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Classification Tests for Hydroxyl-

And Carbonyl-Containing Compounds



Dupaya, Julian Victor M., Estacio, Jerwin Caesar A., Farnacio, Rebecca Ruth, Gabito, Jose
Luis F., Gallo, Cian Carlo M., Galvez, Joshua M.
Group no.4, 2D-Medical Technology, Faculty of Pharmacy, University of Santo Tomas

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, Fehlings 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. Fehlings Test and Tollens Silver Mirror Test are tests for aldehydes. Iodoform
test is a test for methyl carbinol and methyl carbonyl groups.

Introduction

Hydroxyl group is used to
describe 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




Alcohols are characterized by
one 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 (H
2
O) 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of the hydrogen atoms has been
replaced by an alkyl group, typically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 pK
a
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 (C
6
H
5
OH), 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, C
2
H
5
OH, (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
CH
3
CH(OH)CH
2
CH
3
(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, C
4
H
10
O 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 C
3
H
8
O. 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, C
6
H
5
CH
2
OH, 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, C
6
H
5
CHO (also
known as benzenecarbonal) is a
colorless liquid aldehyde with a
characteristic almond odor. It boils at
180C, 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, CH
3
CHO (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 dyestuffs, and as a
preservative.

Figure 11 Structure of Acetaldehyde



N-butyraldehyde (also known as
butanal) is an organic compound with
the formula CH
3
(CH
2
)
2
CHO. This
compound is the aldehyde derivative of
butane. It is a 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
acid, polyvinyl butyral, methyl amyl
ketone). It is also used as an
intermediate to make pharmaceuticals,
agrochemicals, antioxidants, rubber
accelerators, textile auxiliaries,
perfumery and flavors.

Figure 12 Structure of n-
Butyraldehyde



Acetone (also known as
propanone) is the organic compound
with the formula (CH
3
)
2
CO. 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



Acetophenone is the organic
compound with the formula
C
6
H
5
C(O)CH
3
. It is the simplest
aromatic ketone. This 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 hydroperoxide for
use in the production of propylene oxide

Figure 14 Structure of Acetophenone



The hydroxyl- and carbonyl-
containing compounds were analyzed
by utilization of different tests such as
testing the solubility of alcohols in water,
Lucas Test, Chromic Acid Test (Jones
Oxidation), 2,4-Dinitrophenylhydrazone
Test, Fehlings Test, Tollens Silver
Mirror Test, and Iodoform Test.

Most organic compounds are not
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.

Fehlings 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.

Two to three drops of the sample were
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
dichromate solution and 5 drops of
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.

A drop of a liquid sample was placed
into a small sample. 5 drops of 95%
ethanol was added and well shaken.
Afterwards, 3 drops of 2,4-DNP was
added and if no yellow or orange
precipitate formed, the solution was
allowed ro stand for at least 15 minutes.

E. Fehlings Test

This test was performed on
acetaldehyde, n-butyraldehyde,
acetone, benzaldehyde, and
acetophenone.
Fehlings reagent was prepared by
mixing equal amounts of Fehlings A
and Fehlings B. Fehlings A was
prepared by dissolving 7 g of hydrated
copper (II) sulfate in 100-ml of water.
Fehlings B was prepared by mixing 35
g of Potassium sodium tartrate and 10 g
of Sodium hydroxide in 100-ml water.

1-ml of freshly prepared Fehlings
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 placed in a beaker of boiling water
and changes within 10-15 minutes were
observed.

F. Tollens Silver Mirror Test

This test was performed on
acetaldehyde, benzaldehyde, acetone,
n-butyraldehyde, and acetophenone.

The reagent was prepared by adding 2
drops of 5% Sodium hydroxide solution
to 2-ml of 5% Silver nitrate solution and
mixing thoroughly. Next, only enough
2% ammonium hydroxide (concentrated
ammonium hydroxide is 28%) was
added drop by drop and with stirring to
dissolve the precipitate. Adding excess
ammonia will cause discrepancies on
the result of the test.

Four test tubes with 1-ml of freshly
prepared Tollens reagent were
prepared. Two drops each of the
samples were then added. The mixture
was shaken and allowed to stand for 10
minutes. If no reaction has occurred, the
test tube was placed in a beaker of
warm water (35-50
o
C) for 5 minutes.
Observations were recorded.

