Classification Tests for Hydroxyl- and Carbonyl- Containing Compounds

Reyes, K.O., Rivera, G.I., Samonte, A.A., Soliven, R.Y.*, Sotto, K.C.
2CMT, Faculty of Pharmacy, UST

Abstract

Hydroxyl- or carbonyl- containing samples were given to the group for analysis. Hydroxyl
group refers to a functional group containing OH- when it is a substituent in an organic compound
whereas carbonyl group refers to a divalent chemical unit consisting of a carbon and an oxygen
atom connected by a double bond. Hydroxyl group is the characteristic functional group of alcohols
and phenols while carbonyl group is the characteristic functional group of aldehydes and ketones.
The samples were analyzed through tests involving solubility of alcohols in water, Lucas Test,
Chromic Acid Test (Jones Oxidation), 2,4-Dinitrophenylhydrazone (2,4-DNP) Test, Fehling’s Test,
Tollens’ Silver Mirror Test, and Iodoform Test. Lucas Test differentiates primary, secondary, and
tertiary alcohols. Chromic Acid Test is a test for oxidizables or any compounds that possess
reducing property 2,4-DNP Test is a test for aldehydes and ketones. Fehling’s Test and Tollens’
Silver Mirror Test are tests for aldehydes. Iodoform test is a test for methyl carbinol and methyl
carbonyl groups. When solubility of ethanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol
and benzyl alcohol was tested, only benzyl alcohol exhibited insolubility. Upon subjecting n-butyl
alcohol, sec-butyl alcohol, and tert-butyl alcohol to Lucas Test, tert-butyl alcohol formed two layers,
sec-butyl alcohol demonstrated slight turbidity and n-butyl alcohol produced a clear solution. N-
butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-butraldehyde, benzaldehyde, acetone, and
acetophenone underwent Chromic Acid Test (Jones Oxidation). N-butyl alcohol, sec-butyl alcohol,
n-butraldehyde, and benzaldehyde showed a positive result of green or blue-green solution.
Fehling’s Test, 2,4-dinitrophenylhydrazone (2,4-DNP) test, and Tollens’ Silver Mirror Test were
performed on acetone, acetaldehyde, n-butraldehyde, benzaldehyde, and acetophenone. All
compounds produced a positive result of either a yellow or an orange precipitate when subjected to
2,4-DNP test. Acetaldehyde and n-butraldehyde are positive to Fehling’s test forming a crude red
precipitate and benzaldehyde demonstrated turbidity. Acetone and acetophenone produced a
negative result of a clear blue solution under the same test. The samples produced a positive result
of silver mirror except for acetone which produced a grayish-black solution and acetophenone which
formed a gel-like precipitate. Lastly, Iodoform Test was performed on acetaldehyde, acetone,
acetophenone, benzaldehyde, and isopropyl alcohol. All of the compounds exhibited positive result
forming a yellow precipitate excluding benzaldehyde which formed a white suspended precipitate
instead.

