POSTLAB Exer 5

References:
Arora, A. 2006. Hydrocarbons Alkanes, Alkenes, Alkynes.
Bansal, R. 1998. Organic reaction mechanisms. p. 10.
Bettelheim, F. & Landesberg, J. 2010. Laboratory Experiments for Introduction to General,
Organic and Biochemistry. Eighth Edition. p.277
Boikess, R.2014. Chemical Principles for Organic Chemistry. pp. 41-43.
Bruice, P. 2005. Organic Chemistry. Fourth Edition. pp. 144
Daley, R. 2005. Organic chemistry. p.794-796, 955.
Hill, G. & Holman, J. 2000. Chemistry in context. p. 407
Hoffman, R. 2004. Organic Chemistry: An Intermediate Text. pp. 71-75.
Kulkharni, M. 1997. Resonance. Volume 2, Issue 9. pp 69-72.
McMurry, J. Organic Chemistry. p. 22.
Morrison, R. & Boyd, R. 1992. Organic Chemistry. pp. 41, 328
O'Neil, M. J. (2006). The Merck index: An encyclopedia of chemicals, drugs, and biologicals.
Patrick, G. 2005. Organic chemistry. Second edition. p. 105
Pavia, D. 2005. A small scale approach in organic laboratory techniques. p. 481.
Roberts, J. & Caserio, M. Basic Principles of Organic Chemistry. p.
Reaction of Hydrocarbons. Retrieved from http://www.pcc.edu/staff/pdf/662/CH102_Exp_3.pdf.
Singh, M. 2004. Advanced Organic Chemistry: Reactions And Mechanisms. p. 49.

Flammability is the measure of the extent to which a material or substance will support
combustion. Combustion is said to be complete if a blue flame (non-luminous) is produced
which indicates that there is more heat than light (). This also shows that the carbon is
completely oxidized. On the other hand, an indication of an incomplete combustion is a yellow
flame (luminous) where there is much light than heat. In contrast to the former combustion, this
incomplete combustion shows that the carbon is not completely oxidized.
The first test known as the ignition test brings about a chemical change; some decompose and
blacken, while others burst into flame. Based on the experiment, this was done to determine the
flammability and the presence of unsaturation or high carbon to hydrogen ratio of each organic
compound (Pavia, 2005). The degree of unsaturation or simply the C:H ratio is calculated based
on the formula (McMurry, ). Results would reveal that the higher the C:H ratio, the higher is the
luminosity. Luminosity is assessed by the presence of a yellow flame and soot (Pavia, 2005).
Five organic compounds were used in this part namely cyclohexane, methylcyclohexane,
cyclohexene,benzene, and toluene. The first compound used was cyclohexane (Refer to Fig.
5.3.). Cyclohexane is a cycloalkane which has a molecular formula of C6H12 (). After
undergoing the ignition test, cyclohexane produced a yellow flame, therefore it was not sooty.
The reaction involved here is
Next is the methylcyclohexane (Refer to Fig.5.4.) which is also a cycloalkane with a molecular
formula of C7H14 (). It produced a yellow flame, thus it was not sooty. The reaction involved
here is
Meanwhile, cyclohexene (Refer to Fig.5.5.) is a cycloalkene with a chemical formula of
C6H10(). It is less sooty and the flame produced was a yellow-colored one. The reaction
involved here is
Benzene (Refer to Fig. 5.6.), an aromatic hydrocarbon with a molecular formula C6H6, was very
sooty and the flame produced was a bright yellow one. This observation led to the reaction, .
Lastly is the toluene (Refer to Fig. 5.7.), an aromatic compound and a monosubstituted benzene
derivative which has a molecular formula of C7H7 (). After the ignition test, it was sooty and the
flame produced was a bright yellow one. The reaction for this is
Based on the results, aromatic compounds burn with sooty flame due to incomplete combustion
which causes the formation of an unburned carbon. They are compounds whose molecular
formulas would lead to a high degree of unsaturation (Morrison & Boyd, 1992). Aromatic
compounds are followed by the unsaturated hydrocarbons and lastly by the saturated ones.
Bromine test was performed to look for the presence of double bonds. The reagent used was
bromine in dichloromethane solution. In this experiment, dichloromethane serves as the solvent
that will bring bromine in contact with the hydrocarbons. Since hydrocarbons are covalent
compounds and do not dissolve in ionic solvent, they tend to dissolve in a solvent that has similar
properties with it particularly in polarity. Hydrocarbons are nonpolar, thus dichloromethane,
based on its structure (Refer to Fig. 5.8.), is a good medium since it is also nonpolar and inert
towards hydrocarbons and bromine.
Two sets of test tube were prepared together with the hydrocarbons. The hydrocarbons used are
cyclohexane, methylcyclohexane, cyclohexene, benzene, and toluene. One set was placed under
the light while the other one was wrapped with a carbon paper. The general process that will take
place is called halogenation. The halogen used in this experiment was bromine; thereby, the
process is known as bromination. This process proceeds by different mechanisms. First is the
free radical substitution, a mechanism by which alkanes and alkylbenzenes undergo bromination.
This mechanism requires light or heat in order to produce bromine radical which will react with
the hydrocarbon. The addition of halogen to an alkane is a substitution reaction and only one
atom of halogen is replaced by one hydrogen atom. The positive sign of such reaction is
indicated once the red-orange color of bromine faded and an evolution of gas (HBr) happens.

