I.

Introduction

Meanwhile, the pi bond is a result of p orbital overlap between the carbon atoms. Therefore, the
double bond becomes an electron-rich site that can react with electrophilic reagents or oxidizing
agents.

Last of the aliphatic group are the alkynes, which contain the carbon-carbon triple bond in their
structure as the functional group (see Figure 5.3.). Said triple bond is composed of a carbon-
carbon sigma bond -- but both carbons are also sp-hybridized -- and two carbon-carbon pi
bonds. Due to this, alkenes and alkynes undergo somewhat similar chemical reactions, though
alkynes with the triple bond present at the end of the carbon chain, or connected to the
terminal carbon, experience a special reaction involving the cleavage of the carbon-hydrogen
(sp-s) bond.

V. Dicussion

In this exercise, the hydrocarbon samples used were almost entirely liquid, save for acetylene
gas, which is a generated alkyne. The liquid samples used were alkanes and cycloalkanes, alkenes
and cycloalkenes, as well as aromatic rings. In order to be able to differentiate them from one
another, several tests were employed.

The first test is combustion, which, when a hydrocarbon is reacted with sufficient oxygen,
produces carbon dioxide and water when done to completion, however incomplete combustion
may occur in the event of limited oxygen, which may produce deadly carbon monoxide (Bylikin
et al. 2014). In this test, the liquid samples were ignited and the color of the flame as well as the
amount of soot produced was observed. Based on the data in Table 5.2., the aromatic
substances produced larger amounts of soot; benzene had heavy sootiness followed by toluene
with medium sootiness. Each combustion reaction can be characterized by the balanced
chemical equations below:

[5.15.]
[5.16.]
[5.17.]
[5.18.]
[5.19.]

Hydrocarbons become more difficult to burn as the molecules increase in size; this is due to their
low volatility, causing only surface molecules to be able to react with oxygen (Clark 2015). Most
hydrocarbons should burn with a blue flame, provided that the combustion reaction is complete,
however increasing the number of carbon atoms in the molecule lessens the probability of a
complete reaction (Clark 2015). Due to this, larger hydrocarbons are most likely to produce a
smoky, yellow flame, such as was seen in the flammability and sootiness of benzene and
toluene.
Halogenation is the replacement of one or more hydrogen atoms in a C-H bond by a halogen
(usually chlorine or bromine); this is a free-radical substitution reaction which occurs upon
exposure to light or high temperature (Capareda et al. 2004). In this exercise, the effect of light
in bromination was observed in different samples of hydrocarbons. Light (or heat), shown as hv
in reactions, weakens the Br--Br bond, and each electron of the bond is taken by its respective
bromine atom, making them bromine radicals. Based on the data in Tabke 5.3., among those test
tubes covered in carbon paper, only cyclohexene observed decolorization as a result of
bromination (see Equation 5.20.), while among those exposed to light, cyclohexane,
methylcyclohexane and toluene observed decolorization (see Equations 5.21., 5.22., 5.23.).

[5.20. -5.23.]

Benzene, as a closed aromatic compound with no substituents, does not react with bromine,
however toluene does react with bromine under light due to the presence of the methyl group
causing the formation of bromobenzyl, as seen in equation 5.23. Based on Table 5.6., the
generated acetylene gas also caused the red-orange bromine solution to decolorize, this is due
to the breaking of one of the pi bonds so that the two bromine atoms may become bonded to
the alkyne (see Equation 5.24.).

[5.24.]

Supposedly, cyclohexene is able to react with bromine under light, and through free-radical
substitution (a stable cyclohexene allylic free-radical will form which will further react with
bromine free radical), forms 3-bromocyclohexene (see Equation 5.25.) (Fatima 2016). However,
this is somehow observed in the test tube not exposed to light, which may be result of
accidental exposure of the contents to light while the test tube exposed to light may have
contained contaminants.

[5.25.]

An allylic radical, in this case, refers to a resonance-stabilized radical in which the unpaired
electron is on an allylic carbon, or a carbon atom bonded to a carbon atom that in turn is doubly
bonded to another carbon atom (Gunawardena 2015); this can be further explained by the
diagram in Figure 5.5.

Figure 5.5. Resonance structures exhibiting an allylic radical.

Similarly, a benzyllic radical is a resonance-stabilized radical in each of two equally stable major
resonance forms of which the unpaired electron is on a benzyllic carbon (Gunawardena 2015);
this can be seen in the diagram in Figure 5.6.

Figure 5.6. Resonance structures exhibiting a benzyllic radical.

Both of the aforementioned systems undergo halogenation, such as an allylic or benzyllic C--H
bond, which particularly weak because the radical formed through the homolytic breaking of C-
H is stabilized by resonance (Ashenhurst 2013).

In terms of the rate at which light-catalyzed bromination takes place, the data in Table 5.7.
concludes that the hydrocarbon that decolorized the fastest was ethylbenzene, followed by
toluene, 2,2,4 - trimethylpentane, and cyclohexane; this can also be seen as the order of
decreasing reactivity. Due to radical stability increasing as the number of carbon substituents
increase, primary hydrogens produce the least stable free-radical while tertiary hydrogens
produce the most stable, and the greater the stability, the weaker the C--H bond strength
(Ashenhurst 2013). Bromine selectively reacts with tertiary bonds over primary and secondary
C--H bonds, thus the reaction between tertiary molecules such as ethylbenzene and toluene
occurs much quicker compared to alkanes such as 2,2,4-trimethylpentane and cyclohexane due
to their weaker bond strength.

