CLASSIFICATION TESTS FOR HYDROCARBONS USING SOLUBILITY,

IGNITION, NITRATION, BAEYERS TEST, BROMINE TEST AND BASIC

OXIDATION TEST
Jasher Christian Boado, Alyanna Cacas, Phoebe Calimag, Caryl Angelica Chin, Haidee Cosilet, John Francis Creencia
Group 2, 2BMT, Faculty of Pharmacy, University of Santo Tomas

ABSTRACT
Hydrocarbons are classified as saturated, actively unsaturated, aromatic or an arene based on various
classification tests involving test for solubility in concentrated H
2
SO
4
, ignition, active unsaturation using Baeyers
test and Bromine test, aromaticity using nitration test, and basic oxidation test. This experiment aims to
differentiate the intrinsic physical and the chemical properties of hydrocarbons, and to determine if it is
saturated, actively unsaturated, aromatic or an arene. The sample compounds hexane, heptane, cyclohexane,
cyclohexene, benzene and toluene were analyzed for their physical state in room temperature, color, and odor.
Using solubility test, a drop of a sample was added cautiously into 1ml of concentrated H
2
SO
4.
Using the
Baeyers Test and/or Bromine test in which 2 drops of 2% KmnO
4
solution and 10 drops of 0.5% Br
2
in CCl
4

reagent, respectively, was added into 5 drops of a sample in a dry test tube, was shaken vigourously until the
reagent is decolorized compared with water. Using Nitration test, 8 drops of nitrating mixture was added into 5
drops of a sample in a dry test tube, was observed for the formation of a yellow oily layer or droplet and was
diluted with 20 drops of water. Using Basic Oxidation test, 8 drops of 2% KmnO
4
solution and 3 drops of 10%
NaOH solution was added into 4 drops of a sample in a dry test tube and was heated in a water bath for 2
minutes. A sample was described as immiscible or immisicible using solubility test, as actively unsaturated using
Baeyers and Bromine tests, as aromatic using nitration test and as an arene using basic oxidation test.
INTRODUCTION
Hydrocarbons are the simplest organic
compounds containing only the elements carbon
and hydrogen. They can be classified in many
ways. One, a hydrocarbon skeleton can be acyclic
(open chained) or cyclic (closed chain). Two, a
hydrocarbon can be classified as aliphatic or
aromatic based on its sources and properties.
Aliphatic (from the Greek: aleiphar meaning fat or
oil) describes a hydrocarbon that resembles long
carbon-chain molecules derived from animal fats,
but more conviniently, when the chemical structure
contains no ring. Aromatic describes a hydrocarbon
that resembles pleasant smelling plant extracts, but
more conviniently, when the chemical structure
contains a ring (Carey, 2014). Aliphatic
hydrocarbons can be divided into an alkane, alkene
or alkyne based on the types of bonds they contain.
Alkanes are saturated hydrocarbons that contain
only carbon-carbon single bonds. Alkenes and
Alkynes are unsaturated hydrocarbons that contain
a carbon-carbon double bond or triple bond,
respectively. As mentioned, saturated is a way to
describe a bond, meaning each carbon (a
tetravalent atom) contains the maximum number of
bonds attached to it. Thus, a hydrocarbon that is
saturated has all sigma bonds however it is actively
unsaturated when it has both sigma bond and pi
bonds. Moving on, aromatic hydrocarbons can be
classified as an arene when it contains an alkyl side
chain (Brown & Poon, 2014).
The sample compounds used in this
experiment are hexane, heptane, cyclohexane,
cyclohexene, benzene and toluene. Hexane, C
6
H
14
,
is a chemical made from crude oil. Heptane, C
7
H
16
,
is a chemical derived from the fractional distillation
of petroleum. Cyclohexane, C
6
H
12
, is a colorless
liquid cycloalkane that is made by passing benzene
and hydrogen under pressure over a heated Raney
nickel catalyst at 150
o
C or by the reduction of
cyclohexanone. Cyclohexene, C
6
H
10
, is a colorless
liquid cycloalkene that is prepared by dehydration of
cyclohexanol by thermal reaction of ethylene-
propylene-butadiene. Benzene, C
6
H
6
, is a liquid
aromatic hydrocarbon found in gasoline and other
fuels (National Center for Biotechnology
Information, n.d.). Toluene, C
7
H
8
, is a liquid
aromatic hydrocarbon that occurs naturally in crude
oil and in the tolu tree (ATSDR, 2011).
The objectives of this experiment are to
differentiate the intrinsic physical and the chemical
properties of hydrocarbons using these compunds,
and to determine if they are saturated, actively
unsaturated, aromatic or an arene.
MATERIALS AND METHODS
The sample compounds used in this
experiment are hexane, heptane, cyclohexane,
cyclohexene, benzene and toluene. The reagents
used in the different classification tests are
concentrated H
2
SO
4
, concentrated HNO
3
, 2%
KmnO
4
solution, 0.5% Br
2
in CCl
4
reagent, and 10%
NaOH solution.
Members of the group were assigned tasks
and collected the materials used in the experiment.
A. Physical State, color, and odor
The sample compounds hexane, heptane,
cyclohexane, cyclohexene, benzene and toluene
were observed and noted for their physical state as
solid, liquid or gas at room temperature, for their
color and for their appearance as either clear or
turbid. Next, the odor was described by wafting the
hand over the mouth of the test tube containing a
sample.
B. Solubility in Concentrated H
2
SO
4