Bond-breaking can occur in two ways: heterolysis and homolysis (Hoffman, 2004). Both
electrons of a bond in heterolysis are moved to the more electronegative atom (out of a pair of
bonded atoms), resulting in a cation and anion (Hoffman, 2004). In homolysis, however, the two
atoms have a low electronegativity difference so when the bond breaks, one electron is
transferred to each atom, resulting in free radicals, atoms with unpaired electrons (Hoffman,
2004). In the first step of bromination of alkanes, known as initiation, heat (200-400 C) or
ultraviolet light (h) is being applied to a mixture of the alkane and bromine which causes the -
bond of the molecular bromine(Br2) to undergo homolysis, generating bromine radicals, Br; Br2
undergoes homolysis as there is no difference in electronegativity between the identical bromine
atoms.Br are formed in low concentration, resulting in a net increase in the concentration of free
radicals within the system. The next step in the bromination of alkanes is propagation. Here, a
hydrogen atom is preoccupied from the hydrocarbon by a Br to produce a new free radical, R,
and hydrobromic acid, H-Br.R then attacks Br2 to yield the alkyl bromide, R-Br, and Br, thus
regenerating the free radical needed for propagation. Note that there is no net change in the
concentration of radicals. In the last step of bromination of alkanes, termination, the free radicals
formed in the reaction (Br and R) combine with each other to give different molecules (Br2, R-
Br, and R-R), resulting in a net decrease in radical concentration and a decrease in the rate of the
reaction.
(Insert reaction)
As a result, the steps of initiation, propagation, and termination, constitute a free-radical chain
mechanism for bromination of alkanes, and the overall reaction can be summarized in the
following chemical equation:
The second mechanism is the electrophilic addition which can take place even in the dark;
however, as a result, no HBr is produced. This particular mechanism involves the bromination of
alkenes and alkynes. In this reaction of alkenes (or alkynes), the bond of the double bond (or
triple bond) is used to form a bond to an incoming electrophile and is no longer present in the
product (Patrick, 2005). Moreover, a new substituent has been added to each of the carbon atoms
(Patrick, 2005). The sign of reaction is decolorization of reagent but without evolution of the gas.
Based on the results, no reaction took place in the dark for cyclohexene as it belongs to a family
of alkenes which is much more reactive and undergoes addition reaction. The double bond of the
cyclohexene breaks down and becomes single bonds which bromine atoms bonded to each of the
carbon atoms that shared the double bond. Thus, the yellowish brown solution turns cloudy as it
forms dibromocyclohexane and the blue litmus paper turns pink as it is acidic.
(Insert reaction)
Since aromatic compounds are resistant to the addition reaction which is generally a
characteristic of unsaturated compounds, these aromatic compounds undergo electrophilic
substitution reactions (Morrison & Boyd, 1992).
Another purpose in this experiment was to determine the relative rates of bromination for n-
hexane, 2,2,4-trimethylpentane, toluene, cyclohexane, ethylbenzene. In the experiment, toluene
undergoes bromination at a faster rate even though it is brominated at primary carbon which is
explained by the resonance stabilization of the benzylic free radical. Movement of electrons from
the bond orbital toward the vacant p orbital of the methyl cation decreases the charge on the
carbon and causes a partial positive charge to develop on the carbon bonded by the bond.
Therefore, the positive charge is no longer localized solely on one atom, but is spread out over a
greater volume of space. This dispersion of the positive charge stabilizes the carbocation because
a charged species is more stable if its charge is spread out over more than one atom. According to
Singh (2005), delocalization of electrons by the overlap of a bond orbital with an empty p orbital
is called hyperconjugation. In contrast to resonance where overlap of and lone-paired electrons
is involved, the hyperconjugation structures are written involving overlap of sigma electrons
with the adjacent bond (Singh, 2005).
According to Arora (2006), when there is a large difference in the reactivity of different types of
hydrogens in the hydrocarbons molecule, only one product is formed under suitable conditions.
The order of reactivity for different types of hydrogens is
Benzylic, allylic > tertiary > secondary > primary > vinylic = aryl (Arora, 2006). Arora (2006)
further stated that the high reactivity of allylic and benzylic hydrogens is due to the stabilization
of the allylic and benzylic free radicals formed during the reactions by resonance. An allylic
radical is a resonance-stabilized radical in each of the two resonance forms of which the unpaired
electron is on an allylic carbon. On the other hand, benzylic radical is
In addition to this, Daley (2005) indicated that there is a small difference in the stability for
radicals than for carbocations. For instance a result, radical reactions are often less selective than
reactions with carbocations (Daley, 2005). Additionally, incoming radicals are very sensitive to
steric factors, so they attack the least hindered carbon of the double bond (Daley, 2005). As a
conclusion, the greater the number of alkyl substituents bonded to the positively charged
carbon, the more stable the carbocation is (Bruice, 2005).t
Acetylene (Refer to Fig. 5.) is a gas characterized by its explosive nature. It results an
unsaturated hydrocarbon by its triple C- C bond. Acetylene (ethyne) is formed when water reacts
with calcium carbide, which is shown below.
(Insert reaction)
Upon the addition of bromine in dichloromethane, acetylene produced a clear solution and the
red-orange color disappeared. This should happen both in light and dark reactions; however, it
was not observed in the light reaction. Since the result did not match with the

