LABORATORY ACTIVITY 12
REACTIONS OF ALDEHYDES AND
KETONES
Reactions of Aldehydes and Ketones may be
grouped into:
1. Oxidation – Reduction to the Carbonyl
Group
2. Addition to the Carbonyl Group
3. Condensation and Polymerization
Reactions
Aldehydes are readily oxidized to the
corresponding carboxylic acids. Ketones are
difficult to oxidize. Therefore, aldehydes are
stronger reducing agents than ketones.
Mild oxidizing agents like Tollen’s reagent (Ag+)
and Fehling’s reagent (Cu2+) are readily
reduced by aldehydes to silver mirror and brick
red precipitate of Cu2O respectively. Aromatic
aldehydes reduce Tollen’s reagent but not
Fehling’s. Ketones do not reduce either of the
two reagents.
RCHO + 2 Ag+ + 3 OH- → RCOO + Ag + 2 HOH
RCHO + 2 Cu 2+ + 5 OH- → RCOO + Cu2O +
3 HOH
Aldehyde and ketones may also be
differentiated by the Schiff’s fuschin test. The
reaction with aldehydes produces a violet –
purple or magenta red color (characteristic blue
shade in red).
With phenylhydrazine, aldehydes and ketones
form addition compounds which may be used
for their identification because of the
characteristics crystalline shapes and melting
points of their phenylhydrazines.
H H
ǁ HOH ǁ
RCCH3 + H2NNHC6H5 → RC=NNHC6H5
Aldehydes and methyl ketones give solid
addition products with NaHSO3.
H H
ǁ ǁ
RCCH3 + NaHSO3 → RCCH3 + NaSO3
Methylcarbonyl Compounds like
acetaldehyde and acetone form a yellow
crystalline precipitate by reaction with I2 in the
presence of dilute alkali. Alcohols of the type
RCHOHCH3 also give the iodoform test.
Condensation reaction involving the carbonyl
group is illustrated by the aldol condensation.
When acetaldehyde is warmed with dilute
NaOH. 2 molecules unite between the carbonyl
group of one end and the alpha carbon of
another as shown:
[OH]- 2 CH3 CHO → CH3 CHCH2 CHO
ǁ
OH
Aldol compound (B – hydroxy aldehyde)
The aldol molecule has a reactive aldehyde
group and the reaction mmay be repeated
indefinitely forming aldehyde resin. This is what
takes place when acetaldehyde is heated with
strong NaOH.
Aldehydes that do not have any alpha –
hydrogen do not undergo aldol condensation.
Such aldehydes undergo Cannizaro reaction
when treated with strong NaOH. ~CHO + NaOH
→ ~COOna + CH2OH
FORMALDEHYDE
• Formaldehyde is a colorless poisonous
gas synthesized by the oxidation
of methanol and used as an antiseptic,
disinfectant. Formaldehyde, solutions
(formalin) (corrosive) appears as a
colorless liquid with a pungent irritating
odor
SILVER NITRATE
• Silver nitrate is an inorganic compound
with the chemical formula AgNO3. In its
solid form, silver nitrate is coordinated in
a trigonal planar arrangement. It is often
 used as a precursor to other silver-
containing compounds. It is used in
making photographic films, and in
laboratory setting as a staining agent in
protein visualization in PAGE gels and in
scanning electron microscopy
AQ AMMONIA
• “Spirit of Hartshorn”
• Ammonia occurs naturally and is
produced by human activity. It is an
important source of nitrogen which is
needed by plants and animals. Bacteria
found in the intestines can produce
ammonia. Ammonia is a colorless gas
with a very distinct odor. This odor is
familiar to many people because
ammonia is used in smelling salts, many
household and industrial cleaners, and
window-cleaning products. Ammonia gas
can be dissolved in water. This kind of
ammonia is called liquid ammonia or
aqueous ammonia. Once exposed to
open air, liquid ammonia quickly turns
into a gas. Ammonia is applied directly
into soil on farm fields, and is used to
make fertilizers for farm crops, lawns,
and plants. Many household and
industrial cleaners contain ammonia
SODIUM HYDROXIDE
• Sodium hydroxide is also known
as lye or soda , or caustic soda. At room
temperature, sodium hydroxide is a white
crystalline odorless solid that absorbs
moisture from the air. It is a synthetically
manufactured substance. When
dissolved in water or neutralized with
acid it releases substantial amounts of
heat, which may prove sufficient to ignite
combustible materials. Sodium hydroxide
is highly
FEHLING’S RGT A & B
• Fehling's A is a blue aqueous solution
of copper (II) sulfate
pentahydrate crystals, while Fehling's B
is a clear solution of aqueous potassium
sodium tartrate (also known as Rochelle
salt) and a strong alkali (commonly sodi
um hydroxide)
SCHIFF FUSCHIN’S RGT
• The Schiff test is a chemical test used to
check for the presence of aldehydes in a
given analyte. This is done by reacting
the analyte with a small quantity of a
Schiff reagent (which is the product
formed in certain dye formulation
reactions such as the reaction
