Analysis of Hydrocarbons

Mark B. Carascal**, Vince Ivan M. Camangeg, Keith Oreil A. Castillejo, Jasper Lorenz C. Choy

Group 2, 2-Microbiology, Department of Biological Sciences, College of Science, University of Santo

Tomas, Espaa Manila

ABSTRACT: Hydrocarbons can be categorized as saturated aliphatic, unsaturated

aliphatic, aromatic and substituted aromatic. Different chemical analyses were used to
identify the unknown substance based on the reactivities of its functional groups.
Defining the reaction mechanisms of the following tests provided a proof on the
expected products and its distinguishable properties. Nitration reaction differentiated
aliphatic (i.e.: hexane, cyclohexene) from aromatic (i.e.: naphthalene, toluene)
hydrocarbon, bromine test detected the presence of unsaturation (i.e.:double bond in
cyclohexene) while oxidation reaction identified if the aromatic hydrocarbon possessed
substituents (i.e.: alkyl group in toluene). Elemental analysis is also available for a more
rigorous way of identification of the unknown sample, although this aspect was not done
in the experiment.

INTRODUCTION

Hydrocarbon is a class of organic compound that contains only carbon and hydrogen
atoms. It serves as the skeleton to various forms of organic compounds and is readily
abundant in the natural environment. There are two broad groups of hydrocarbons
namely aliphatic hydrocarbon and aromatic hydrocarbon. Aliphatic hydrocarbons
comprise of straight chain and cyclic organic compounds that does not contain an
alternating double bonds with delocalized electrons. Aliphatic hydrocarbon can be
saturated or unsaturated. Saturated hydrocarbons are called alkanes and contain the
maximum amount of hydrogen atoms a carbon-carbon skeleton can accommodate. Its
molecular formula can be determined by CnH2n+2. This class is usually unreactive and is
hard to identify via common chemical analysis. Unsaturated hydrocarbon, on the other
hand, is classified as either alkenes or alkynes. Alkene contains carbon-carbon double
bonds and is generally expressed in the molecular formula C nH2n. Alkynes contain
carbon-carbon triple bonds and is generally expressed in the molecular formula CnH2n-2.

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The presence of pi bonds in these compounds renders it nucleophilic and readily
reactive to electrophiles. Cyclic hydrocarbons are closed ring structures that may differ
in stability based on angle strain and torsional strain. 1 Aromatic compounds are those
which contain benzene ring , a six-carbon ring with alternating double bonds and
delocalized electrons. Aromatic compounds are inert in most cases except when
hydrogen atoms from benzene are substituted with halogens or alkyl groups.

Chemists use several analytic techniques to determine the identity of an unknown

hydrocarbon. One of the most common and inexpensive way of doing this is through
chemical analysis. In this method, a specific chemical reaction will proceed through the
interaction of the sample with the given reagent. The result will then be compared to a
known standard which will then dictate the identity of the compound. Nitration reaction is
a classic example of electrophilic aromatic substitution. It is based from the fact that the
electron-withdrawing nitro group, once in contact with the aromatic ring, will deactivate
the ring towards further reaction with electrophiles. 2 Because of its selective reaction
with aromatic compounds, nitration test can be used to determine if the unknown
hydrocarbon is aliphatic (without reaction) or aromatic (with reaction). On the other
hand, bromination reaction is a substitution reaction that involves two steps. The first
step involves the formation of a cyclic bromonium ion while the second step involves a
classic backside attack of an SN2 mechanism.2This test is frequently used as a
qualitative test for the detection of unsaturation. Lastly, basic oxidation reaction of the
aromatic side chain is based on the oxidation of benzylic carbon to a carboxyl group
which are very similar to benzylic halogenation. 3This reaction allows the differentiation
between a substituted aromatic ring and a non-substituted one.