rules or principles involve in the test, this explains that there are errors in the results acquired.
This can be attributed in various factors such as contamination of the sample used.
Along with bromine test, Baeyers Test is also a test for the presence of unsaturation or double
bonds. This test was done by adding 3 drops of hydrocarbon to a mixture of a cold dilute neutral
potassium permanganate solution which was the reagent used. Potassium permanganate is an
inorganic compound and is a very strong oxidizing agent.
A positive result is indicated by the loss of the purple color and the formation of a brown
precipitate MnO2, provided the molecule contains no easily oxidizable group. Based on Table
5.4., there was no observable reaction when drops of KmnO4 were added to cyclohexane since
the solution remained purple in color except that a double layer is formed on the surface of the
solution. The double layer formed was due to the oil present in the benzene ring of the
cyclohexane. Because the compound is an alkane in nature, it is expected that there would be no
reaction. Because alkanes are nonpolar in nature, they are generally unreactive towards polar
reagents such as oxidizing agents (Hill & Holman, 2000). The same goes with the
methylcyclohexane where no indication of precipitate was formed simply because the compound
belongs to the family of alkane which do not display a reaction with oxidizing agents as
mentioned above. On the other hand, benzene and toluene, which are both aromatic compounds,
did not react because both contain a certain number of conjugated double bonds and are
especially stable due to their resonance structures (https://www.boundless.com). The bonding is
said to be strong than what is expected for a conjugated structure, and it is more depicted as
delocalized electron density shared between all the atoms in the ring
(https://www.boundless.2.........com). Among the five compounds, only cyclohexene formed a
reaction with KMnO4. Upon the addition of KMnO4, there was a decolorization of the purple-
colored solution which indicates the presence of alkenes. One property of alkenes which explains
why cyclohexene reacted with KMnO4 solution is that alkenes are readily oxidized at room
temperature (). The reaction that takes places is oxidation which causes the purple solution to
turn brown color. There is also brown precipitate formed and the surface of the solution has
double layers. The purple solution changes color to brown because potassium permanganate is
reduced to manganese dioxide, which is the brown precipitate. The double layers exist due to the
same reason as in the cyclohexane. As a conclusion, the reaction involved in Baeyers test is a
redox reaction because Mn7+ is reduced to Mn4+ while alkene is oxidized to diol.
(Insert reaction)
Separately, acetylene reacted with potassium permanganate. Evidence that the reaction has
occurred is the rapid disappearance (within a few seconds) of the purple permanganate color. The
resulting reaction product was typically a brown solid. This means that there is a presence of
unsaturation since acetylene belongs to the family alkyne.
(Insert reaction)
Second to the last is the Tollens test which indicates the presence of terminal alkynes. The
reagent used is known as Tollens reagent, a weak oxidizing agent composed of ammoniacal
silver nitrate [Ag(NH3)2+]. The positive result is detected by the formation of an insoluble
substance or a gray precipitate. Based on the results, cyclohexane, methylcyclohexane,
cyclohexane, benzene, and toluene did not produce a reaction when 10 drops of the reagent was
added. This means that the compounds above are not terminal alkynes. Acetylene (Refer to Fig.
5.) being a terminal alkyne gives a grayish white precipitate of silver acetylide with ammoniacal
silver nitrate solution.
(Insert reaction)