A drop of the sample compound was added
in a test tube containing 1 ml of concentrated
H
2
SO
4.
A sample was described as immiscible or
misicible when they form a layer or not.
C. Ignition Test
3 drops of the liquid sample was placed in a
small evaporating dish and was observed as
flammable or not by putting a lighted match on it.
The flame was observed as either luminous or non-
luminous, and if it produced soot or not.
D. Tests for active unsaturation
a. Baeyers test
5 drops of the sample was placed in a
dry test tube. Then, 2 drops of 2%
KmnO
4
solution was added into it and
was shaken vigorously. The extent of
decolorization of the reagent was
observed.

b. Bromine test
5 drops of the sample was placed in a
dry test tube. Next, 10 drops of 0.5%
Br
2
in CCl
4
reagent was added into it
and was shaken vigorously. The extent
of decolorization of the reagent was
observed or when the red-brown
bromine was discharged. Optionally, a
blue litmus paper on a glass rod was
put on the mouth of the test tube and
any color changed was noted. Then the
sample was compared with water as a
negative control.
E. Nitration test
A nitrating mixture was prepared by adding
2ml of concentrated HNO
3
and 2ml of concentrated
H
2
SO
4
in an erlenmeyer flask immersed in an
evaporating dish containing water. The sample was
cooled at room temperature.
5 drops of the sample was placed in a dry
test tube. Then, 8 drops of the nitrating mixture was
added on the sample and was shaken. Any
formation of a yellow oily layer or droplet was
observed and was diluted with 20 drops of water. A
sample that resulted in no apparent reaction was
heated in a water bath at approximately 50
o
C for 10
minutes and was observed.
F. Basic Oxidation test
4 drops of the sample was placed in a dry
test tube. Then, 8 drops of 2% KmnO
4
solution and
3 drops of 10% NaOH solution was added into it
and heated in a water bath for 2 minutes. Any color
change and formation of a brown precipitate was
observed.



RESULTS AND DISCUSSION
Table 1: Results
HEXANE HEPTANE CYCLOHEXANE CYCLOHEXENE BENZENE TOLUENE
Condensed
structural
formula





Physical
state at RT
Liquid Liquid Liquid Liquid Liquid Liquid
Appearance Clear Clear Clear Clear Clear Clear
Color Colorless Colorless Colorless Colorless Colorless Colorless
Odor Plastic balloon-
like
Chlorine odor Detergent-like Acetone-like Flowery odor Rugby-like
Solubility in
concentrated
H2SO4
Formation of a
black layer
Formation of a
clear oily layer
Formation of a
clear oily layer
Formation of an
orange layer
Formation of
a yellow
green layer
Formation
of a clear
oily layer
Inference Immiscible Immiscible Immiscible Immiscible Immiscible Immiscible
Ignition test Luminous
flame
Luminous flame Luminous flame Luminous flame Luminous
flame with
soot
Luminous
flame with
soot
Inference Flammable Flammable Flammable Flammable Flammable Flammable
Baeyers test No formation
of brown
suspension
No formation of
brown suspension
No formation of
brown
suspension
Formation of
brown
suspension
No formation
of brown
suspension
No
formation of
brown
suspension
Bromine test No change No change No change Reddish Brown
to colorless
No change No change
Inference Not actively
unsaturated
Not actively
unsaturated
Not actively
unsaturated
(+) actively
unsaturated
Not actively
unsaturated
Not actively
unsaturated
Nitration Formation of a
clear oily layer
Formation of a
clear oily layer
Formation of a
clear oily layer
Black Formation of
a yellow oily
layer
Formation
of a yellow
oily layer
with brown
ppt
Inference Aliphatic Aliphatic Aliphatic Not aromatic Aromatic Aromatic
Basic
oxidation
No precipitate No precipitate No precipitate Bluish green to
brown precipitate
No
precipitate
Bluish black
Inference Not an arene Not an arene Not an arene Not an arene Not an arene Arene

A. Physical State, Color, and Odor
The Physical properties of hydrocarbons
determine thier reactivity. Aliphatic hydrocarbons:
alkane (C
n
H
2n+2
), cycloalkane (C
n
H
2n
), alkene
(C
n
H
2n-2
) and alkyne (C
n
H
2n-4
) consist only of weak
dispersion forces. This forces account for their low
boiling points thus they exist in such physical state
at room temperature. They are less dense than
water, thus they are non-polar and soluble in each
other (Brown & Poon, 2014).
Aromatic hydrocarbons have physical
properties that vary depending on the nature of their
substituent. Alkylbenzenes, such as the sample
toluene, are like aliphatic hydrocarbons. They are
nonpolar and have lower boiling point than
benzenes with a polar substituent. These account
for their physical state at room temperature. Being
an aromatic hydrocarbon, toluene has a distinct
smell (Greenshields & Rossini, 1958).