Elemental analysis is another technique employed to determine the identity of the

compound based on the reactivitiesof the elements comprising its functional groups. Its
basic aims are: to determine the elemental composition of a pure sample, to find out the
elemental content of a particular element in an analytical sample and to assess the
purity of the organic substance in question. Several analytical methods, some involving
complex analyzers, are employed depending on the elements to detect. For carbon and
hydrogen, some techniques involved are the use of Perkin-Elmer Model 240 Elemental

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Analyzer, Hewlett-Packard (F&M) CHN Analyzer and Carlo-Erba Elemental Analyzer.
For nitrogen, Kjeldahl method and Dumas method are commonly used. Oxygen can be
detected bypyrolytic reduction and iodometry or through coulometry. 8 In general,
common elemental analysis methods include gravimetry, titrimetry and potentiometry.

The experiment aims to characterize and differentiate the unknown hydrocarbon using
common chemical analysis (i.e.: nitration test, bromine test and basic oxidation). The
experiment also aims to familiarize the students with the various classes of
hydrocarbons.

EXPERIMENTAL SECTION

Unknown samples were procured from the instructors with the identity of being hexane,
cyclohexene, naphthalene or toluene. Five drops of the samples had undergone parallel
chemical tests. One sample will be tested to all the reactions regardless of the result in
the previous one. Four reference standards (hexane, cyclohexene, naphthalene and
toluene) were also tested so as to provide a basis of comparison on the result of the
unknown (this also aids in faster identification). For the nitration reaction, eight drops of
the nitrating reagent (1:1 H2SO4-HNO3) were added to the sample. The mixture was
then shaken well until a yellow precipitate or oil was produced. If no visible change had
occurred, the mixture was placed in a water bath (preferably 30-400C) until the desired
reaction took place. The resulting mixture was then compared to the standards and
recorded. For the bromine test, a 5% bromine reagent was prepared (5mL of bromine
dissolved in 95mL dichloromethane). The reagent (reddish brown in color) was then
added to the sample and was observed for decolorization. The number of drops to
decolorize the sample was then counted and quantitatively compared to that of the
standards. Lastly, for oxidation reaction, 3 drops of 2% aqueous KMnO 4 solution (2 mL
KMnO4 dissolved in 95 mL water, deep purple-pink in color) and 2 drops of NaOH were
added to the sample and heated for two minutes. The presence of brown precipitate
and the decolorization of the solution were noted and compared to the standards.
Positive and negative results were interpreted as shown by the table below:

Test Positive result Negative result

Nitration Yellow precipitate/oil No reaction
Bromination More drops of reagent to Less drops of reagent to
decolorize decolorize
Basic Oxidation Brown precipitate and No reaction
decolorization
Table 1: interpretation of results for the three chemical analyses

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RESULTS AND DISCUSSION

The following results were obtained in the reaction of the standards with the different
chemical analyses performed:

Sample Results
Nitration Bromination Basic Oxidation
Hexane No reaction (-) 3 drops to No reaction (-)
decolorize (-)
Cyclohexene No reaction (-) >10 drops to Brown precipitate,
decolorize (-) decolorization (+)
Naphthalene Yellow precipitate 3 drops to No reaction (-)
(+) decolorize (-)
Toluene Yellow Oil (+) 3 drops to Brown precipitate,
decolorize (-) decolorization (+)
Table 2: results of the chemical tests performed in the analysis

Nitration reaction determines the presence of benzene ring in a compound. The general
mechanism in this kind of reaction is an electrophilic aromatic substitution. The first step
is the rate determining step while the second step is a proton transfer from the
cyclohexadienyl cation:4

Figure 1: mechanism on the nitration of an aromatic ring. Step 1 includes the nucleophilic
attack of double from benzene to the nitrocation, nitronium ion to form cyclohexdienylcation
intermediate. Step 2 includes proton transfer from cyclohexadienylcation to water which
ultimately yields nitrobenzene and hydronium ion . (image from www.slcc-science.org)

In the mechanism, it was clearly understood that nitronium ion serves as the
electrophile and therefore plays a critical role in the production of the desired product.
The nitrating reagent ensures that the amount of nitronium ion in the reaction was
optimized to hasten the overall process (take note that the first step in Figure 1 is the
rate determining step and involves the nitronium ion). A commonly used nitrating

