Philippine Science High School System

Resource Material in Chemistry 3 EXPERIMENT

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Reactions of Carbonyl Compounds:

Aldehydes and Ketones
OBJECTIVES
Compare the solubility of simple aldehydes and ketones in water.
Describe visual indicators of chemical reactions involving aldehydes and ketones.
Write chemical formulas and balanced chemical equations representing reactions
of aldehydes and ketones.
Explain the relative reactivity of aldehydes and ketones to certain reagents.

INTRODUCTION

The basic structural similarity between aldehydes and ketones is the

presence of a carbonyl group which consists of a carbon atom, called the
carbonyl carbon, doubly bonded to an oxygen atom. An aldehyde, however,
contains at least one hydrogen atom attached to its carbonyl carbon while a
ketone always has none because, two alkyl groups, R, or carbon atoms are
attached instead.
O O

C C
R H R R’
aldehyde ketone
The carbonyl group is involved in numerous important reactions in
organic chemistry; mainly as a result of the polarization of the carbon-oxygen-π-
bond due to the relatively high electronegativity of the oxygen atom resulting in a
dipolar resonance structure for this functional group (C +– O–). Hence, the
carbonyl group can give a molecule its polar character allowing it to be soluble in
water. However, unlike water and alcohols, aldehydes and ketones cannot form
H-bonds with molecules of their own kind; hence, have lower boiling points
compared to the former.

- –
O O O
or or
C C C
+ R + R’

Carbonyl group reactions can be grouped into nucleophilic addition

reactions and oxidation reactions. Addition reactions are one of the most
important carbonyl reactions. In addition reactions, the electrophilic carbonyl
carbon atom is attacked by nucleophiles (Lewis bases or electron-pair donors)

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 and the oxygen atom, in turn, reacts with electron-poor electrophiles (Lewis acids
or electron-pair acceptors) as shown in schemes 1 and 2.

Scheme 1. - H
E
O O E O

C C C
H
Nu-E H Nu H
Nu

Scheme 2.
H
E
+ E O
O Nu-E O
H +H -
C Nu C
C
H
Nu

Many addition reactions of carbonyl groups are acid catalyzed (Scheme

3) especially when electrically neutral nucleophiles like water, alcohols, ammonia
and ammines are involved. As in Scheme 2, the acid attacks the electronegative
oxygen, which bears a partial negative charge, to create a carbocation that
subsequently reacts with the nucleophile. Some are also base-catalyzed in which
a negatively charged nucleophile like the hydroxide, hydride, carbanion, alkoxide
or cyanide ion attacks the carbonyl carbon first forming an alkoxide ion
intermediate that is eventually protonated by an added acid or solvent (Sheme 4).
The strength of the nucleophile and the structure of the carbonyl compound
determine whether the equilibrium lies on the side of the carbonyl compound (1)
or the tetrahedral adduct (2).

Scheme 3.

Scheme 4.

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 The nucleophilic addition of hydrides and Grignard reagents to aldehydes
and ketones can lead to the reduction of the carbonyl group which produces
primary and secondary alcohols, respectively.

The carbonyl group in aldehydes can also be oxidized to form carboxylic

acids. This occurs through intermediate hydrates which are formed by a
reversible addition of water to the carbonyl group (Scheme 5).

Scheme 5.

The carbonyl group can also enhance the acidity of hydrogens on carbons
directly attached to the carbonyl group (α-hydrogen atoms). As a result, the α-
carbon atom can become nucleophilic, either through deprotonation reaction to
form an enolate ion (Scheme 6) or by keto-enol equilibration (tautomerization) to
form the enol (Scheme 7). Enolates or enols can then react with electrophiles at
the α-carbon to give a net substitution reaction of the electrophile for the α-
hydrogen.