Introduction

Hydroxyl group is used to describe Alcohols are characterized by one

the functional group –OH when it is a
substituent in an organic compound.
Hydroxyl groups are especially important
in biological chemistry because of their
tendency to form hydrogen bonds both as
donor and acceptor. This property is also
related to their ability to increase
hydrophilicity and water solubility. The
hydroxyl group is especially predominant
in the family of molecules known as
carbohydrates. Hydroxyl group is the
characteristic functional group of alcohols
and phenols.
Figure 1 Structure of a Hydroxyl-
containing compound
or more hydroxyl (−OH) groups attached
to a carbon atom of an alkyl group
(hydrocarbon chain). Alcohols may be
considered as organic derivatives of water
(H2O) in which one of the hydrogen atoms
has been replaced by an alkyl group,
typically represented by R in organic
structures. Because of hydrogen bonding,
alcohols tend to have higher boiling points
than comparable hydrocarbons and ethers
Alcohols, like water, can show either acidic
or basic properties at the O-H group. With
a pKa of around 16-19 they are generally
slightly weaker acids than water, but they
are still able to react with strong bases
such as sodium hydride or reactive metals
such as sodium. The salts that result are
called alkoxides. Alcohols have an odor
that is often described as “biting” and as
“hanging” in the nasal passages.
There are three classifications of
alcohols by the carbon to which the
hydroxyl group is attached. Primary
alcohols are those in which the hydroxyl
group is attached to the carbon with only
one carbon attached. Secondary alcohols
are compounds in which the OH- is
attached to a carbon which has two other
carbons attached. Tertiary alcohols are
compounds in which a hydroxyl group is
attached to a carbon with three attached
carbons.
Phenols are aromatic compounds in
which a hydroxide group is directly
bonded to an aromatic ring system. They
are very weak acids, and like alcohols,
form ethers and esters. The main phenols
are phenol itself, cresol, resorcinol,
pyrogallol, and picric acid.
Phenol itself (C6H5OH), also known as
carbolic acid, is a white, hygroscopic
crystalline solid, isolable from coal tar, but
made by acid hydrolysis of cumene
hydroperoxide, or by fusion of sodium
benzenesulfonate with sodium hydroxide.
Formerly used as an antiseptic, phenol
has more latterly been used to make
bakelite and other resins, plastics, dyes,
detergents, and drugs.
The hydroxyl- containing
compounds used in the experiment are
ethanol, n-butyl alcohol, sec-butyl alcohol,
tert-butyl alcohol, isopropyl alcohol, and
benzyl alcohol.
Ethanol, C2H5OH, (also known as
ethyl alcohol, pure alcohol, grain alcohol,
or drinking alcohol) is the second member
of the aliphatic alcohol series. It is a clear,
colorless, volatile, and flammable liquid
which is completely miscible with water
and organic solvents. It burns with a
smokeless blue flame that is not always
visible in normal light. Ethanol has
widespread use as a solvent of substances
intended for human contact or
consumption, including scents, flavorings,
colorings, and medicines. In chemistry, it
is both an essential solvent and a
feedstock for the synthesis of other
products.
Figure 2 Structure of Ethanol
N-butyl alcohol (also known as n-
butanol, 1-Butanol or 1-butyl alcohol) is a
four carbon straight chain alcohol. It is a
volatile, clear liquid with a strong alcoholic
odor, and is miscible with water. It is a
highly refractive compound which
corrodes some plastics, and rubbers. It is
miscible with many organic solvents, and
incompatible with strong oxidizers. N-
butanol is used as a direct solvent and as
an intermediate in the manufacture of
other organic chemicals.
Figure 3 Structure of n-butyl alcohol
Sec-butyl alcohol with the formula
CH3CH(OH)CH2CH3 (also known as sec-
butanol, 2-butyl alcohol, or 2-butanol) is a
flammable, colorless liquid that is soluble
in 12 parts water and completely miscible
with polar organic solvent such as ethers
and other alcohols.
Figure 4 Structure of sec-butyl alcohol
Tert-Butanol, C4H10O is a colorless
liquid or white solid, depending on the
ambient temperature. It is the simplest
tertiary alcohol. and one of the four
isomers of butanol. tert-Butanol is a clear
liquid with a camphor-like odor. It is very
soluble in water and miscible with ethanol
and diethyl ether. It is unique among the
isomers of butanol because it tends to be
a solid at room temperature, with a
melting point slightly above 25 °C. As a
tertiary alcohol, tert-butanol is more
stable to oxidation and less reactive than
the other isomers of butanol. tert-Butanol
is used as a solvent, as a denaturant for
ethanol, as an ingredient in paint
removers, as an octane booster for
gasoline, as an oxygenate gasoline
additive, and as an intermediate in the
synthesis of other chemical commodities,
other flavors and perfumes.
Figure 5 Structure of tert-butyl alcohol
Isopropyl alcohol (also propan-2-
ol, 2-propanol is a common name for a
chemical compound with the molecular
formula C3H8O. It is a colorless, flammable
chemical compound with a strong odor. It
is the simplest example of a secondary
alcohol, where the alcohol carbon is
attached to two other carbons. Being a
secondary alcohol, isopropyl alcohol can
be oxidized to acetone, which is the
corresponding ketone. Isopropyl alcohol
dissolves a wide range of non-polar
compounds. It is also relatively non-toxic
and evaporates quickly. Thus it is used
widely as a solvent and as a cleaning fluid,
especially for dissolving lipophilic
contaminants such as oil.
Figure 7 Structure of Isopropyl alcohol
Benzyl alcohol, C6H5CH2OH, is a
colorless liquid with a mild pleasant
aromatic odor. It is a useful solvent due to
its polarity, low toxicity, and low vapor
pressure. Benzyl alcohol is partially
soluble in water (4 g/100 mL) and
completely miscible in alcohols and diethyl
ether. Like most alcohols, it reacts with
carboxylic acids to form esters. Benzyl
alcohol is used as a general solvent for
inks, paints, lacquers, and epoxy resin
coatings. It is also a precursor to a variety
of esters, used in the soap, perfume, and
flavor industries. It is often added to
intravenous medication solutions as a
preservative due to its bacteriostatic and
antipruritic properties.
Figure 6 Structure of Benzyl alcohol
Carbonyl group is a divalent
chemical unit consisting of a carbon (C)
and an oxygen (O) atom connected by a
double bond. The group is a constituent of
carboxylic acids, esters, anhydrides, acyl
halides, amides, and quinones, and it is
the characteristic functional group of
aldehydes and ketones. Carboxylic acid
(and their derivatives), aldehydes,
ketones, and quinones are also known
collectively as carbonyl compounds.
Aldehydes and ketones contain carbonyl
groups attached to alkyl or aryl groups
and a hydrogen atom or both. These
groups have little effect on the electron
distribution in the carbonyl group; thus,
the properties of aldehydes and ketones
are determined by the behaviour of the
carbonyl group. In carboxylic acids and
their derivatives, the carbonyl group is
attached to one of the halogen atoms or
to groups containing atoms such as
oxygen, nitrogen, or sulfur. These atoms
do affect the carbonyl group, forming a
new functional group with distinctive
properties.