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reagent is a mixture of concentrated sulfuric acid and nitric acid which enhances the
production of NO2+ as described by the equations:2

Equation 1: increase in the production of ntironium ion using anhydrous nitric acid
(accomplished by sulfuric acid). (image fromchemistry.tutorvista.com)

Looking back at Table 2, it can be seen that naphthalene and toluene exhibited a
positive result in nitration test. Analysing the structure of the two compounds, it can be
inferred that they will be reactive to the nitronium ion because of the presence of the
benzene ring (connect Figure 1 with the structures below):

Figure 2: structures of naphthalene and toluene showing the benzene ring skeleton. (image from
escola.britannica.com.br)

The other samples (hexane and cyclohexene) were not reactive to the nitronium ion
since no benzene ring was present in their structures. The yellow precipitate/ oil formed
in the reaction is actually the nitrobenzene (in naphthalene) or the nitrotoluene (in
toluene) by products.

Bromination reaction detects the presence of unsaturation in a chemical system. It is an

example of an electrophilic addition reaction which involves the formation of cyclic
bromonium ion intermediate and finally a dibromoalkyl product as described in the
following mechanism:2

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Figure 3:mechanism of the bromination of alkene. First step includes nucleophilic attack of the
double bond from the alkene to the partially positive bromide of the bromine molecule to form
cyclic bromonium ion. Second step involves a classic backside S N2 sequence wherein a
bromide ion attacks a carbon from bromonium ion to form a dibromoalkyl product. (image
fromresearch.cm.utexas.edu)

Bromine molecule is generally symmetric but as it approaches the electron-rich pi bond

of the unsaturated hydrocarbon, an induced polarization occurs which caused it to
become an electrophile. The rate determining step in this reaction is the first step and is
endothermic. It is often a selective reaction since only the more stable radical (usually
the secondary) is formed faster and a single radical halogenated product predominates
(a trans-dibromoalkane).5

A red bromine solution is usually prepared by dissolving bromine in a carbon

tetrachloride solution but because of the toxic nature of this solvent, methylene chloride
(dichloromethane) can be used as a substitute. The solvent will deteriorate in a light-
induced, free-radical substitution that produces hydrogen bromide gas overtime, but this
can be prevented by storing the reagent in a brown glass bottle. Not all pi bonds of
unsaturated hydrocarbon reacts with the bromine solution. Only those that are electron
rich and are not substituted with electron withdrawing groups will induce the formation of
the colorless dibromoalkane product. 6In the experiment, it can be noticed that only
cyclohexene is positive in the bromination reaction (see Table 2). More drops of
bromine reagent before the system was decolorized means that a colorless
dibromoalakne was successfully formed in a fast rate until all the bromide was
consumed. The reaction mechanism can be shown below (It differs from Figure 3 since
the reaction now deals with a cycloalkane):

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Equation 2: reaction of cyclohexene with bromine reagent (red) to form a colorless 1,2-
dibromocyclohexane. (image fromchemwiki.ucdavis.edu)

It can be noticed that naphthalene and toluene also contains unsaturation (double
bonds) but is not reactive to the bromine reagent. This phenomenon can be explained
by the fact that the double bonds in these two compounds are resonance stabilized with
their electrons delocalized. It was mentioned earlier that the bromine reagent is
unreactive to double bonds with electron-withdrawing groups.

Basic oxidation reaction determines the presence of substituent (preferably alkyl) in an

aromatic system. It entails the conversion of alkyl groups in the benzylic carbon into
benzoic acid. It is a two-step, mechanistic reaction which involves the abstraction of a
benzylic hydrogen by the oxidizing agent and the oxidation of the benzylic carbon to a
carboxyl group (this process cleaves off any remaining carbon atoms on the side chain
except in the case of tert-butylbenzene).3 The overall reaction is shown in the equation:

Equation 3:conversion of alkyl benzene into benzoic acid via side chain oxidation reaction.
(image fromcourses.chem.psu.edu)