between sodium bisulfite and fuchsin)
PHENYLHYDRAZINE RGT
• Phenylhydrazine is used to form
phenylhydrazones of natural mixtures of
simple sugars in order to render the
differing sugars easily separable from
each other. This molecule is also used
to induce acute hemolytic anemia in
animal models
POTASSIUM IODIDE
• Potassium Iodide is a metal halide
composed of potassium and iodide with
thyroid protecting and expectorant
properties. Potassium iodide can block
absorption of radioactive iodine by the
thyroid gland through flooding the thyroid
with non-radioactive iodine and
preventing intake of radioactive
molecules, thereby protecting the thyroid
from cancer causing radiation. In
addition, this agent acts as an
expectorant by increasing secretion of
respiratory fluids resulting in decreased
mucus
SULFURIC ACID
• Sulfuric acid is a colorless oily liquid. It is
soluble in water with release of heat. It is
corrosive to metals and tissue. It will char
wood and most other organic matter on
contact, but is unlikely to cause a fire. “Oil
of Vitriol”
HYDROCHLORIC ACID
 • Hydrochloric Acid. Your stomach makes
it naturally to help digest your lunch.
It's used industrially to process steel, the
material of choice for suspension bridges
and cars and trucks. Hydrochloric acid is
also used in the production of batteries,
photoflash bulbs and fireworks
ETHER
• Ether is an organic compound in which
two carbon atoms are linked through
an oxygen atom (C-O-C). An ether may
be a product of the condensation of
alcohols. Ether also refers loosely to
diethyl-ether, a colorless, volatile, highly
inflammable liquid used in industry and
biomedical research, and historically
important as an anesthetic agent
BENZALDEHYDE
• Benzaldehyde (C6H5CHO), the simplest
representative of the aromatic
aldehydes, occurring naturally as the
glycoside amygdalin. Prepared
synthetically, it is used chiefly in the
manufacture of dyes, cinnamic acid, and
other organic compounds, and to some
extent in perfumes and flavoring agents
ACETOPHENONE
• Acetophenone (C6H5COCH3),
organic compound used as an ingredient
in perfumes and as a chemical
intermediate in the manufacture of
pharmaceuticals, resins, flavoring
agents, and a form of tear gas. It also has
been used as a drug to induce sleep
METHANOL
• a nondrinking type of alcohol (also known
as wood alcohol and methyl alcohol)
which is mostly used to create fuel,
solvents and antifreeze. A colorless
liquid, it is volatile, flammable, and unlike
ethanol, poisonous for human
consumption
SODIUM HYPOCHLORITE
• “Bleach”
• Sodium hypochlorite solutions are clear,
greenish to yellow liquids with an odor
of chlorine. Calcium hypochlorite is a
white solid that readily decomposes
in water releasing oxygen and chlorine.
It also has a strong chlorine odor. Neither
compound occur naturally in the
environment. Sodium and calcium
hypochlorite are used primarily as
bleaching agents or disinfectants. They
are components of commercial bleaches,
cleaning solutions, and disinfectants for
drinking water and
waste water purification systems and
swimming pools
DIOXANE
• 1,4-Dioxane is a clear liquid that easily
dissolves in water. It is used primarily as
a solvent in the manufacture of chemicals
and as a laboratory reagent; 1,4-
dioxane also has various other uses that
take advantage of its solvent
properties. 1,4-Dioxane is a trace
contaminant of some chemicals used in
cosmetics, detergents, and shampoos
GLACIAL ACETIC ACID
an
• “Acetic acid”
• Acetic acid is one of the simplest
carboxylic acids. It is an important
chemical reagent and industrial
chemical. Acetic acid is produced and
excreted by certain bacteria, notably the
Acetobacter genus and Clostridium
acetobutylicum. These bacteria are
found universally in foodstuffs, water,
and soil, and acetic acid is produced
naturally as fruits and some other foods
spoil. Acetic acid is also a component of
the vaginal lubrication of humans and
other primates, where it appears to serve
as a mild antibacterial agent. Acetic acid
is found to be associated with
phenylketonuria, which is an inborn erro
EVAPORATED MILK 3. Mix well. Allow to stand for 5 minutes. If no
results is observed, warm over a water bath for
• Evaporated milk, known in some 2-3 minutes. Record your observations
countries as "unsweetened
condensed milk", is a shelf-stable
canned cow's milk product where about
FEHLING’S TEST
60% of the water has been removed from
fresh milk. It differs from sweetened 1. Mix 1 mL of Fehling’s solution A and B.
condensed milk, which contains added
2. Add 2 drops of acetaldehyde. Warm in a
sugar
water bath.
