Carbonyl Compounds: Aldehydes and Ketones

Dilag, Cyril Alexandria M.

De La Salle University - Dasmarias
Dasmarias, Cavite Philippines

Abstract
Qualitative tests may be used to determine the presence or absence of aldehyde and ketones.
Both functional groups give positive result with 2,4-dinitrophenylhydrazine as indicated by the formation of
an orange-yellow precipitate. To differentiate an aldehyde from ketone, Tollens and Benedicts reagent
may be used. Since aldehydes are easily oxidized, they give positive result to Tollens and Chromic acid
test. Iodoform test is used to determine the presence of methyl ketones and acetaldehyde. Four samples
were placed on a separate test tubes namely acetone, acetaldehyde, benzaldehyde, and cyclohexane
and six tests were conducted on each of the samples in order to determine the solubility and their
reactions to each of the tests, Acetone was negative to Tollens and Jones test, acetaldehyde was
positive in all the test, benzaldehyde was positive on 2,4-DNP test, and cyclohexane was positive in 2,4DNP test only. Unknown 1 and 2 were identified by comparing their solubility and reaction profile against
that of the known compounds and the result was an acetone and an acetaldehyde, respectively.

Introduction
Aldehydes and ketones are organic compounds which incorporate a carbonyl functional group,
C=O. The carbon atom of this group has two remaining bonds that may be occupied by hydrogen or alkyl
or aryl substituents. If at least one of these substituents is hydrogen, the compound is an aldehyde. If
neither is hydrogen, the compound is a ketone. The IUPAC system of nomenclature designs a
characteristic suffix to these classes, -al to aldehydes and one to ketones. For example, H 2C=O is a
methanol more commonly called formaldehyde. Since an aldehyde carbonyl group must always lie at the
end of a carbon chain, it is by default position C-1 and therefore defines the numbering direction. A ketone
carbonyl group may be located anywhere within a chain or ring, and its position is given by a locator
number. Chain numbering normally starts form the end nearest the carbonyl group. In cyclic ketones the
carbonyl group is assigned position 1 and the number is not cited in the name, unless more than one
carbonyl group is present.

Materials and Methods

The materials used in the experiment were 5 small test tubes, 1 stirring rod, litmus paper (red and
blue), and 1 spot plate. While the reagents used in the experiment were distilled water, 5% NaOH, 5%
NaHCO3, 5% HCl, and Compound 1, 2, 3, 4, and 5.
3-5 drops of acetone, acetaldehyde, benzaldehyde, and cyclohexane were placed on separate dry test
tubes. Six tests were performed to each of the samples and for every test, a new set of samples were
prepared on various tests. Two tests were done, the solubility test which comprises of solubility in water
and sodium hydroxide and chemical test which includes Tollens test, 2,4-DNP test, Iodoform test, and

Jones test. After each test reactions were observed and classified as insoluble/non reactive, slightly
soluble/slow reaction, and soluble/fast reaction.
The solubility test were soluble in water, 5 drops of distilled water in each sample were added and
observed, while in NaOH, 5 drops of 10% NaOH in each samples were added and observed.
For chemical reactions 2,4-DNP test, added was 1 mL of 95% ethanol and 1 mL 2,4dinitrophenylhydrazine reagent per sample. For 10 minutes, it was allowed to stand and was observed.
Then for the Iodofrom test, 2 mL of distilled water per sample were added. The test tube was placed in a
hot water bath (60 degrees) for 3-4 minutes. Iodoform reagent was added while shaking until brown color
appeared for 2 minutes. It was again kept in a water bath for 5 minutes and the reaction was observed.
Lastly, 4 drops of Jones reagent (Chromic acid) was added while shaking the sample and was allowed to
stand for 10 minutes. And the reaction was observed.