B. Solubility in Concentrated H
2
SO
4

Figure 1: Solubility Reaction Mechanism

Figure 2: Solubility in concentrated H2SO4

The solubility of hydrocarbons is based on
the principile Like dissolves Like. The solubility or
miscibility of the compoundsin H
2
SO
4
can indicate
their acidity and basicity. They can indicate a weak
base (can be protonated) or a neutral compound
(cannot be protonated) (Smith, 2006).

Generally, saturated hydrocarbons
specifically alkanes are not as reactive as other
hydrocarbons. The reasons are alkanes do not
have double or triple bonds that can react with acid
to form carbocations and they have no leaving
groups making them incapable of E1, E2, SN1 or
SN2 reactions. However, unsaturated hydrocarbons
specifically alkenes are more reactive than alkanes
because they can undergo addition reactions
(Carey, 2014). Thus, sulfuric acid reacts differently
with both alkenes and aromatic hydrocarbons (refer
to Figure 1). In alkenes, sulfuric acid adds to
cyclohexene via an acid catalyzed addition however
it wont react with cyclohexane. In aromatic
hydrocarbons, sulfuric acid reacts with toluene via
sulfonation. This is conferred by the formation of an
orange layer (refer to Figure 2). Aromatic
hydrocarbons such as toluene are also reactive
because they undergo nucleophilic aromatic
substitution reactions (Giovine, 2011).
C. Ignition Test
Most hydrocarbons burn over a flame since
carbon and hydrogen react with oxygen to produce
carbon dioxide and water (refer to figure 3)
(Giovine, 2011).
Figure 3: Ignition Reaction Mechanism

Figure 4: Ignition of toluene produced soot

The ignition test was performed in essence
that high carbon to hydrogen ratio equates to high
luminosity. A high degree of luminosity accounts for
the luminous flame, an orange flame which may
produce soot. Aromatic compounds, such as
benzene and toluene (refer to figure 4), burn with
sooty flame due to incomplete combustion causing
the formation of an unburned carbon. Complete
combustion is indicated by a non-luminous flame
which is a blue flame. It produces more heat than
light; hence the carbon is completely oxidized
(Smith, 2006).
D. Tests for active unsaturation
a. Baeyers test

Figure 5: Nitration test result
Baeyers test result indicates that
cyclohexene is positive for active unsaturation
confirming that it contains a double bond in its
chemical structure. Cyclohexene decolorized the
purple solution then formed a brown precipitate.
The addition of KmnO
4
solution caused Mn
7+
to be
reduced to Mn
4+
in the process of redox reaction.
(Smith, 2006). Alkenes react with potassium
permanganate (KMnO4) to give a diol and MnO
2

while Aromatic compounds do not react because of
their stability (Greenshields & Rossini, 1958).
b. Bromine test
Bromine solution in carbontetrachloride is
used to identify alkanes, alkenes and alkynes.
Bromine test only reacted with cyclohexene thus it
is actively (+) unsaturated. Saturated hydrocarbons
will only react with bromine only if there is UV light
thus no reaction occurred. Aromatic hydrocarbons
will only react with bromine if there is a strong Lewis
acid catalyst such as FeBr
3
(Giovine, 2011).
E. Nitration test
Nitration test is used to determine
aromaticity. Benzene and toluene gave a positive
result by forming a yellow oily layer; hence, the two
compounds are aromatic. The H
2
SO
4
acts as a
catalyst facilitating the formation of the electrophile
nitronium ion (NO
2
+). The reaction involves
electrophilic substitution because hydrogen is
replaced by nitronium ion (Hoggett, et.al., 1971).
F. Basic Oxidation test

Figure 6: Basic Oxidation Reaction Mechanism
Basic oxidation used potassium
permanganate which is a strong oxidizing agent.
Figure 6 shows the reaction as potassium
permanganate oxidizes the carbon-carbon double
or triple bond by replacing them with a hydroxy
group (-OH group). Thus the carbons charge
changes from being +1 to +2 by losing an electron
(oxidized). When it dissolves in water, it produces
intense purple solution. NaOH was used to
determine whether the samples will form a
precipitate (Giovine, 2011).
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