LABORATORY ACTIVITY 12 ǁ ǁ

REACTIONS OF ALDEHYDES AND RCCH3 + NaHSO3 → RCCH3 + NaSO3

KETONES
Methylcarbonyl Compounds like
acetaldehyde and acetone form a yellow
crystalline precipitate by reaction with I2 in the
Reactions of Aldehydes and Ketones may be
presence of dilute alkali. Alcohols of the type
grouped into:
RCHOHCH3 also give the iodoform test.
1. Oxidation – Reduction to the Carbonyl
Condensation reaction involving the carbonyl
Group
group is illustrated by the aldol condensation.
2. Addition to the Carbonyl Group
When acetaldehyde is warmed with dilute
3. Condensation and Polymerization
NaOH. 2 molecules unite between the carbonyl
Reactions
group of one end and the alpha carbon of
Aldehydes are readily oxidized to the another as shown:
corresponding carboxylic acids. Ketones are
[OH]- 2 CH3 CHO → CH3 CHCH2 CHO
difficult to oxidize. Therefore, aldehydes are
stronger reducing agents than ketones. ǁ
Mild oxidizing agents like Tollen’s reagent (Ag+) OH
and Fehling’s reagent (Cu2+) are readily
Aldol compound (B – hydroxy aldehyde)
reduced by aldehydes to silver mirror and brick
red precipitate of Cu2O respectively. Aromatic The aldol molecule has a reactive aldehyde
aldehydes reduce Tollen’s reagent but not group and the reaction mmay be repeated
Fehling’s. Ketones do not reduce either of the indefinitely forming aldehyde resin. This is what
two reagents. takes place when acetaldehyde is heated with
strong NaOH.
RCHO + 2 Ag+ + 3 OH- → RCOO + Ag + 2 HOH
RCHO + 2 Cu 2+ + 5 OH- → RCOO + Cu2O + Aldehydes that do not have any alpha –
3 HOH hydrogen do not undergo aldol condensation.
Such aldehydes undergo Cannizaro reaction
Aldehyde and ketones may also be
when treated with strong NaOH. ~CHO + NaOH
differentiated by the Schiff’s fuschin test. The
→ ~COOna + CH2OH
reaction with aldehydes produces a violet –
purple or magenta red color (characteristic blue
shade in red).
FORMALDEHYDE
With phenylhydrazine, aldehydes and ketones
form addition compounds which may be used • Formaldehyde is a colorless poisonous
for their identification because of the gas synthesized by the oxidation
characteristics crystalline shapes and melting of methanol and used as an antiseptic,
points of their phenylhydrazines. disinfectant. Formaldehyde, solutions
(formalin) (corrosive) appears as a
H H colorless liquid with a pungent irritating
ǁ HOH ǁ odor