Results and Discussion

Solubili
ty in H2O

Solubilit
y in NaOH

+
-

+
-

+
+
+
+

+
+
-

+
+
+
-

+
+
+

+
-

+
+

+
+

2,4-DNP
test

Tollen
s test

Iodofor
m test

Jon
es test

SAMPLES
Acetone
Acetaldehyde
Benzaldehyde
Cyclobenzaldehyd
e
Unknown 1
Unknown 2
Legend:
++ Fast reaction/Completely soluble
+

No reaction/Insoluble

Slow reaction/Slightly soluble

Identities of Unknown Samples

Sample 1: Acetone
Sample 2: Acetaldehyde
Solubility in H2O
The carbonyl residue in acetone which is polar in nature due to the difference in electronegativity
between C and O, forms an overall molecular dipole in acetone. This molecular dipole is nearly identical

to water in fact, acetone has a dielectric constant of about 77 while waters dielectric constant is about
80 at room temperature thus would be soluble in water.
Hydrogen bonding does occur between acetone and water as the oxygen of acetones carbonyl
can hydrogen bond with the O-H bonds of water. However, the presence of such hydrogen bonding would
in fact only lend to the ability of the two types of molecules to be miscible with each other.
Acetaldehyde is soluble in all proportions. The reason for the solubility is that acetaldehyde cant
hydrogen bond with themselves; they can hydrogen bond with water molecules.
One of the slightly positive hydrogen atoms in a water molecule can be sufficiently attracted to
one of the lone pairs on the oxygen atom of an aldehyde or ketone for a hydrogen bond to be formed.
Benzaldehyde is soluble in water 0.6 g/100 mL (20 degrees Celsius). It has fairly low solubility
because it is a non-polar hydrocarbon with a alow solubility because it is a non-polar hydrocarbon with a
low percentage of oxygen in the molecule.
Cyclohexanone is slightly soluble in water (5-10 g/100 mL), but miscible with common organic
solvents. But in the experiment, the cyclohexanone is not soluble in water. It may be caused by the
amount of cyclohexanone and the solvent that makes it insoluble in water.
Solubility in NaOH
Acetone and acetaldehyde are not soluble in sodium hydroxide, while benzaldehyde and
cyclohaxanone are indeed fast soluble in NaOH. The presence of cyclic structure may cause why this 2
samples are soluble in water.
2,4-DNP Test
It is also called Bradys test, used to qualitatively detect carbonyl factionality of a ketone or
aldehyde functional group. A positive test is signalled by a yellow or red precipitate (DNP). If the carbonyl
compound is aromatic, then the precipitate will be red, if aliphatic it will be yellow color. The reaction
between 2,4 DNP and ketone is
RRC=0 + CuH3(NO2)2NHNH2 ----- C6H3(NO2)2NHNCRR + H2O
This reaction is described as condensation reaction, with 2 molecules joining together with loss of
water. It is also considered an addition-elimination reaction: nucleophilic addition of the NH 2 group to the
C=O carbonyl group followed by the removal of H 2O molecule.
All of the samples have a fast and positive test in 2,4-DNP because all of them belong to the
ketone or aldehyde functional group.
Tollens Test
This chemical test is commonly used to determine whether a known carbonyl containing
compound is an aldehyde or ketone. A positive test for Tollens reagent result in an elemental silver
precipitating out of solution, occasionally onto the inter surface of the reaction vessel, producing a

characteristic and memorable silver mirror precipitate. The acetone and cyclohexanone will not react with
Tollens test because they belong to the functional group of ketone and Tollens test is used only to
determine the presence of functional group, aldehyde.
Iodoform Test
It is called haloform test. It is used to determine the presence of ketone. This is a chemical
reaction which produces a haloform (CHX3 where X is a halogen) through the process of halogenations.
Jones Test
A positive test for aldehyde and primary or secondary alcohols consists in the production of an
opaque suspension with a green to blue color. Tertiary alcohols give no visible reaction within 2 seconds
the solution remaining orange in color. Disregard any changes after 15 seconds. Aldehydes are better
characterized in other ways. The color usually develops in 5-15 seconds.

