CHEMISTRY LABORATORY 503

Activity No. 5
Aldehydes and Ketones

Aries Jay Bernal Reyes

MST Chemistry

Date Performed: September 24, 2016

Date Submitted: October 1, 2016

I-
a.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 oxidizing agent used in these reactions is normally a solution of sodium or
potassium dichromate (VI) acidified with dilute sulfuric acid. If oxidation occurs, the
orange solution containing the dichromate (VI) ions is reduced to a green solution
containing chromium (III) ions. The net effect is that an oxygen atom from the oxidizing
agent removes a hydrogen from the -OH group of the alcohol and one from the carbon to
which it is attached.
A Grignard reagent has a formula RMgX where X is a halogen, and R is an alkyl or
aryl (based on a benzene ring) group. For the purposes of this page, we shall take R to be
an alkyl group.
In the first stage, the Grignard reagent adds across the carbon-oxygen double bond:

Dilute acid is then added to this to hydrolyze it.

A small amount of potassium dichromate (VI) solution is acidified with dilute

sulfuric acid and a few drops of the aldehyde or ketone are added. If nothing happens in
the cold, the mixture is warmed gently for a couple of minutes - for example, in a beaker
of hot water.
 The orange dichromate (VI) ions have been reduced to green chromium (III) ions by
the aldehyde. In turn the aldehyde is oxidized to the corresponding carboxylic acid.

The electron-half-equation for the reduction of dichromate (VI) ions is:

Combining that with the half-equation for the oxidation of an aldehyde under acidic
conditions:

Give the overall equation:

Tollens' reagent contains the diamminesilver (I) ion, [Ag (NH 3)2]+. This is made from
silver (I) nitrate solution. You add a drop of sodium hydroxide solution to give a
precipitate of silver (I) oxide, and then add just enough dilute ammonia solution to
redissolve the precipitate. To carry out the test, you add a few drops of the aldehyde or
ketone to the freshly prepared reagent, and warm gently in a hot water bath for a few
minutes. Aldehydes reduce the diamminesilver (I) ion to metallic silver. Because the
solution is alkaline, the aldehyde itself is oxidized to a salt of the corresponding
carboxylic acid.
Fehling's solution and Benedict's solution are variants of essentially the same thing.
Both contain complex copper (II) ions in an alkaline solution. Fehling's solution contains
copper (II) ions complex with tartrate ions in sodium hydroxide solution. Complexing
the copper (II) ions with tartrate ions prevents precipitation of copper (II) hydroxide.
Benedict's solution contains copper (II) ions complex 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.

b. Objective/s:
i. To be able to determine the properties and characteristics of aldehydes and
ketones using various tests.
c.Statement of the Problem
i. What test/s determines the properties and characteristics of aldehydes and ketones?
d. Limitation of the Study
i. The experiment is limited only in determining the characteristics and properties of
aldehydes and ketones
e.Methodology
i. The method used in determining the characteristics and properties of aldehydes
and ketones is done using various tests like Sodium bisulfite test, Schiff’s test,
 Tollen’s test, Fehling’s test, Sodium nitroprusside test, Special test for
Benzaldehyde, Iodoform test and Molisch test.

II- Results and discussion

1. Sodium bisulfite test

Substance used Reagent/s added Observation

Benzaldehyde White precipitate formed

NaHSO3

Acetone No precipitate formed

Discussion:
In this experiment, benzaldehyde and acetone was reacted with sodium
bisulfite. Benzaldehyde produces a white precipitate whereas acetone did not. Most
aldehydes and methyl ketones give a bisulfite addition product. A small quantity of
the aldehyde or methyl ketone to be tested is added to a saturated solution of
sodium bisulfite, NaHSO 3 . The formation of a white precipitate is a positive
test. This particular nucleophile (HSO3-) is quite bulky, and therefore cannot react
with sterically hindered carbonyls. This reaction can be used to separate sterically
hindered carbonyl compounds from those which are not sterically hindered.

2. Schiff’s test

Substance used Reagent/s added Observation

Formalin Violet color was formed

Acetone No change in color

Schiff’s Reagent

Benzaldehyde Dark pink color was

formed

Acetophenone No change in color

Discussion:
In this experiment, formalin produced a violet color solution and benzaldehyde
giving a dark pink color solution whereas acetone and acetophenone having no
 changes in color. This is because most aldehydes give a positive Schiff's test.
Schiff’s Reagent is basic, Fuchsin, p-rosaniline hydrochloride, which has been
treated with sulfur dioxide to form a colorless solution. When a small quantity of
aldehyde is mixed with Schiff's reagent, a rapid color change occurs. The
complex formed is deep purple or magenta in color. This test is quite sensitive for
aldehydes which are soluble in Schiffs reagent. Insoluble aldehydes give a slow
positive test at the interface. Small cyclic ketones give a slight color change.

3. Tollen’s Test

Substance used Reagent/s added Observation

It formed a shiny
Formalin substance on the sides of
the test tube

Tollen’s reagent It formed a shiny

5% Glucose substance on the sides of
the test tube

Benzaldehyde No reaction occurred

Acetone No reaction occurred

Discussion:
In this experiment, only formalin and glucose produced a shiny substance on the
sides of the test tube whereas in benzaldehyde and acetone, no reaction occurred.
Tollens' reagent is a chemical reagent used to determine the presence of an aldehyde,
aromatic aldehyde and alpha-hydroxy ketone functional groups. The reagent consists
of a solution of silver nitrate and ammonia. A positive test with Tollens' reagent is
indicated by the precipitation of elemental silver, often producing a characteristic
"silver mirror" on the inner surface of the reaction vessel.

4. Fehling’s Test

Substance used Reagent/s added Observation

Formalin It formed a brick – red

precipitate
 5% glucose It formed a brick – red
precipitate

Fehling’s A
Benzaldehyde Fehling’s B No change occurred

Acetone No change occurred

Discussion:
In this experiment, only formalin and glucose produced a brick – red precipitate
upon the reaction to fehling’s reagent whereas benzaldehyde and acetone gave no
reaction to fehling’s reagent.
5. Sodium nitroprusside test

Substance used Reagent/s added Observation

Acetone It formed a brown color

5% Sodium nitroprusside soln.
5% NaOH
Glacial Acetic aicd
Ethyl methyl ketone It formed a brown color
soln.

Discussion:

6. Iodoform test

Substance used Reagent/s added Observation

Acetone It formed an unpleasant

odor and a yellow
precipitate
Iodine in KI soln.

Ethyl methyl ketone It formed an unpleasant

odor and a yellow
precipitate

Ethyl acetate It formed an unpleasant

odor and a black
precipitate

Discussion:
 7. Special test for Benzaldehyde

Substance used Observation

Benzaldehyde It formed crystals after an hour

Discussion:

8. Molisch’s test

Substance used Reagent/s added Observation

5% Glucose Violet color formed at the

junction of 2 liquids

Molisch reagent
5% Starch Conc. H2SO4 Violet color formed at the
junction of 2 liquids

Benzaldehyde A golden brown color soln

was formed
Discussion:

III- Conclusion and recommendation

IV- Questions
1. Explain the reactivity of aldehydes and ketones towards nucleophilic reagents.
2. Give the principle involved in:
a. 2,4 – dinitrophenylhydrazine test
b. Sodium bisulfite test
c. Tollen’s test
d. Fehling’s test
3. Why does glucose give a positive fehling’s test?
4. What is the clinical significance of Sodium nitroprusside test?
5. What other compounds give a positive iodoform test? Explain.
6. What is the significance of Molisch’ test?
7. What is the basis of Molisch’