RCCH3 + H2NNHC6H5 → RC=NNHC6H5 SILVER NITRATE

Aldehydes and methyl ketones give solid • Silver nitrate is an inorganic compound
addition products with NaHSO3. with the chemical formula AgNO3. In its
solid form, silver nitrate is coordinated in
H H a trigonal planar arrangement. It is often
 used as a precursor to other silver- sodium tartrate (also known as Rochelle
containing compounds. It is used in salt) and a strong alkali (commonly sodi
making photographic films, and in um hydroxide)
laboratory setting as a staining agent in
SCHIFF FUSCHIN’S RGT
protein visualization in PAGE gels and in
scanning electron microscopy • The Schiff test is a chemical test used to
check for the presence of aldehydes in a
AQ AMMONIA
given analyte. This is done by reacting
• “Spirit of Hartshorn” the analyte with a small quantity of a
• Ammonia occurs naturally and is Schiff reagent (which is the product
produced by human activity. It is an formed in certain dye formulation
important source of nitrogen which is reactions such as the reaction
needed by plants and animals. Bacteria between sodium bisulfite and fuchsin)
found in the intestines can produce
PHENYLHYDRAZINE RGT
ammonia. Ammonia is a colorless gas
with a very distinct odor. This odor is • Phenylhydrazine is used to form
familiar to many people because phenylhydrazones of natural mixtures of
ammonia is used in smelling salts, many simple sugars in order to render the
household and industrial cleaners, and differing sugars easily separable from
window-cleaning products. Ammonia gas each other. This molecule is also used
can be dissolved in water. This kind of to induce acute hemolytic anemia in
ammonia is called liquid ammonia or animal models
aqueous ammonia. Once exposed to
open air, liquid ammonia quickly turns POTASSIUM IODIDE
into a gas. Ammonia is applied directly • Potassium Iodide is a metal halide
into soil on farm fields, and is used to composed of potassium and iodide with
make fertilizers for farm crops, lawns, thyroid protecting and expectorant
and plants. Many household and properties. Potassium iodide can block
industrial cleaners contain ammonia absorption of radioactive iodine by the
SODIUM HYDROXIDE thyroid gland through flooding the thyroid
with non-radioactive iodine and
• Sodium hydroxide is also known preventing intake of radioactive
as lye or soda , or caustic soda. At room molecules, thereby protecting the thyroid
temperature, sodium hydroxide is a white from cancer causing radiation. In
crystalline odorless solid that absorbs addition, this agent acts as an
moisture from the air. It is a synthetically expectorant by increasing secretion of
manufactured substance. When respiratory fluids resulting in decreased
dissolved in water or neutralized with mucus
acid it releases substantial amounts of
heat, which may prove sufficient to ignite SULFURIC ACID
combustible materials. Sodium hydroxide • Sulfuric acid is a colorless oily liquid. It is
is highly soluble in water with release of heat. It is
FEHLING’S RGT A & B corrosive to metals and tissue. It will char
wood and most other organic matter on
• Fehling's A is a blue aqueous solution contact, but is unlikely to cause a fire. “Oil
of copper (II) sulfate of Vitriol”
pentahydrate crystals, while Fehling's B
is a clear solution of aqueous potassium HYDROCHLORIC ACID
 • Hydrochloric Acid. Your stomach makes SODIUM HYPOCHLORITE
it naturally to help digest your lunch.
• “Bleach”
It's used industrially to process steel, the
material of choice for suspension bridges • Sodium hypochlorite solutions are clear,
and cars and trucks. Hydrochloric acid is greenish to yellow liquids with an odor
also used in the production of batteries, of chlorine. Calcium hypochlorite is a
white solid that readily decomposes
photoflash bulbs and fireworks
in water releasing oxygen and chlorine.
ETHER It also has a strong chlorine odor. Neither
compound occur naturally in the
• Ether is an organic compound in which
environment. Sodium and calcium
two carbon atoms are linked through
hypochlorite are used primarily as
an oxygen atom (C-O-C). An ether may
bleaching agents or disinfectants. They
be a product of the condensation of
are components of commercial bleaches,
alcohols. Ether also refers loosely to
cleaning solutions, and disinfectants for
diethyl-ether, a colorless, volatile, highly
drinking water and
inflammable liquid used in industry and
waste water purification systems and
biomedical research, and historically
swimming pools
important as an anesthetic agent
DIOXANE
BENZALDEHYDE
• 1,4-Dioxane is a clear liquid that easily
• Benzaldehyde (C6H5CHO), the simplest
dissolves in water. It is used primarily as
representative of the aromatic
a solvent in the manufacture of chemicals
aldehydes, occurring naturally as the
and as a laboratory reagent; 1,4-
glycoside amygdalin. Prepared
dioxane also has various other uses that
synthetically, it is used chiefly in the
take advantage of its solvent
manufacture of dyes, cinnamic acid, and
properties. 1,4-Dioxane is a trace
other organic compounds, and to some
contaminant of some chemicals used in
extent in perfumes and flavoring agents
cosmetics, detergents, and shampoos
ACETOPHENONE
GLACIAL ACETIC ACID
• Acetophenone (C6H5COCH3), an
• “Acetic acid”
organic compound used as an ingredient
• Acetic acid is one of the simplest
in perfumes and as a chemical
carboxylic acids. It is an important
intermediate in the manufacture of
chemical reagent and industrial
pharmaceuticals, resins, flavoring
chemical. Acetic acid is produced and
agents, and a form of tear gas. It also has
excreted by certain bacteria, notably the
been used as a drug to induce sleep
Acetobacter genus and Clostridium
METHANOL acetobutylicum. These bacteria are
found universally in foodstuffs, water,
• a nondrinking type of alcohol (also known and soil, and acetic acid is produced
as wood alcohol and methyl alcohol) naturally as fruits and some other foods
which is mostly used to create fuel, spoil. Acetic acid is also a component of
solvents and antifreeze. A colorless the vaginal lubrication of humans and
liquid, it is volatile, flammable, and unlike other primates, where it appears to serve
ethanol, poisonous for human as a mild antibacterial agent. Acetic acid
consumption 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 CANNIZZARO REACTION
of Sodium hypochlorite (chlorox). Observe
1. In a small flask place 1 mL of benzaldehyde
yellow precipitate.
and 2mL of 50% NaOH solution.
2. Stopper tightly and shake until a permanent
COMPARISON OF OXIDATION RATES OF emulsion is formed. Allow to stand overnight.
ALDEHYDES AND KETONES Observe any change.
1. Place 2 mL of 0.05% KMnO4 solution in each 3. Transfer the mixture to a test tube. Add 5 mL
of the 4 test tubes. To one tube add 2 drops of water. Note any separation of layers.
acetaldehyde. Shake. Note the rate of
4. Extract the upper layer with 3 mL of ether.
decolorization by comparison with a control tube
Shake gently. Separate the ether layer. What
of dilute KMnO4 solution.
compound dissolve in the ether?
2. Do likewise with acetone, benzaldehyde and
5. Transfer the aqueous layer in a beaker. Add
acetophenone.
a drop of phenolphthalein indicator. Carefully
3. Record observations and possible inferences acidify with conc. HCl. Allow to stand for a few
in the data table. minutes. Decant and filter the crystals of benzoic
acid
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

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