Figure 7 Structure of a Carbonyl-
containing compound
An aldehyde is an organic
compound containing a terminal carbonyl
group. This functional group, called an
aldehyde group, consists of a carbon atom
bonded to a hydrogen atom with a single
covalent bond and an oxygen atom with a
double bond. Thus the chemical formula
for an aldehyde functional group is
-CH=O, and the general formula for an
aldehyde is R-CH=O. The aldehyde group
is occasionally called the formyl or
methanoyl group. The word aldehyde is a
combination of parts of the words alcohol
and dehydrogenated, because the first
aldehyde was prepared by removing two
hydrogen atoms (dehydrogenation) from
ethanol. Molecules that contain an
aldehyde group can be converted to
alcohols by the addition of two hydrogen
atoms to the central carbon oxygen
double bond (reduction). Organic acids
are the result of the introduction of one
oxygen atom to the carbonyl group
(oxidation). Aldehydes are very easy to
detect by smell. Some are very fragrant,
and others have a smell resembling that
of rotten fruit.
Figure 8 Structure of Aldehyde
Ketone features a carbonyl group
(C=O) bonded to two other carbon atoms.
They differ from aldehydes in that the
carbonyl is placed between two carbons
rather than at the end of a carbon
skeleton. They are also distinct from other
functional groups, such as carboxylic
acids, esters and amides, which have a
carbonyl group bonded to a hetero atom.
Ketone compounds have important
physiological properties. They are found in
several sugars and in compounds for
medicinal use, including natural and
synthetic steroid hormones.
Figure 9 Structure of Ketone
Some of the carbonyl-containing
compounds used in the experiment are
benzaldehyde, n-butraldehyde,
acetaldehyde, acetone and acetophenone.
Benzaldehyde, C6H5CHO (also
known as benzenecarbonal) is a colorless
liquid aldehyde with a characteristic
almond odor. It boils at 180°C, is soluble
in ethanol, but is insoluble in water. It is
formed by partial oxidation of benzyl
alcohol, and on oxidation forms benzoic
acid. It is called oil of bitter almond, since
it is formed when amygdalin, a glucoside
present in the kernels of bitter almonds
and in apricot pits, is hydrolyzed, e.g., by
crushing the kernels or pits and boiling
them in water; glucose and hydrogen
cyanide (a poisonous gas) are also
formed. It is also prepared by oxidation of
toluene or benzyl chloride or by treating
benzal chloride with an alkali, e.g., sodium
hydroxide. Benzaldehyde is used in the
preparation of certain aniline dyes and of
other products, including perfumes and
flavorings.
Figure 10 Structure of Benzaldehyde
Acetaldehyde, CH3CHO (also known
as ethanol) is a colorless liquid aldehyde,
sometimes simply called aldehyde. It is
soluble in water and ethanol.
Acetaldehyde is made commercially by the
oxidation of ethylene with a palladium
catalyst. It is used as a reducing agent
(e.g., for silvering mirrors), in the
manufacture of synthetic resins and Acetophenone is the organic
dyestuffs, and as a preservative. compound with the formula C6H5C(O)CH3.
It is the simplest aromatic ketone. This
Figure 11 Structure of Acetaldehyde colourless, viscous liquid is a precursor to
useful resins and fragrances.
Acetophenone can be obtained by a
variety of methods. In industry,
acetophenone is recovered as a by-
product of the oxidation of ethylbenzene,
which mainly gives ethylbenzene
N-butyraldehyde (also known as hydroperoxide for use in the production of
butanal) is an organic compound with the propylene oxide
formula CH3(CH2)2CHO. This compound is
the aldehyde derivative of butane. It is a Figure 14 Structure of Acetophenone
colourless flammable liquid that smells
like sweaty feet. It is miscible with most
organic solvents. n-Butyraldehyde is used
as an intermediate in the manufacturing
plasticizers, alcohols, solvents and
polymers (such as 2-Ethylhexanol, n-
butanol, trimethylolpropane, n-butyric The hydroxyl- and carbonyl-
acid, polyvinyl butyral, methyl amyl containing compounds were analyzed by
ketone). It is also used as an intermediate utilization of different tests such as testing
to make pharmaceuticals, agrochemicals, the solubility of alcohols in water, Lucas
antioxidants, rubber accelerators, textile Test, Chromic Acid Test (Jones Oxidation),
auxiliaries, perfumery and flavors. 2,4-Dinitrophenylhydrazone Test,
Fehling’s Test, Tollens’ Silver Mirror Test,
Figure 12 Structure of n-Butyraldehyde and Iodoform Test.