FERROUS CHLORIDE
3. Repeat steps 1 and 2 for acetone,
• Ferrous chloride is a greenish white benzaldehyde and acetophenone.
crystalline solid. It is soluble in water. It is
4. Record observations
noncombustible. It is used in sewage
treatment, in dyeing of fabrics, and for
many other uses.
SCHIFF’S FUCHSIN TEST
PHENOLPHTHALEIN
1. Place 2 mL of saturated NaHSO3 and 0.5 mL
• Phenolphthalein, (C20H14O4), an of ethyl alcohol in 4 separate test tubes. Filter off
organic compound of the phthalein family any precipitate. Then add 0.5 mL of each of the
that is widely employed as an acid- following: acetaldehyde, acetone,
base indicator. As an indicator of a benzaldehyde and acetophenone into 4
solution's pH, phenolphthalein is separate test tubes.
colorless below pH 8.5 and attains a pink
2. Set aside. Observe the rate at which the color
to deep red hue above pH 9.0
develops. Record the time interval
POTASSIUM PERMANGANATE
• Permanganic acid (HMnO4), potassium
ADDITION OF SODIUM BISULFITE
salt. A highly oxidative, water-soluble
compound with purple crystals, and a 1. Place 2 mL of saturated NaHSO3 and 0.5 mL
sweet taste. “MINERAL CHAMELEON’ of ethyl alcohol in 4 separate test tubes. Filter off
any precipitate. Then add 0.5 mL of each of the
following: acetaldehyde, acetone,
Procedures benzaldehyde and acetophenone into 4
separate test tubes.
TOLLEN’S TEST
2. Shake vigorously for a minute. Place the tube
1. To 5 mL of 1% AgNO3 solution, add 1 drop of in a freezing mixture. Observe any change in
6N NaOH solution. Then add dropwise of
odor and in appearance
ammonia solution, shaking after each addition
until the precipitate which forms at first just
dissolves. Avoid adding more than what is
IODOFORM TEST
needed to dissolve the precipitate.
1. Prepare 4 test tubes, then to each tube place
2. Add to the 4 clean test tubes 2 mL of freshly
5 mL of 10% KI solution. Add 2 drops of the
prepared Tollen’s reagent and add separately 2
carbonyl compounds.
drops of the following: acetone, acetaldehyde,
benzaldehyde and acetophenone.
2. Add slowly with shaking 5 mL of 5-7% solution
of Sodium hypochlorite (chlorox). Observe
yellow precipitate.
COMPARISON OF OXIDATION RATES OF
ALDEHYDES AND KETONES
1. Place 2 mL of 0.05% KMnO4 solution in each
of the 4 test tubes. To one tube add 2 drops of
acetaldehyde. Shake. Note the rate of
decolorization by comparison with a control tube
of dilute KMnO4 solution.
2. Do likewise with acetone, benzaldehyde and
acetophenone.
3. Record observations and possible inferences
in the data table.
4. Heat in a water bath. Add more KI solution to
give a permanent brownish iodine color.
5. Observe any change in appearance and odor
CANNIZZARO REACTION
1. In a small flask place 1 mL of benzaldehyde
and 2mL of 50% NaOH solution.
2. Stopper tightly and shake until a permanent
emulsion is formed. Allow to stand overnight.
Observe any change.
3. Transfer the mixture to a test tube. Add 5 mL
water. Note any separation of layers.
4. Extract the upper layer with 3 mL of ether.
Shake gently. Separate the ether layer. What
compound dissolve in the ether?
5. Transfer the aqueous layer in a beaker. Add
a drop of phenolphthalein indicator. Carefully
acidify with conc. HCl. Allow to stand for a few
minutes. Decant and filter the crystals of benzoic
acid

SPECIAL ALDEHYDE REACTIONS

FORMALDEHYDE MILK TEST
1. To 2 mL of diluted (1:10) whole milk in a test
tube, add 2 drops of 30-40% formaldehyde
solution (formalin) and 2 drops of 10% Ferric
Chloride. Mix thoroughly.
2. Hold the test tube in an inclined position and
pour off carefully 1 mL of concentrated H2SO4
down the sides of the tube. Observe the
interface between the 2 layers.
3. Compare milk without any formalin

RESIN FORMATION
1. Place 3 mL of 6N NaOH in a test tube. In
another, mix 0.5 mL of 6N NaOH and 2.5 mL of
water.
2. To both test tubes add 10-15 drops each of
acetaldehyde solution. Warm the mixtures.
3. Observe all changes in color and in
appearances