxidizing agents. Only methanol, 2-propanol, and formalin got a positive result. Methanol is a primary
alcohol, 2-propanol is the secondary alcohol and formalin is aldehyde. Primary alcohols can be oxidized
because of the presence of hydrogen (H) attached to the carbon where OH is also attached. As the
potassium dichromate and sulfuric acid mix in the methanol, oxidation takes place. The primary alcohol
first oxidizes to aldehyde and will become carboxylic acid. Sometimes the reaction gets stuck in to
aldehyde and not further oxidizes in carboxylic acid because of the insufficient amount of oxidizing
reagent present in the reaction. The methanol when subjected to potassium dichromate and sulfuric
acid, it became a formaldehyde. When it further oxidized, it turned out to be a formic acid. For the
secondary alcohol, 2-propanol oxidizes in ketones. The 2-propanol that was oxidized is now called
propanone because of the ketone present. For aldehydes when it mixed with the potassium dichromate
and sulfuric acid, it became carboxylic acid. This is the same as the second part of the oxidation of the
methanol, forming formaldehyde to formic acid. So for the formalin in the experiment, it became formic
acid when it is subjected to the reagents. The blue color after the reaction tells that the mixtures oxidized
while the orange color tells that theres no reaction occurred. Unfortunately, tertiary alcohols can be
oxidize with the reagents because the carbon where the OH group attached doesnt have any hydrogen
left for oxidation; thus, giving primary and secondary alcohols reacted to dichromate test [8] [9] [10].
Tollens test used [Ag(NH
3
)
2
OH] or the tollens reagent to identify the presence of aldehyde in a
material or solution. It is also used to differentiate aldehydes from ketones. Aldehydes are ready for
oxidation while ketones are not. The reagent contains a diamminesilver(l) ion which is [Ag(NH
3
)
2
]
+

Only formalin reacted to [Ag(NH
3
)
2
OH] because formalin is an aldehyde. Aldehydes dissolves
[Ag(NH
3
)
2
]
+
to a metallic or silver ion because of the reason that the solution is alkaline and aldehydes
oxidizes to carboxylic acid [10] [15].
Lucas test uses the reagents HCl and ZnCl
2
. It is a test for differentiation between alcohols which
is in primary, secondary, and tertiary. It is also a test to know which would be the fastest one to react. In
the experiment, 3-butanol is the only reacted to the reagents because of being the tertiary alcohol.
However, secondary alcohol will also react if given more time. Secondary alcohol reacts slowly than the
tertiary alcohol. Primary alcohol will not react to these reagents. The more the carbon is present, the
more the reaction would be faster. The presence of insoluble layer in the solution will give a positive
reaction. The lucas test undergoes a SN1 reaction-mechanism because the chloride in ZnCl
2
is a good
leaving group and replaces the hydroxyl group. The final product in this test is alkyl halide. It is water
insoluble thats why there is turbidity in the reaction [7] [9] [11].
2,4-Dinitrophenylhydrazine (DNPH) test is for the presence of carbonyl group in molecules. Its
reagent is DNPH. It can also be called a Bradys reagent if DNPH is in a mixture of methanol and
sulfuric acid. Obviously, alcohols cant have a positive result in this reaction because of having a singly
bonded of oxygen to a carbon. Carbonyl groups consist of oxygen double bonded to a carbon. A
precipitation is involved because DNPH reagent condenses with carbonyl groups in formalin and
acetone. In this reaction, the water molecules lost from the combined DNPH and chemical sample. This
is why precipitation occurs. The upper part is the water and the lower part is 2,4-dinitrophenylhydrazone
(DNP). This reaction is an addition-elimination reaction. The DNPH adds first in the carbon=oxygen
(addition stage) to intermediate the compound and lose H
2
O (elimination stage). The colors on this test
also give indication on what is happening in the reaction. The yellow color indicates that the carbonyl
group in unknown is unconjugated; the red-orange color indicates the carbonyl group is conjugated,
while the orange color indicates carbonyl group is not conjugated [5] [9] [10].
Iodoform test involves potassium iodide (KI) and chlorox (NaOCl). In this test, NaOCl will
oxidize the methylcarbonyl group in the molecules. This group is a carbonyl group which is carbon that
is attached to a methyl (CH
3
) group. NaOCl is an oxidizing agent. It oxidizes the iodide in potassium
iodide to iodine. Hydroxide ions are contained in NaOCL which is also an alkaline. It reversibly reacts
with the water so the chloric acid may form. Even though iodoform test involves carbonyl groups,
alcohol can get a positive result. It is because of exhibiting a methyl group directly attached to where the
alcohol group is located. The reaction in alcohols and carbonyl groups is the same. In the experiment,
acetone got a positive result because it has carbonyl group in it [1] [5] [6] [13] [14].
Experimental
Preparation for Dichromate test. 8 drops of sample, 2 drops of 10% K2Cr2O7, and 2 drops of
6M H2SO4 were mixed and combined to each of the 8 test tubes. The results were observed and
recorded by the proponents.
Preparation for Tollens test. 2 mL of tollens reagent and 5 drops of sample were mixed and put
to each of the 8 test tubes. The test tubes with the mixed chemicals were subjected to water bath for 5
minutes. The results were observed and recorded by the proponents.
Preparation for Lucas test. 5 drops of sample and 20 drops of combined HCl and ZnCl2 were
mixed and put to respective test tubes. The test tubes were shook. The results were observed and
recorded.
Preparation for DNPH test. 5 drops of sample and 2 mL of DNPH reagent were mixed and put
into test tubes. The test tubes were subjected to 15-minute water bath. The results were observed and
recorded.
Preparation for Iodoform test. 5 drops of sample, 1 mL 10% KI, an 1 mL NaOCl were mixed
and combined to 8 test tubes. The test tubes were subjected to 5-minute water bath. All the results were
observed and recorded.

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