Most organic compounds are not

Acetone (also known as
propanone) is the organic compound with
the formula (CH3)2CO. This colorless,
mobile, flammable liquid with a
characteristic sweetish smell is the
simplest example of the ketones. Acetone
is miscible with water and serves as an
important solvent in its own right,
typically as the solvent of choice for
cleaning purposes in the laboratory.
Figure 13 Structure of Acetone
soluble in water with the exception of low
molecular-weight amines and oxygen-
containing compounds like alcohols,
carboxylic acids, aldehydes, and ketones.
Low molecular-weight compounds are
generally limited to those with fewer than
five carbon atoms.
Lucas Test often provides
classification information for alcohols, as
well as a probe for the existence of the
hydroxyl group. Substrates that easily
give rise to cationic character at the
carbon bearing the hydroxyl group
undergo this test readily; primary alcohols
do not give a positive result. Since the
Lucas Test depends on the appearance of
the alkyl chloride as a second liquid
phase, it is normally applicable only to
alcohols that are soluble in the reagent.
This limits the test in general to
monofunctional alcohols lower than hexyl
and certain polyfunctional molecules.
Chromic Acid Test (Jones
Oxidation) detects the presence of a
hydroxyl substituent that is on a carbon
bearing at least one hydrogen, and
therefore oxidizable.
2,4-Dinitrophenylhydrazone Test
can be used to qualitatively detect the
carbonyl functionality of a ketone or
aldehyde functional group.
Fehling’s Test and Tollens’ Silver
Mirror Test are used to detect aldehydes.
However, Fehling's solution can only be
used to test for aliphatic aldehydes,
whereas Tollens' reagent can be used to
test for both aliphatic and aromatic
aldehydes.
Iodoform Test is a test for methyl
carbinol (secondary alcohol with adjacent
methyl group) and methyl carbonyl group.
Methodology
A. Solubility of Alcohols in Water
Five test tubes were labelled
accordingly and ten drops each of ethanol,
n-butyl alcohol, sec-butyl alcohol, tert-
butyl alcohol, and benzyl alcohol were
placed into the test tubes by the use of a
Pasteur pipette. 1-ml of water was then
added dropwise to the tube containing
alcohol and the mixture was shaken
thoroughly after each addition. If
cloudiness resulted, 0.25-ml of water at a
time was added continuously with
vigorous shaking until a homogeneous
dispersion results. The total volume of
water added was noted. If cloudiness
resulted after the addition of 2.0-ml of
water, the alcohol is said to be soluble in
water. The results were noted down.
B. Lucas Test
This test was performed on n-butyl
alcohol, sec-butyl alcohol, and tert-butyl
alcohol.
Lucas reagent was prepared by
dissolving 16 g of anhydrous zinc chloride
in 10-ml of concentrated hydrochloric
acid. The mixture was then allowed to
cool.
50-mg or 2-3 drops of the sample
was added to 1-ml of the reagent in a
small vial or test tube and the mixture
was shaken vigorously for a few seconds.
The mixture was allowed to stand at room
temperature. The rate of formation of the
cloudy suspension or the formation of two
layers were observed.
C. Chromic Acid Test (Jones Oxidation)
This test was performed on n-butyl
alcohol, sec-butyl alcohol, tert-butyl
alcohol, n-butyraldehyde, benzaldehyde,
acetone, and acetophenone.
1 drop of liquid or a small amount
of the solid sample was dissolved in 1-ml
of acetone in a small vial or test tube. 2
drops of 10% aqueous Potassium
chromate solution and 5 drops of 6M
sulphuric acid were added into the
mixture.
D. 2,4-dinitrophenylhydrazone (or 2,4-
DNP Test)
This test was performed on
acetone, acetaldehyde, n-butyraldehyde,
benzaldehyde, and acetophenone.
The reagent was prepared by
slowly adding a solution of 3 g of 2,4-
dinitrophenylhydrazine in 15-ml of
concentrated sulphuric acid, while stirring
to a mixture of 20-ml of water and 70-ml
of 95% ethanol. The solution was then
stirred and filtered.
 allowed to stand for 10 minutes. If no
A drop of a liquid sample was reaction has occurred, the test tube was
placed into a small sample. 5 drops of placed in a beaker of warm water (35-50
o
95% ethanol was added and well shaken. C) for 5 minutes. Observations were
Afterwards, 3 drops of 2,4-DNP was added recorded.
and if no yellow or orange precipitate It was noted that if Tollens’
formed, the solution was allowed ro stand reagent is left unused for a period of time,
for at least 15 minutes. it may form explosive silver. This was
avoided by neutralizing unused reagent
E. Fehling’s Test with a little nitric acid and discarded
afterwards.
This test was performed on
acetaldehyde, n-butyraldehyde, acetone, G. Iodoform Test
benzaldehyde, and acetophenone.
This test was performed on
Fehling’s reagent was prepared by acetaldehyde, acetone, acetophenone,
mixing equal amounts of Fehling’s A and benzaldehyde, and isopropyl alcohol.
Fehling’s B. Fehling’s A was prepared by
dissolving 7 g of hydrated copper (II) 2 drops of each sample was placed
sulfate in 100-ml of water. Fehling’s B was into its own small vial or test tube. 20
prepared by mixing 35 g of Potassium drops of fresh chlorine bleach (5% Sodium
sodium tartrate and 10 g of Sodium hypochlorite) was slowly added while
hydroxide in 100-ml water. shaking to each test tube and then,
mixed. The formation of a yellow
1-ml of freshly prepared Fehling’s participate was noted.
reagent was placed into each test tube. 3
drops of the sample to be tested was
added in to the tube. The tubes were then Results and Discussion
placed in a beaker of boiling water and
changes within 10-15 minutes were Table 1 Solubility of Alcohol in Water
observed. Alcohol Condensed Amount of Solubility in
Structural Formula Water (in ml) Water
needed to
F. Tollens’ Silver Mirror Test produce a
homogeneou
s dispersion
This test was performed on Ethanol CH3CH2OH 1 ml Miscible
acetaldehyde, benzaldehyde, acetone, n- N-butyl CH3CH2CH2CH2OH 2 ml Miscible
butyraldehyde, and acetophenone. alcohol
Sec- 1 ml Miscible
butyl
The reagent was prepared by alcohol
adding 2 drops of 5% Sodium hydroxide Tert- 1 ml Miscible
solution to 2-ml of 5% Silver nitrate butyl
solution and mixing thoroughly. Next, only alcohol
enough 2% ammonium hydroxide
(concentrated ammonium hydroxide is Benzyl N/A Immiscible
alcohol
28%) was added drop by drop and with
stirring to dissolve the precipitate. Adding
excess ammonia will cause discrepancies
Table 1 shows alcohols such as
on the result of the test.
ethanol, n-butyl alcohol, sec-butyl alcohol,
tert-butyl alcohol, and benzyl alcohol and
Four test tubes with 1-ml of freshly
their solubility in water.
prepared Tollens’ reagent were prepared.
