Carbonyl Compounds: Aldehydes and Ketones

Alina May Aguilar

Diana Teresa Gatus
Ida Isabella Montesa
Aubrey Muriele Ramos
Brent Tenorio

De La Salle University-Dasmarias
Dasmarias City, Cavite, Philippines

ABSTRACT
The experiment shows the solubility and reactions of different aldehydes and ketones. Five
drops of acetone, acetaldehyde, benzaldehyde and cyclohexanone were prepared in separate
test tubes. Five drops of water and NaOH were added to each of the samples in each test tube
in different set ups. The compounds that were soluble in water were acetone and
cyclohexanone while none of the compounds were soluble in NaOH. For the 2,4-DNP tests,
one milliliter of ninety five percent ethanol and one milliliter 2,4-DNP were added in each
sample. All compounds showed the carbon-oxygen double bond in aldehyde and ketone as the
results of all compounds appeared positive with a bright yellow orange precipitate. For Tollens
test, two milliliters Tollens reagent was added in each sample and was kept for ten minutes.
The oxidation determined the presence of aldehyde and ketone in the Tollens test. Only
acetaldehyde and benzaldehyde were oxidized. For the Iodoform test, two milliliters of distilled
water was added to the sample, placed inside sixty degrees Celsius water bath for several
minutes then the Iodoform reagent was added. The presence of CH 3CO in aldehydes and
ketones were determined by this test. The compounds aldehyde and acetone came up positive.
Another test to determine the oxidation reaction was the Jone's test where 4 drops of chromic
acid solution were added and stood for ten minutes. Different tests were done to determine the
presence of aldehyde and ketone.

INTRODUCTION
The carbonyl group (C=O), found in aldehydes, ketones, and esters is a very important functional group
that is involved in several common reactions. This particular functionality is unique because of the polarization
(dipolar resonance) between the carbon-oxygen bond.

O
O
O
O

C
R'

R'

carbonyl group

R'

ketone

aldehyde

Due to the resonance of the C-O bond, there are a variety of reactions where the electrophilic carbon is
attacked by nucleophiles (Lewis bases) and the oxygen reacts with corresponding electrophiles (Lewis acids).
The result of the reaction is the addition of a Nu-E to the bond of the carbonyl group. The two most common
mechanisms are outlined below, although they may vary based on the reagent and reaction conditions.

O
C

E+

Nu

Eq. 6.1

Nu

Nu-E (or Nu-)

Nu-E (or Nu-)
O

O
C

E
Eq. 6.2

Nu
Nu
Carbonyl groups can also increase the acidity of hydrogen atoms (hydrogens on carbons directly
attached to the carbonyl), which allows the -carbon to become nucleophilic. This may be achieved through a
deprotonation reaction, forming an enolate ion (Eq.6.3), or by keto-enol equilibration (tautomerization) to form the
enol (Eq. 6.4). These enolates and enols then react (at the -carbon) with electrophiles, resulting in a substitution
reaction between the hydrogen and the electrophile.
O
C

O
C

:B

O
C

O
C

E+
C

H-B
O
C

Eq. 6.3

:B
O
C

:B
H

OH
C

E+

O
C

H
E

O
C

Eq. 6.4
+ BH

The carbonyl groups in both aldehydes and ketones will be examined in this experiment. Although the
two groups often react similarly, aldehydes commonly react faster than ketones (with the same reagent) due to
less steric hindrance at the carbonyl group. Aldehydes are also more easily oxidized than ketones. You will
examine the similarities and differences between ketones and aldehydes and then use those skills to accurately
identify an unknown compound containing a carbonyl group.

MATERIALS AND METHODS

Three to five drops of benzaldehydde, acetaldehyde, acetone and acetone were placed in separate dry
test tubes and prepared for each of the tests. This experiment tested the solubility in water and sodium hydroxide
as well as the chemical test which included Tollens test, 2,4-DNP, Iodoform test and the Jones test. After each
test, their reactions were observed and classified as insoluble or non-reactive, slightly soluble or slow reaction and
soluble or fast reaction. The solubility test involved: solubility in water, five drops of distilled water was added to
each sample and observe, while in NaOH, five drops of ten percent NaOH was added to each of the samples and
observed. For the 2,4-DNP test, one milliliter of ninety five percent ethanol and one milliliter of 2,4dinitrophenylhydrazine reagent was added per sample For Tollens test, two milliliters of Tollens reagent was

added to each of the samples and allowed to stand for ten minutes before observing the reaction. For the
Iodoform test, two milliliters of distilled water was added per sample and placed in a hot water bath of sixty
degrees Celsius for three to four minutes. While being shook, Iodoform reagent was added until brown color
appeared for two minutes. It was kept in the water bath again for five minutes and the reaction was observed. For
the Jones test, while being shook four drops of Chromic Acid was added to each sample and made to stand for
ten minutes before the reaction was observed.