Acetone is an extremely polar molecule and has a dielectric constant of 77 (H 2o is 80), and
hence is capable of forming ++ bonding with water.
On the other hand benzophenone, has a very low polarity and also does not ++ bonds and hence
is insoluble in water.
Aldehydes are more susceptible to oxidation that ketones due to (1) Steric Reason, ketones are
sterically hindered than aldehyde, due to presence of alkyl group on both the side of carbonyl carbon,
making them less reactive towards nucleophilic attack. And (2) Electonic Reason, 2 bulky alkyl groups
near the carbonyl part in ketones reduce the electrophilicity in ketones than one such group in aldehyde.
The boiling point of ketones and aldehydes are less than the corresponding carboxylic acid
because in ketones and aldehydes, hydrogen bonding is not present between the molecules. But in
carboxylic acid, the molecules get associated due to hydrogen bonding. This increases the boiling point of
the carboxylic acids.
The aldehyde and ketone contain carbonyl group C=O, which provide site for addition reaction
through the following mechanism:

Following additions may occur to carbonyl group

-

Addition of hydrogen cyanide (HCN)

Addition of sodium hydrogen sulphile (NaHSO3)

Addition of alcohols

Addition of ammonia and its derivatives

Addition of Grignard reagents

Other tests that may be used to distinguish aldehyde and ketones are (A) Fehlings Test and (B)
Schiffs Reagent Test.
A. Fehlings Test
It is given by aliphatic aldehydes. This is used to distinguish between aldehydes and
keyones. It is a mild oxidizing agent which oxidizes aldehydes but not ketones. Therefore,
ketones do not give this test. The general equation for this is
R-CHO + 2Cu2+ + 50H -------> RCOO + Cu2O
B. Benedicts Test
Benedict's solution contains copper(II) ions complexed with citrate ions in sodium
carbonate solution. Again, complexing the copper(II) ions prevents the formation of a precipitate this time of copper(II) carbonate. Both solutions are used in the same way. A few drops of the
aldehyde or ketone are added to the reagent, and the mixture is warmed gently in a hot water
bath for a few minutes.
Ketone - No change in the blue solution.
Aldehyde - The blue solution produces a dark red precipitate of copper(I) oxide.
Aldehydes reduce the complexed copper(II) ion to copper(I) oxide. Because the solution
is alkaline, the aldehyde itself is oxidized to a salt of the corresponding carboxylic acid. The
equations for these reactions are always simplified to avoid having to write in the formulae for the
tartrate or citrate ions in the copper complexes. The electron-half-equations for both Fehling's
solution and Benedict's solution can be written as:

2Cu2 + complexed + 2OH + 2e Cu2O + H2O

Combining that with the half-equation for the oxidation of an aldehyde under alkaline
conditions:
RCHO + 3OH RCOO + 2H2O + 2e
To give the overall equation:
RCHO + 2Cu2 + complexed + 5OH RCOO + Cu2O + 3H2O

First, Tollen's reagent should always be prepared fresh (never stored) because of the danger of
the formation of explosive "fulminating silver" in the liquid. This is a black precipitate that can explode at
the slightest touch or disturbance, even while still in the liquid. If there is any evidence of a black
precipitate in the reagent, the container should not be touched or moved! See the link below for details.
Left-over Tollen's reagent should be promptly disposed of by carefully acidifying it. Acidifying it
with nitric acid as suggested above will render it safe, but will leave the silver in solution. Using dilute
hydrochloric acid will conveniently precipitate the silver as the solid chloride for recovery.
Note that "fulminating silver" is not silver fulminate (AgONC) or silver azide (AgN3), both of which
are white and - though sensitive - are far less so than the black material. Rather, it appears to be a
complex material the composition of which has been variously described. The link says it's largely silver
nitride (Ag3N) and silver imide (Ag2NH). In any case, the fact that it's complex and contains both silver
and nitrogen is universally agreed.

Pertinent General Reactions:

(1) 2,4-DNP test:

(2) Tollens test:

(3) Iodoform test:

(4) Jones test:

References
(1) Mcmurry. Simanek. 2008. Fundamentals of Organic Chemistry-6th Edition. Thompson
Corporation Retrieved on March 7, 2015
(2) http://www.springerlink.com/content/q07v0462287v44uk/ - Retrieved on March 7, 2015
(3) http://en.wikipedia.org/wiki/Solubility#Solubility_of_organic_compounds Retrieved on March 7
(4) http://www.wellesley.edu/Chemistry/chem211lab/Orgo_Lab_Manual/Appendix/ClassificationTests/
solubility.html - Retrieved on March 10, 2015
(5) http://faculty.swosu.edu/william.kelly/pdf/ketone.pdf - Retrieved on March 10, 2015