Two drops each of the samples were then
added. The mixture was shaken and
 Ethanol, n-butyl alcohol, sec-butyl
alcohol, and tert-butyl alcohol are all
miscible with water with the exception of
benzyl alcohol which exhibited insolubility.
The table shows that all alcohols
are soluble in water except under C 6.
There are different factors affecting
solubility. One of which is number of
carbon atom wherein the higher the
number of carbon atoms, the more
insoluble the alcohol is in water. Another
factor is the branching of carbon chain in
which the more branching present, the
more soluble (with the same number of
carbons) it is. Lastly, the presence of
polar functional groups (-OH, -NH2,
-CO2H) also tends to affect alcohol
solubility in water. A compound with polar
functional group is more soluble in water.
As stated, all alcohols are soluble
in water except under C6. Hence, ethanol,
n-butyl alcohol, sec-butyl alcohol, and
tert-butyl alcohol are all miscible with
water. Ethanol has two carbon atoms,
while the other three all have four carbons
since they are all derivatives of the
alcohol, butanol. Benzyl alcohol is
immiscible with water because it is an
aromatic alcohol.
Ethanol is the most soluble alcohol
followed by tert-butyl alcohol, sec-butyl
alcohol, and n-butyl alcohol. Ethanol
exhibits fastest solubility because it has
only two carbon atoms as compared to
the butanol derivatives having four carbon
atoms. Tert-butyl alcohol is the most
soluble among the butanol derivatives
because it has the most branching
substituents present.
Table 2 Reaction of Sample Compounds to
Lucas Test
Substance Condensed Reaction
Structural Formula
n-butyl CH3CH2CH2CH2OH Clear
alcohol solution
Sec-butyl Clear
alcohol solution
Tert- Turbid Immiscible
butyl solution
and
alcohol
formation
of two
layers
Table 2 shows the reaction of
butanol derivatives to Lucas Test. N-butyl
alcohol and sec-butyl alcohol yielded a
clear solution when subjected to Lucas
Test whereas tert-butyl alcohol resulted to
a cloudy immiscible suspension which
eventually formed two layers.
Lucas Test differentiates primary,
secondary, and tertiary alcohols. Reagents
used include anhydrous ZnCl2 and HCl.
Positive result is based on turbidity (alkyl
chloride formation) and the rate of the
reaction was observed. Tertiary alcohols
form the second layer in less than a
minute. Secondary alcohols require 5-10
minutes before formation of second layer
while primary alcohols are usually
unreactive. Based on Table 2, tert-butyl
alcohol immediately formed two layers;
hence, it is known to be a tertiary alcohol.
Sec-butyl alcohol when subjected to Lucas
test resulted to a clear solution although
theoretically, a secondary alcohol
dissolves to give a clear solution (provided
R does not have too many carbon atoms
in the chain.), then form chlorides (cloudy
solution) within five minutes. N-butyl
alcohol was unreactive and is considered
to be the primary alcohol. Generally, the
order of reactivity of the alcohols toward
Lucas reagent is 3°>2°>1° because the
reaction rate is much faster when the
carbocation intermediate is more
stabilized by a greater number of electron
donating alkyl group bonded to the
positive carbon atom. This means that the
greater the alkyl groups present in a
compound, the faster its reaction would
be with the Lucas solution.
Inference
Miscible
Miscible
The reaction of alcohols with
halogen acids is a displacement reaction in
which the reactive species is the Secondary alcohols are
conjugate acid of the alcohol R-OH2+, and intermediate in reactivity between primary
as might be expected, is analogous to the and tertiary alcohols. Although they are
replacement reactions of organic halides not appreciably affected by concentrated
and related compounds with silver nitrate hydrochloric acid alone, they react with it
and iodide ion. The effects of structure on fairly rapidly in the presence of anhydrous
reactivity in these reactions are closely zinc chloride; a cloudy appearance of the
related. Thus, primary alcohols do not mixture is observed within 5 minutes, and
react perceptibly with hydrochloric acid in about 10 minutes, a distinct layer is
even in the presence of zinc chloride at usually visible.
ordinary temperatures; chloride ion is too
poor a nucleophilic agent to effect a Table 3 Reaction of Sample Compounds to
concerted displacement reaction, on the Chromic Acid Test
one hand, and the primary carbonium ion Substance Condensed Reaction
Structural Formula
is too unstable to serve as an
n-butyl alcohol CH3CH2CH2CH2OH Clear blue
intermediate in the carbonium solution
mechanism, on the other. Hydrogen Sec-butyl alcohol Clear blue
bromide and Hydrogen iodide, which have solution
anions with nucleophilic reactivity
increasing in that order, are increasingly Tert-butyl alcohol Clear yellow
reactive toward primary alcohols. These solution
are nucleophilicity orders to be expected
in hydroxylic solvents.
n-butyraldehyde Clear blue
Tertiary alcohols react with solution
concentrated hydrochloric acid so rapidly
that the alkyl halide is visible within a few
minutes at room temperature, at first as a Benzaldehyde Clear green
solution
milky suspension and then as an oily
layer. The acidity of the medium is
increased by the addition of the
Acetone Clear yellow
anhydrous zinc chloride (a strong Lewis solution
acid), and the reaction rate is increased
further. This reaction is not a nucleophilic
displacement comparable to that acetophenone Clear yellow
undergone by primary alcohols but rather solution
proceeds by way of a carbonium ion
intermediate. The high reactivity of
tertiary alcohols is a consequence of the
relatively great stability of the Chromic Acid Test/Dichromate
intermediate carbonium ion. Allyl alcohol, Test/Jones Test is a test for oxidizables or
although a primary alcohol, yields a any compounds that possess reducing
carbonium ion that is relatively stable property (has an alpha acidic hydrogen.
because its charge is distributed equally Reagent used includes 10% Potassium
on the two terminal carbon atoms. chromate and 6 M sulfuric acid.
CH2=CH-CH2OH→[CH2=CHCH2+↔+CHCH=CH2]
As might be expected, it reacts rapidly
Table 3 shows the reaction of n-
with Lucas reagent with the evolution of
butyl alcohol, sec-butyl alcohol, tert-butyl
heat. Allyl chloride may be caused to
alcohol, n-butyraldehyde, benzaldehyde,
separate by dilution of the mixture with
acetone, and acetophenone to Chromic
ice water.
Acid test. N-butyl alcohol. sec-butyl
alcohol, benzaldehyde, and n-
butyraldehyde resulted to a clear blue or acetophenone Orange
precipitate
green solution whereas tert-butyl alcohol,
acetone, and acetophenone resulted to a
clear yellow solution.