RESULTS AND DISCUSSION

The reaction of the different samples is classified into two different tests: the solubility test and the
chemical test. The solubility test is comprises with solubility in water and in sodium hydroxide, while for the
chemical tests are 2,4-DNP test, Tollens test, Iodoform test and lastly the Jones test. Below is the table for the
reaction of each sample into different tests:

Samples
acetone
Acetaldehy
de
Benzaldehy
de
cyclohexan
one

Solubility Test
Solubilit
Solubility
y in
in water
NaOH
++
-

Chemical Test
2,4DNP
Test
++

Tollen'
s test

Iodofor
m Test

Jone's
Tes

++

++

++

++

++

++

++

++

++

Table 1 Results of Solubility and Chemical test

Table 1 shows that acetone, acetaldehyde and benzaldehyde are soluble in water; benzaldehyde and
cyclohexanone are soluble in sodium hydroxide; all have positive results in the 2,4-DNP test; acetaldehyde and
benzaldehyde have positive results in Tollens test; only acetone results positive in the Iodoform test while in the
Jones test benzaldehyde and cyclohexanone have positive results.
SOLUBILITY IN WATER:
Acetone (CH3COCH3) has a carbonyl residue which due to the difference in electronegativity between C
and O is polar, forms an overall molecular dipole in acetone. This molecular dipole is nearly identical to water--in
fact, acetone has a dielectric constant of about seventy seven while water's dielectric
constant is about eighty at room temperature and 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. It has fairly low solubility because it is a non-polar hydrocarbon with a
low percentage of oxygen in the molecule.

Cyclohexanone is slightly soluble in water, but miscible with common organic solvents. But in this
experiment the cyclohexanone is not soluble in water. It may be caused by the amount of cyclohexanone and the
solvent that makes it soluble in water.
SOLUBILITY IN NaOH:
Acetone and Acetaldehyde is not soluble in NaOH, while benzaldehyde and cyclohexanone is fast soluble
in sodium hydroxide. The solubility in water may be caused by the presence of cyclic structure in these two
samples.

2, 4-DINITROPHENYLHYDRAZINE TEST:
This test is used to qualitatively detect functionality of a ketone or aldehyde functional group and is also
called Bradys test. A yellow or red precipitate (known as a dinitrophenylhydrazone) signals a positive test. If the
carbonyl compound is aromatic, then the precipitate will be red; if aliphatic, then the precipitate will have a yellow
color. The reaction between 2, 4-DNP and ketone is shown below:
RR'C=O + C6H3(NO2)2NHNH2 C6H3(NO2)2NHNCRR' + H2O
All of the sample 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. Silver mirror precipitate shows positive results for this test. Occasionally the elemental silver
precipitating out of the solution onto the inner surface of the reaction vessel produces a characteristic and
memorable silver mirror on the inner vessel surface.
Benzaldehyde and Acetaldehyde having the presence of aldehyde positively reacted with the Tollens test
and produced silver mirror precipitate. Tollens test is used only to determine the presence of functional group of
aldehyde that is why Acetone and Cyclohexanone did not react with Tollens test because they belong to the
functional group of ketone.

IODOFORM TEST:
This test is also called the haloform test and is used to determine the presence of ketone. Through the
process of halogenation this chemical reaction produced a haloform (CHX 3, where X is a halogen)

Figure 1. Reaction of Methyl Ketone with Iodine in basic medium

Figure 1 shows the reaction pathway of Methyl Ketone with Iodine in NaOH, a basic medium.

Figure 2. Reaction of Acetone with Iodoform test.

Figure 2 shows the reaction pathway of Acetone with Iodine in NaOH, a basic medium.
JONES TEST:
The Jones Oxidation allows a relatively inexpensive conversion of secondary alcohols to ketones and of
most primary alcohols to carboxylic acids. The oxidation of primary allylic and benzylic alcohols gives aldehydes.
Jones described for the first time a conveniently and safe procedure for a chromium (VI)- based oxidation, that
paved the way for some further developments such as Collinks Reactionz aznd pyridinzdvium dichromate, which
also enabled the oxitaion of primary alcohols to aldehydes.
Positive results for aldehydes and primary or secondary alcohols consist of the formation of an opaque
suspension with a green to blue color. Tertiary alcohols remain orange in color and give no visible reaction within
two seconds. Aldehydes developed color in five to fifteen seconds.

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