It was noted that if Tollens reagent is
left unused for a period of time, it may
form explosive silver. This was avoided
by neutralizing unused reagent with a
little nitric acid and discarded
afterwards.

G. Iodoform Test

This test was performed on
acetaldehyde, acetone, acetophenone,
benzaldehyde, and isopropyl alcohol.

Two drops of each sample was placed
into its own small vial or test tube. 20
drops of fresh chlorine bleach (5%
Sodium hypochlorite) was slowly added
while shaking to each test tube and
then, mixed. The formation of a yellow
participate was noted.

Results and Discussion

Table 1 Solubility of Alcohol in Water

Alcohol
Condensed
Structural Formula
Amount of
Water (in ml)
needed to
produce a
homogeneou
s dispersion
Solubility
in Water
Ethanol CH3CH2OH 1 ml Miscible
N-butyl
alcohol
CH3CH2CH2CH2OH 1.5 ml Miscible
Sec-butyl
alcohol

1 ml Miscible
Tert-butyl
alcohol

1 ml Miscible
Benzyl
alcohol

N/A Immiscible

Table 1 shows alcohols such as
ethanol, n-butyl alcohol, sec-butyl
alcohol, tert-butyl alcohol, and benzyl
alcohol and their solubility in water.

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 C
6.
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 Structural
Formula
Reaction Inference
n-butyl
alcohol
CH3CH2CH2CH2OH
Clear
solution
Miscible
Sec-butyl
alcohol

Clear
solution
Miscible
Tert-butyl
alcohol

Formation
of two
layers with
cloudy
suspension
Immiscible

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 ZnCl
2

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.






The reaction of alcohols with
halogen acids is a displacement
reaction in which the reactive species is
the conjugate acid of the alcohol R-
OH
2
+
, and as might be expected, is
analogous to the replacement reactions
of organic halides and related
compounds with silver nitrate and iodide
ion. The effects of structure on reactivity
in these reactions are closely related.
Thus, primary alcohols do not react
perceptibly with hydrochloric acid even
in the presence of zinc chloride at
ordinary temperatures; chloride ion is
too poor a nucleophilic agent to effect a
concerted displacement reaction, on the
one hand, and the primary carbonium
ion is too unstable to serve as an
intermediate in the carbonium
mechanism, on the other. Hydrogen
bromide and Hydrogen iodide, which
have anions with nucleophilic reactivity
increasing in that order, are increasingly
reactive toward primary alcohols. These
are nucleophilicity orders to be expected
in hydroxylic solvents.

Tertiary alcohols react with
concentrated hydrochloric acid so
rapidly that the alkyl halide is visible
within a few minutes at room
temperature, at first as a milky
suspension and then as an oily layer.
The acidity of the medium is increased
by the addition of the anhydrous zinc
chloride (a strong Lewis acid), and the
reaction rate is increased further. This
reaction is not a nucleophilic
displacement comparable to that
undergone by primary alcohols but
rather proceeds by way of a carbonium
ion intermediate. The high reactivity of
tertiary alcohols is a consequence of the
relatively great stability of the
intermediate carbonium ion. Allyl
alcohol, although a primary alcohol,
yields a carbonium ion that is relatively
stable because its charge is distributed
equally on the two terminal carbon
atoms. As might be expected, it reacts
rapidly with Lucas reagent with the
evolution of heat. Allyl chloride may be
caused to separate by dilution of the
mixture with ice water.

Secondary alcohols are
intermediate in reactivity between
primary and tertiary alcohols. Although
they are not appreciably affected by
concentrated hydrochloric acid alone,
they react with it fairly rapidly in the
presence of anhydrous zinc chloride; a
cloudy appearance of the mixture is
observed within 5 minutes, and in about
10 minutes, a distinct layer is usually
visible.