Primary, secondary alcohols and
aldehydes give a positive visible result.
Positive result exhibits a green or blue-
green solution; hence, n-butyl alcohol,
sec-butyl alcohol, and n-butyraldehyde all
formed either blue or green solutions.
Chromic acid test involves redox reaction.
Primary, secondary alcohols and
aldehydes undergo oxidation and
chromium undergoes reduction (from Cr +6
to Cr+3). Primary, secondary alcohols and
aldehydes will reduce the orange-red
chromic acid/sulfuric acid reagent to an
opaque green or blue suspension of
Cr(III) salts in 2-5 seconds. A primary
alcohol reacts with chromic acid to yield
aldehyde, which is further oxidized to
carboxylic acid. A secondary alcohol reacts
with chromic acid to yield ketone, which
does not oxidize further. A tertiary alcohol
is usually unreactive.
2,4-Dinitrophenylhydrazone (2,4-
DNP) test is a test for carbonyl groups It
gives a positive result for aldehydes and
ketones. Its mechanism is condensation or
addition and elimination. The test involves
nucleophilic addition of NH2 to C=O and
elimination of H2O. Reagents used include
2,4-dinitrophenylhydrazine, ethanol, and
H2SO4. Positive result is the formation of a
red-orange precipitate (conjugated
carbonyl compounds) or yellow precipitate
(non-conjugated carbonyl compounds).
Table 4 shows the reaction of
acetaldehyde, n-butyraldehyde,
benzaldehyde, acetone, and acetophenone
to 2,4-DNP test. All the samples exhibited
positive result because they all formed
either a yellow or an orange precipitate.
Hence, 2,4-DNP test proved that the
samples are carbonyl-containing
compounds and are either aldehydes or
ketones.