Scheme 4.
O O O O
H :B E
C C C E C
-
C C C C
H H H H
H H H H

Scheme 5.
:B
H H H
O +
O +
O O O
H H :B E E
C C C E C C
C C C C C
H H H H H
H H H H H

In this laboratory activity, you shall explore some properties and

reactions of aldehydes and ketones which can be used to differentiate one from
the other. On the basis of Schemes 1 to 7, you will be explaining the observable
results of reactions of aldehydes and ketones to certain reagents as acids, bases,
alcohols, and other metal ions. The different tests for aldehydes and ketones
include tests for the oxidation of the carbonyl group such as the Tollen’s Test,
Fehling’s Test (or Benedict’s Test as an alternative), Bordwell-Wellman’s
(Chromic Acid) Test and Schiff’s Test. Another test, called the Iodoform Test, is
also used which is uniquely anchored in the halogenation reaction of any alpha
methyl group giving a haloform and the corresponding carboxylic acid.

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PROCEDURE

Pre-Laboratory Tasks:
1. Completely fill out the blanks (for group member names) and columns 1 to 3
of Table 1 in the Laboratory Report.
2. Using available Material Safety Data Sheets (MSDS), summarize in a table
(separate sheet) the following information for all the test compounds and test
reagents (excluding distilled H2O) involved in this experiment: (a)
Compound Name (IUPAC and Common Name), (b) Chemical Formula, (c)
physical properties such as melting point, boiling point and flash point, (d)
incompatibilities with other reagents and (e) hazards/toxic effects.
3. Submit the above to your instructor at least three (3) days prior to the conduct
of the experiment.

CAUTION
The reagents in this experiment can emit irritating and toxic vapors.
Wear laboratory goggles and protective gloves.
Wear masks with carbon filter, except in Procedure A - Step 2.
Perform all experiments under the fume hood.
Stopper or seal (with parafilm) all test tubes when taken out of the
fume hood.

Materials: test tubes, test tube rack, droppers, fume hood

Test compounds:
formaldehyde, acetaldehyde, benzaldehyde, acetone, cyclohexanone or
acetophenone,
Test reagents:
0.1 M AgNO3, 6 M NH4OH, 6 M NaOH, chromic acid solution, Fehling’s
Reagent (or Benedict’s Reagent), I2/KI solution, Shiff’s Reagent, Sodium
Carbonate (s), distilled water

A. Odors of Aldehydes and Ketones

4. Place 1 mL (or 20 drops) of each test compound separately in test tubes and
label them according their listing on Table 1 of the Laboratory Report sheet.
Also write their chemical formulas and structures in Table 1.
5. Carefully detect the odor of each compound by wafting then record your
observations on the Laboratory Report sheet.
Question 1: Which between aldehydes and ketones generally have a stronger odor?
Question 2: How can you relate the differences in structure of the compounds to their
odor strength?

B. Water Solubility
1. To the solutions in Procedure A, add 5 mL of water.
2. Seal the test tubes with parafilm and vigorously swirl each one while
securing the seal with your thumb for at least 15 seconds to mix the contents
making.

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 3. Let the mixture stand for 1 minute. Sketch a picture of the liquids or mixture
in the Laboratory Report Sheet and assess which compounds are miscible
with water.
4. For any solutions that are immiscible, note the relative density of the
compounds with respect to water.
5. Dispose of the solutions in the waste bottle labelled “Organic Waste”.

Question 3: How can the relative differences in water solubility or miscibility of the test
compounds be accounted for?