Basic oxidation is not only limited to alkyl groups it can also occur on side chains like
alkenyl, alkynyl and acyl groups3 (see Figure 4) and on rare cases, in benzene ring itself
(although under very severe reaction conditions especially in tert-butylbenzene).7

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 Alkenyl Group Alkynyl Group Acyl Group

Figure 4:other side chains reactive to basic oxidation. (image fromwww.sciencedirect.com)

The most common oxidizing agent used for the process is hot, alkaline potassium
permanganate solution (chromic acid prepared by adding sodium sichromate to sulfuric
acid is not used despite of its strong oxidizing ability since it does not react with either
benzene or alkyl).4 The purple colored solution provides a pathway in the conversion of
substituted benzene into carboxylic acid (through the OH group in the base) althoguh
some amount of energy is needed for the reaction to procee. However, under the usual
condition, the carboxylic acid product of the oxidation is formed as a potassium salt,
which is the one responsible for the brown precipitate formed in the reaction. 4

Equation 4:conversion of alkyl benzene into potassium benzoate under normal oxidation
conditions (compare to Equation 3 where the side chain oxidation does not involve formation of
potassium salt); note that the formation of benzoic acid is an acid catalysed step. (image
fromwww.tutorvista.com)

Looking at Table 2, it can be seen that cyclohexene and toluene exhibited a positive
result for oxidation reaction. Consideriong the structure of toluene (see Figure 2), it can
be inferred that indeed it will form a brown precipitate (from potassium salt, although
not easily observed). The methyl group will be oxidized to carboxyl group with
potassium ion attached (as described earlier). On the other hand , the result of the
cyclohexene can be questioned since it does not contain any side chain group. This can
be expalined by the oxidation of the double bond to form a brown precipitate of MnO 2 as
shown in the reaction:

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Equation 5:oxidation of unsaturated hydrocarbon with permanganate ion to form manganese
dioxide precipitate. (image from en.wikipedia.org)

Hereby, oxidation reactions can also be used to detect for unsaturated of an unknown
compound.

It can be seen in Table 2 that only hexane does not exhibit any reaction to any chemical
tests conducted in the analysis. Hexane belongs to the saturated aliphatic hydrocarbon
group which was generally deemed to be unreactive. This class of hydrocarbon
contains the maximum amount of hydrogen that can be bonded to a carbon-carbon
skeleton which makes the formation of any additional bond almost impossible to occur
(see Figure 5). This hydrocarbon is also non-polar as exhibited by the almost close
electronegativity values of CH bonds and by just a fleeting dipole interactions (London
forces) that it possess.1 Alkanes cannot be detected by common chemical analysis
because of these characteristics.

Figure 5:structural formula of hexane (C6H14). (image fromcommunity.fortunecity.ws)

CONCLUSIONS

Based from the results of the parallel chemical analyses of the unknown samples, it can
be established that the unknown sample without reactivity to any test procedures is a
saturated aliphatic hydrocarbon (i.e.: hexane). On the other hand, an unknown sample
with a positive result in the bromination and oxidation reactions but renders negative
result in the nitration reaction is an unsaturated aliphatic hydrocarbon (i.e.:
cyclohexene). Meanwhile, an unknown sample with a positive result for nitration

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reaction but with negative results to both bromination and oxidation raections is a non-
alkylated aromatic hydrocarbon (i.e.: naphthalene). Lastly, an unknown sample that is
positive to both nitration and oxidation reactions but is negative on bromination reaction
is an alkylated aromatic hydrocarbon (i.e.: toluene). Nitration reaction detects the
presence of benzene ring in a compound that is why both naphthalene and toluene are
rendered positive. Bromination reaction, on the other hand, detects the presence of
unsaturation, hence cyclohexene is the only positive sample. Lastly, oxidation reaction
detects both the presence of alkyl and other side chains in aromatic ring and the
presence of unsaturation which renders cyclohexene and toluene positive. Hexane is
unreactive to all tests since it is an alkane.

REFERENCES

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