Table 3 Reaction of Sample Compounds to
Chromic Acid Test

Substance
Condensed
Structural Formula
Reaction
n-butyl alcohol CH3CH2CH2CH2OH
Blue-green
Solution
Sec-butyl alcohol

Blue-green
Solution
Tert-butyl alcohol

Blue-green
Solution
Acetaldehyde

Red-Orange
Solution
n-butyraldehyde

Lime-Green
Solution
Benzaldehyde

Red-Orange
Solution
Acetone

Blue-green
Solution
acetophenone

Blue-green
Solution
Isopropyl Alcohol

Blue-green
Solution

Chromic Acid Test/Dichromate
Test/Jones Test is a test for oxidizables
or any compounds that possess
reducing property (has an alpha acidic
hydrogen. Reagent used includes
chromium trioxide and concentrated
sulphuric acid.

Table 3 shows the reaction of n-
butyl alcohol, sec-butyl alcohol, tert-
butyl alcohol, n-butyraldehyde,
benzaldehyde, acetone, and
acetophenone to Chromic Acid test. N-
butyl alcohol. N-butyl alcohol, Sec-butyl
alcohol, tert-butyl alcohol, n-
butyraldehyde, acetone and
acetophenone resulted to a blue-green
or lime-green solution whereas
acetaldehyde and benzaldehyde
resulted to a red-orange solution.






Primary, secondary alcohols and
aldehydes give a positive visible result.
Positive result exhibits a lime-green or
blue-green solution; hence, n-butyl
alcohol, sec-butyl alcohol, and n-
butyraldehyde all formed either lime-
green or blue-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.

Table 4 Reaction of Sample Compounds to
2,4-DNP Test

Substance
Condensed
Structural Formula
Reaction
Acetaldehyde

Yellow
precipitate
n-butyraldehyde

Yellow
solution
Benzaldehyde

Orange-
Yellow
precipitate
Acetone

Orange-Red
precipitate
acetophenone

Orange-Red
precipitate

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 NH
2
to
C=O and elimination of H
2
O. Reagents
used include 2,4-dinitrophenylhydrazine,
ethanol, and H
2
SO
4
. Positive result is
the formation of a orange-red 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.





The reaction of 2,4-DNPH with
aldehydes and ketones in an acidic
solution is a dependable and sensitive
test. Most aldehydes and ketones
yield dinitrophenylhydrazones that are
insoluble solids. The precipitate may be
oily at first and become crystalline on
standing. A number of ketones,
however, give dinitrophenylhydrazones
that are oils. A further difficulty with the
test is that certain allyl alcohol
derivatives may be oxidized by the
reagent to aldehydes and ketones,
which then give a positive result. 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 198
o
C). 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 or red color should be interpreted
with caution, since it may be due to
contamination by an impurity.

Table 5 Reaction of Sample Compounds to
Fehlings Test

Substance
Condensed
Structural Formula
Reaction
Acetaldehyde

Brick-Red
precipitate
n-butyraldehyde

Brick-Red
precipitate
Benzaldehyde

No
Decolorization
Acetone

No
Decolorization
acetophenone

No
Decolorization

Fehlings Test is a test for
aldehydes. Reagents include CuSO4,
NaOH ( Cu
2+
in alkaline solution).
Positive result is the formation of brick-
red precipitate.

As shown in Table 5,
acetaldehyde and n-butyraldehyde
exhibited positive result. Acetaldehyde,
in particular turned from blue to muddy
green then formed a brick-red
precipitate upon heating. These three
sample compounds which exhibited
positive result to Fehlings test are all
aldehydes.

Fehlings test involves redox
reaction wherein aldehyde is oxidized to
carboxylic acid and ketones do not
undergo oxidation. Copper is reduced
(from Cu
2+
to Cu
+
).



Table 6 Reaction of Sample Compounds to
Tollens Silver Mirror Test

Substance
Condensed
Structural Formula
Reaction
Acetaldehyde

Silver Mirror
n-butyraldehyde
Silver Mirror
Benzaldehyde

Silver Mirror
Acetone

Black
Solution
acetophenone

Black
Solution

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

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
Structural
Formula

Reaction
Acetaldehyde


Yellow
precipitate
Benzaldehyde


Brownish-
Red Oily
Droplet
Acetone

Yellow
precipitate
acetophenone


Yellow
precipitate
Isopropyl
alcohol


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):



References

BOOKS:

Bayquen, A., Sarile, A. et al. (2014). Laboratory
Manual In Organic Chemistry. Quezon City,
Philippines. C & E Publishing Inc. Pg. 107-112

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