C. Tollen’s Test
This test involves Tollen’s reagent which contains silver ion in its
ammonia complex, [Ag(NH3)2]2+, that serves as an oxidizing agent. In the
process, the silver ion is reduced to metallic silver deposited on the walls of a
glass reaction vessel as a silver mirror indicating a positive result.
1. Obtain 6 small (4”) test tubes and one large (6”) test tube and thoroughly
wash with soap and water, and rinse them with distilled water. Tollen’s test is
very sensitive to impurities; hence, all test tubes to be used in this part must
be thoroughly cleaned.
2. To the large test tube, add 2 mL of the 0.1 M AgNO3 solution to each test
tube. Add 10 drops of 6 M NaOH and mix thoroughly. A black precipitate,
Ag2O, should form.
3. Carefully add 6 M NH4OH dropwise just until the black precipitate dissolves.
Too much NH4OH may lead to failure of the test.
4. Dilute the final mixture to about 6 mL with distilled H2O to finally prepare
the Tollen’s Reagent.
5. Carefully divide the Tollen’s reagent equally into the 6 clean labelled test
tubes (about 15-20 drops per test tube). One of which will serve as the control
or blank.
6. Add four (4) drops of the test compounds separately into test tubes with the
Tollen’s reagent.
7. Shake each mixture, and then allow it to stand for 5-10 min. If no reaction
occurs, place the tube in a beaker of warm water (35-50°C) for 5 min.
8. Record your observations in the Laboratory Report. A positive test is denoted
by the deposition of a silver mirror on the sides of the test tube. Number the
compounds that showed a positive result from the one which reacted the
earliest (1) to the one which reacted last. Write NA for compounds that tested
negative to Tollen’s Test.
9. Place the content of all test tubes in the appropriate container labeled Tollen's
Waste Only. Remove any silver mirror deposits with a few drops of 8 M
nitric acid, and drain this into the same waste container. Immediately destroy
any excess Tollens’ reagent with nitric acid because it can form an explosive
fulminate on standing.

Question 4: What common structural feature can be seen in the compounds that showed a
positive result in the Tollen’s Test?

Question 5: How can such structural feature make a compound susceptible to silver ion
oxidation?

Question 6: How could the poor or non-reactivity of some test compounds to the Tollen’s
Reagent be explained?

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 D. Bordwell-Wellman’s (Chromic Acid) Test
The Bordwell-Wellman reagent contains the dichromate ion, Cr2O72–, in a
sulfuric acid solution. The dichromate can oxidize carbonyl groups while its
orange Cr6+ is reduced to blue-green Cr3+.
1. Add 6-8 drops of the test compounds into 5 separate clean labelled 4” test
tubes
2. Add 2 drops of the chromic acid solution into each test tube.
3. Swirl well then heat the test solutions in a water bath for 3-4 minutes.
4. Record any color changes observed. A positive reaction is indicated by a
color change from orange/yellow orange to green or brown. Number the
compounds that showed a positive result from the one which reacted the
earliest (1) to the one which reacted last. Write NA for compounds that tested
negative to this test.
5. Dispose all test solutions used into an inorganic waste jar.

Question 7: What common structural feature can be seen in the compounds that showed a
positive result in the Chromic Acid Test?

Question 8: How can such structural feature make a compound susceptible to chromic
acid oxidation?

Question 9: How could the poor or non-reactivity of some test compounds to chromic
acid be explained?

E. Fehling's Test
The Fehling’s Reagent contains copper (II) sulfate, potassium tartrate and
sodium hydroxide. In this test, the Cu2+ ion can oxidize a carbonyl group while it
is consequently reduced to Cu+ in the form of Cu2O, an orange to red precipitate.
The Benedict’s Test is alternatively performed for this test wherein the
Benedict’s Reagent is used instead. The Benedict’s Reagent, similar to the
Fehling’s reagent, also contains copper (II) sulfate but with the additives sodium
citrate and sodium carbonate instead.
1. Add 2 mL of the Fehling's Solution into 5 separate clean labelled test tubes.
2. Add 5 drops of the test compound separately into these test tubes.
3. Gently swirl the test tubes and place them in a boiling water bath.
4. After 5 minutes, record your observations (color changes or precipitates).
Number the compounds that showed a positive result from the one which
reacted the earliest (1) to the one which reacted last. Write NA for
compounds that tested negative to this test.
5. Dispose all test solutions used into an inorganic waste jar.