Lastly is the tomato juice rainbow experiment. Tomato juice contains lycopene (Fig. 5.) which
is an organic molecule with 13 conjugated double bonds (Kulkarni, 1997). The double bonds of
this red pigmented molecule can be broken using a solution of bromine water.

When the saturated bromine water was added to the tomato juice, the bromine adds to the double
bonds using electrophilic addition. According to Bettelheim & Landesberg (2010), slow stirring
allows the bromine water to penetrate deeper and deeper into the cylinder where the tomato juice
was placed. They also concluded that as the bromine penetrates, more and more double bonds
will react. The bromine can be added in many ways hence changing the conjugation levels within
the lycopene. Therefore, a continuous change, a rainbow of colors occurred. It started with the
reddish tomato color at the bottom of the cylinder, where there is no reaction because the
bromine was not able to reach the bottom. It went to lighter colors on the top of the cylinder,
where most of the reaction of double bonds with bromine took place. A stable charge transfer
complex with a blue color was also formed. Upon further reaction with bromine water lycopene
essentially became pale yellow. The mixture of the blue color with the reddish-orange of the
tomato juice and the pale yellow caused the rainbow colors to form. What happened is that the
colored pigments in the cylinder formed a reaction with bromine and lose their color eventually
as the reaction proceeds (Bettelheim & Landesberg, 2010). In the areas where the concentration
of bromine is highest, the length of the conjugation will be the shortest. In these areas, the
shortest wavelengths will be absorbed, and the longer wavelengths will then be reflected.
Once the ultraviolet or visible light is absorbed by a molecule, the energy goes into increasing
the energy levels of valence electrons. Furthermore, when light is absorbed by the molecule,
these electrons which normally exist in in the ground state are pushed up to higher energy levels
or to an excited state. If the energy level of the excited state is a lot higher than that of the ground
state, a large amount of light energy is required to push the electrons up to the higher level, and
two correspondingly higher energies of light are needed to do this. If the excited state is closer in
energy to the ground state, a respectively lower energy of light is needed.
As a conclusion, the ground states and excited states of the electrons for molecules having
conjugated systems of electrons such as lycopene are closer in energy than for molecules having
the nonconjugated systems (Boissen, 2014). This is an implication that lower energy light is
needed to excite electrons in conjugated systems, which means that lower energy light is
absorbed by conjugated systems at the visible region (Boissen, 2014. According to Boissen
(2014), the degree of conjugation determines the actual energy difference between the ground
and excited states. The more highly conjugated the system the lower the energy difference and
the lower the required energy of light needed to excite the electrons. In other words, molecules
having more conjugated multiple bonds absorb lower energies of light than do molecules having
fewer conjugated multiple bonds (Boissen, 2014).
To distinguish between benzene and ethylbenzene, the chemical test to be used
To distinguish between 1-pentyne and 2-pentyne, the chemical tests to be used are by
ammoniacal silver nitrate test or oxidation. To distinguish between 1-pentyne and 1-pentene, the
chemical tests to be used are by flammability test, bromination or oxidation.

CONCLUSION
The experiment achieved the objectives of differentiating alkanes, alkenes, alkynes and aromatic
hydrocarbons through their properties and visualizing the characteristicreactions of alkanes,
alkenes, alkynes and aromatichydrocarbons and the preparation of acetylene gas