Table 4 Reaction of Sample Compounds to

2,4-DNP Test
Substance Condensed Reaction The reaction of 2,4-DNPH with
Structural Formula
aldehydes and ketones in an acidic
Acetaldehyde Yellow
precipitate solution is a dependable and sensitive
test. Most aldehydes and ketones yield
n-butyraldehyde Orange dinitrophenylhydrazones that are insoluble
solution solids. The precipitate may be oily at first
and become crystalline on standing. A
number of ketones, however, give
Benzaldehyde Yellow dinitrophenylhydrazones that are oils. A
precipitate
further difficulty with the test is that
certain allyl alcohol derivatives may be
oxidized by the reagent to aldehydes and
Acetone Yellow
ketones, which then give a positive result.
precipitate
If the dinitrophenylhydrazone appears to
be formed in very small amount, it may
be desirable to carry out the reaction on
the scale employed for the preparation of
a derivative and to make an estimate of
the yield. The melting point of the solid
should be checked to be sure it is different
from that of 2,4-dinitrophenylhydrazine
(MP 198oC). If necessary, this hydrazone
derivative can be recrystallized from a
solvent such as ethanol. Solvents
containing reactive carbonyl groups should
not be used, as they may result to
formation of another hydrazone.
The color of a 2,4-
dinitrophenylhydrazone may give an
indication as to the structure of the
aldehyde or ketone from which it is
derived. Dinitrophenylhydrazones of
aldehydes or ketones in which the
carbonyl group is not conjugated with
another functional group are yellow.
Conjugation with a carbon-carbon double
bond or with a benzene ring shifts the
absorption maximum towards the visible
and is easily detected by an examination
of the ultraviolet spectrum. However, this
shift is also responsible for a change in
color from yellow to orange-red. In
general, then, a yellow
dinitrophenylhydrazone may be assumed
to be unconjugated. However, an orange
Fehling’s Test is a test for
aldehydes. Reagents include CuSO4,
NaOH ( Cu2+ in alkaline solution). Positive
result is the formation of crude-red
precipitate (Cu2O/cuprous oxide).
As shown in Table 5, acetaldehyde,
n-butyraldehyde, and benzaldehyde
exhibited positive result. Acetaldehyde, in
particular turned from blue to muddy
green then formed a crude red precipitate
upon heating. These three sample
compounds which exhibited positive result
to Fehling’s test are all aldehydes.
Fehling’s test involves redox
reaction wherein aldehyde is oxidized to
carboxylic acid and ketones do not
undergo oxidation. Copper is reduced
(from Cu2+ to Cu+).
Table 6 Reaction of Sample Compounds to
Tollens’ Silver Mirror Test
Substance Condensed Reaction
Structural Formula