Question 10: What common structural feature can be seen in the compounds that showed a
positive result in the Fehling’s Test?

Question 11: How can such structural feature make a compound susceptible to cupric ion
oxidation?

Question 12: How could the poor or non-reactivity of some test compounds to Cu2+ be
explained?

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 F. Shiff’s Test
This test uses a solution of the red dye, Basic Fuchsin or p-rosaniline
hydrochloride, which is rendered colorless on treatment with sulfur dioxide. In
the presence of a reactive carbonyl group, the colorless solution turns magenta.

1. Add 2 mL of the Schiff’s Reagent into 5 separate clean labelled test tubes.
2. Add 5 drops of the test compound separately into these test tubes.
3. Gently swirl the test tubes to mix the contents.
4. After 10 minutes, record your observations (color changes or precipitates).
Number the compounds that showed a positive result from the one which
reacted the earliest (1) to the one which reacted last. Write NA for
compounds that tested negative to this test.
5. Neutralize the solution with small pinches/portions of sodium carbonate until
the fizzing stops the flush the solution down the drain. The amount of p-
rosaniline is negligible (1 mg).

Question 13: To which among the tests is the Schiff’s Test related in terms of the positive
and negative results?

G. Iodoform Test
This test is based on the reaction of a methyl group attached to the
carbonyl group with iodine (I2) in a NaOH solution. The reaction produces a
solid, yellow iodoform, CHI3 which has a strong medicinal odor, and is used as
an antiseptic.
1. Add 1 mL of 6 M NaOH into 5 small labelled test tubes.
2. Add 5 drops of the test compounds separately into the test tubes.
3. Add 3 drops of the iodine I2/KI solution into each test tube.
4. Record your observations (color changes or precipitates).
5. Dispose all test solutions used into an inorganic waste jar.

Question 14: What structural feature is present in the compound/s that showed a positive
result in the Iodoform Test?

Question 15: What makes this structural feature reactive to iodine to allow haloform
formation?

Question 16: Among the tests, which can be used to specifically identify aldehydes?

Question 17: Among the tests for aldehydes and ketones, which is the most advantageous
to use? Why do you say so?

Question 18: Among the tests, which can be used to specifically identify ketones?

Question 19: Based on the qualitative test results, what factors affect the ease of oxidation
of aldehydes and ketones?

Question 20: Have there been deviations from expected results? If so, what could be the
causes of such deviations?

REFERENCES

Blackmond, D.G. (2005). Carbonyl Chemistry. Retrieved from

http://www.ch.ic.ac.uk/local/organic/tutorial/DB_Carbonylnotes1.pdf.

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MacMurry, J. (2011). Fundamentals of Organic Chemistry, 7th ed. Belmont, CA:
Brooks/Cole.
Nalli, T. (2008). Chemistry 209 - Experiment #4 - Aldehydes and Ketones. Retrieved from
http://course1.winona.edu/tnalli/spring05/209labs/expt4.pdf
Robert (2007). Chemistry 283g - 2007: Reactions of Aldehydes and Ketones.
https://instruct.uwo.ca/chemistry/283g/labs/Experiment%206/Experiment%206-
2007.pdf
Shadid, K., and Haikal, A. (2014). Organic Chemistry 1 Laboratory Manual. Islamic
University of Madinah. Retrieved from
http://www.khalidshadid.com/uploads/3/9/2/0/3920808/
islamic_univ._organic_chemistry_practical.pdf
Williamson, K.L., and Masters, K.M. (2011). Macroscale and Microscale Organic
Experiments, 6th ed. Brooks/Cole Cengage Learning, Inc. Belmont, CA.

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_____________________________________________________________
LABORATORY REPORT

Experiment 14: Reactions of Carbonyl Compounds: Aldehydes and Ketones

Names of Group Members : __________________________________________

__________________________________________
__________________________________________

DATA

Table 1. Odor and Solubility of Aldehydes and Ketones

Compound/ Class Solubility in /
Chemical Structure (aldehyde / Odor Miscibility
Formula ketone) with Water
Formaldehyde

Acetaldehyde

Benzaldehyde

Acetone

Hexanone

Question 1: Which between aldehydes and ketones generally have a stronger odor?
_________________________________________________________

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Question 2: How can you relate the differences in structure of the compounds to their
odor strength?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Question 3: How can the relative differences in water solubility or miscibility of the test
compounds be accounted for?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Table 2. Tollen’s Test Results

Test Result
Balanced Chemical Reaction
Compound (+, -, order of (Write NR if the test renders a negative result;
reactivity) Include the states of all reaction species)
Ex. +, 1 or -, NA
Formaldehyde

Acetaldehyde

Benzaldehyde

Acetone

Hexanone

Question 4: What common structural feature can be seen in the compounds that showed a
positive result in the Tollen’s Test?
_________________________________________________________
_________________________________________________________

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Question 5: How can such structural feature make a compound susceptible to silver ion
oxidation?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Question 6: How could the poor or non-reactivity of some test compounds to the Tollen’s
Reagent be explained?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Table 3. Bordwell-Wellman’s (Chromic Acid) Test Results

Test Result
Balanced Chemical Reaction
Compound (+, -, order of (Write NR if the test renders a negative result;
reactivity) Include the states of all reaction species)
Ex. +, 1 or -, NA
Formaldehyde

Acetaldehyde

Benzaldehyde

Acetone

Hexanone

Question 7: What common structural feature can be seen in the compounds that showed a
positive result in the Chromic Acid Test?
_________________________________________________________
_________________________________________________________

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Question 8: How can such structural feature make a compound susceptible to chromic
acid oxidation?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Question 9: How could the poor or non-reactivity of some test compounds to chromic
acid be explained?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Table 4. Fehling’s Test Results

Test Result
Balanced Chemical Reaction
Compound (+, -, order of (Write NR if the test renders a negative result;
reactivity) Include the states of all reaction species)
Ex. +, 1 or -, NA
Formaldehyde

Acetaldehyde

Benzaldehyde

Acetone

Hexanone

Question 10: What common structural feature can be seen in the compounds that showed a
positive result in the Fehling’s Test?
_________________________________________________________
_________________________________________________________

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Question 11: How can such structural feature make a compound susceptible to cupric ion
oxidation?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Question 12: How could the poor or non-reactivity of some test compounds to Cu2+ be
explained?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Table 5. Schiff’s Test Results

Test Result
Balanced Chemical Reaction
Compound (+, -, order of (Write NR if the test renders a negative result;
reactivity) Include the states of all reaction species)
Ex. +, 1 or -, NA
Formaldehyde

Acetaldehyde

Benzaldehyde

Acetone

Hexanone

Question 13: To which among the tests is the Schiff’s Test related in terms of the positive
and negative results?
______________________________________________________________

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Table 5. Iodoform Test Results
Test Result
Balanced Chemical Reaction
Compound (+, -, order of (Write NR if the test renders a negative result;
reactivity) Include the states of all reaction species)
Ex. +, 1 or -, NA
Formaldehyde

Acetaldehyde

Benzaldehyde

Acetone

Hexanone

Question 14: What structural feature is present in the compound/s that showed a positive
result in the Iodoform Test?
_________________________________________________________
_________________________________________________________
Question 15: What makes this structural feature reactive to iodine to allow haloform
formation?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Question 16: Among the tests, which can be used to specifically identify aldehydes?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

75
Question 17: Among the tests for aldehydes and ketones, which is the most advantageous
to use? Why do you say so?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Question 18: Among the tests, which can be used to specifically identify ketones?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Question 19: Based on the qualitative test results, what factors affect the ease of oxidation
of aldehydes and ketones?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

Question 20: Have there been deviations from expected results? If so, what could be the
causes of such deviations?
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________
_________________________________________________________

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