or red color should be interpreted with Acetaldehyde Silver Mirror

caution, since it may be due to
contamination by an impurity.
n-butyraldehyde Silver Mirror

Table 5 Reaction of Sample Compounds to

Fehling’s Test
Substance Condensed Reaction
Structural Formula Benzaldehyde Silver Mirror

Acetaldehyde Crude red

precipitate

n-butyraldehyde Crude red Acetone Clear

precipitate grayish-
black
solution

Benzaldehyde Turbid acetophenone Gel-like

solution; precipitate
oily layer

Acetone Clear blue

solution Tollens’ Silver Mirror test is a test
for aldehydes. The preparation of Tollens
reagent is based on the formation of a
acetophenone Clear blue silver diamine complex that is water
solution
soluble in basic solution. As shown in
Table 6, acetaldehyde, n-butyraldehyde,
and benzaldehyde exhibited positive result
of formation of silver mirror whereas acetophenone Yellow
precipitate
acetone and acetophenone do not.
Acetone resulted to a clear grayish-black
solution while acetophenoe formed a gel-
like precipitate. They are both negative for Isopropyl alcohol Yellow
precipitate
Tollens’ Silver Mirror test. The test proved
that acetaldehyde, n-butyraldehyde, and
benzaldehyde are aldehydes.

Tollens’ Silver Mirror test involves
reduction-oxidation reaction wherein
aldehyde is oxidized to carboxylic acid and
ketones do not undergo oxidation except
alpha-hydroxyketone. Silver is reduced
from Ag+ to Ag0. Formic acid,
hydroxylamine, acyloins, diphenylamine,
and other aromatic amines, as well as a-
naphthol and certain other phenols will
give a positive result. a-Alkoxy and a-
dialkylamino ketones have also been
found to reduce ammoniacal silver nitrate.
In addition, the stable hydrate of
trifluoroacetaldehyde gives a positive
result.
The test often results in a smooth
deposit of silver metal on the inner
surface of the test tube, hence the name
“silver mirror” test. In some cases,
however, the metal forms merely as a
granular gray or black precipitate,
especially if the glass is not scrupulously
clean. The reaction is autocatalyzed by the
silver metal and often involves an
induction period of a few minutes.
Table 7 Reaction of Sample Compounds to
Iodoform Test
Substance Condensed Reaction
Structural Formula
Acetaldehyde Yellow
precipitate
Iodoform Test is a test for methyl
carbinol (secondary alcohol with adjacent
methyl group) and methyl carbonyl
groups. Reagents include 10% KI and
NaClO. Positive result is exhibited by the
formation of yellow crystals or precipitate.
Table 7 shows that among the sample
compounds tested, acetaldehyde,
acetone, acetophenone, and isopropyl
alcohol exhibited positive result.
Compounds with a methyl group next to a
carbonyl group give a positive result with
the iodoform (tri-iodomethane) test.
Ethanol and secondary alcohols with a
methyl group attached to the same carbon
as the –OH group will also give a positive
iodoform test. This is because the iodine
oxidizes the alcohols to a carbonyl
compound with a methyl group next to
the carbonyl group.
When a - methyl carbonyl
compounds react with iodine in the
presence of a base, the hydrogen atoms
on the carbon adjacent to the carbonyl
group (a  hydrogens) are subsituted by
iodine to form tri iodo methyl carbonyl
compounds which react with OH - to
produce iodoform and carboxylic acid  (2):

Benzaldehyde White
suspended
precipitate

Acetone Yellow References

precipitate
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Identification of Organic Compound: A
Laboratory Manual Sixth Edition. John
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Rodewald, L., Roberts, R. (1979). Modern Benzaldehyde. Retrieved September 19,

Experimental Organic Chemistry. New 2010 from
York: Holt, Rinehart and Winston http://www.encyclopedia.com/topic/benza
ldehyde.aspx.
Shriner, Fuson, Curtin. (1964). Systematic
Identification of Organic Compound: A
Laboratory Manual Fifth Edition. John
Wiley & Sons, Inc. New York: Van
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