Baeyer's Test, or the reaction of hydrocarbons with cold, dilute, neutral potassium
permanganate (KMnO4), is used to differentiatiate alkenes and alkynes from alkanes and
aromatic groups. Based on the data in Table 5.4. and also 5.6., only cyclohexene and acetylene
gas reacted "positively", which means that a dark brown, turbid mixture formed upon addition
of KMnO4. This is due to the presence of manganese dioxide (MnO2).

Mangante (VII) ions are a strong oxidizing agent; under acidic conditions, this ion is reduced to
manganese (II), while under alkaline conditions, is first oxidized to green manganate (VI), until
eventually, dark brown MnO2 is formed (Clark 2016). Under neutral conditions, dark brown
MnO2 also precipitates out. From a purely organic perspective, the oxidizing agent donates an
oxygen atom and, together with the H2O present, adds two ethanol groups to the two carbons
involved with the pi bonds. The reaction between cyclohexene and KMnO4, and ethylene and
KMnO4, are as follows:

[5.26.]
[5.27.]

Also known as Tollens' Test, reactions with ammoniacal silver nitrate are most often used to
confirm the presence of alpha-hydroxyl ketones and aldehydes; however, Tollens' Reagent can
also be used to confirm the presence of a terminal alkyne; in the case of acetylene, ammoniacal
silver nitrate reacts with it to form silver acetylide, which will precipitate out of the solution (see
Equation 5.28.) (Chemistry Stack Exchange 2015). As such, no precipitates formed with any of
the samples in Table 5.5., thus the "negative" for the Tollens' Test.

[5.28.]

These various chemical tests may be used to differentiate certain hydrocarbons from one
another. For example: (1) between benzene and ethylbenzene, a light-catalyzed bromination test
may be used, as ethylbenzene will decolorize and benzene will not, (2) between 2-
methylpentane and 2-methyl-2-pentene, Baeyer's Test may be used, as MnO2 will only
precipitate out with the alkene, (3) between toluene and 1-methylcyclohexane, measuring the
rate of light-catalyzed bromination may be used, as toluene decolorizes much quicker due to its
tertiary hydrogens, as compared to the primary and secondary hydrogens in the cycloalkane, (4)
between 1-pentene and 1-pentyne, the ammoniacal silver nitrate test may be used, as silver
acetylide will only precipitate out with 1-pentyne, and lastly (5), between 1-pentyne and 2-
pentyne, the ammoniacal silver nitrate test may be used, as silver acetylide will precipitate out
with 1-pentyne due to the presence of an sp C-H bond.

>> REACTION OF LYCOPENE WITH BROMINE

In a demonstration, lycopene (from tomato paste) reacted with bromine water.

The blue colour of the lowest layer in the ‘rainbow’ is thought to be due to the
predominance of the CT complex. (A complex between two organic molecules in which
an electron from one (the donor) is transferred to the other (the acceptor), becoming
generally distributed throughout the latter; subsequent transfer of a hydrogen atom
completes the reduction of the acceptor; such complex's are generally highly coloured
and may be so observed.

VI. Summary and Conclusion

To be able to differentiate them from one another, several tests were performed to investigate
the liquid hydrocarbon samples, and would later be tested on the generated acetylene gas
(except for the combustion test).

VIII. References

A. Books

BYLIKIN, S., HORNER, G., MURPHY, B., TARCY, D. 2014. Chemistry: Course Companion. Oxford,
UK: Oxford University Press. 249.

CAPAREDA E.P., LACSAMANA M.S., RODRIGUEZ E.B., TALAN R.S. 2004. Basic Organic Chemistry:
Handouts and Problem Sets. 2nd Edition. University of the Philippines Los Banos, Laguna:
Division of Organic Chemistry and Natural Products.

CARET R.L., DENNISTON K.J., TOPPING J.J. 1993. Principles and Applications of Inorganic, Organic
and Biological Chemistry. Dubuque, Iowa: Wm. C. Brown Publishers. 224.

B. Web Sources

ASHENHURST J. 2013. Allylic Bromination. Retrieved October 15, 2017, from:

https://www.masterorganicchemistry.com/2013/11/25/allylic-bromination/

ASHENHURST J. 2013. Selectivity In Free Radical Reactions. Retrieved October 15, 2017, from:
https://www.masterorganicchemistry.com/2013/09/23/selectivity-in-free-radical-reactions/
CHEMISTRY STACK EXCHANGE. 2015. Acetylene and the Tollen's test. Retrieved October 15,
2017, from: https://chemistry.stackexchange.com/questions/23670/acetylene-and-the-tollens-
test

CLARK J. 2016. Alkenes and potassium manganate (VII). Retrieved October 15, 2017, from:
http://www.chemguide.co.uk/organicprops/alkenes/kmno4.html

CLARK J. 2015. The combustion of alkanes and cycloalkanes. Retrieved October 15, 2017, from:
http://www.chemguide.co.uk/organicprops/alkanes/oxygen.html

FATIMA M. 2016. What is the primary product when cyclohexene reacts with bromine in the
presence of UV light? Retrieved October 15, 2017, from: https://www.quora.com/What-is-the-
primary-product-when-Cyclohexene-reacts-with-bromine-in-the-presence-of-UV-light

GUNAWARDENA G. 2015. Allylic Radical. Retrieved October 15, 2017, from:

http://www.ochempal.org/index.php/alphabetical/a-b/allylic-radical/

GUNAWARDENA G. 2015. Benzylic Radical. Retrieved October 15, 2017, from:

http://www.ochempal.org/index.php/alphabetical/a-b/benzylic-radical/

REESER D. 2015. Tomato Juice Rainbow Explained. Retrieved October 15, 2017, from:
http://chemicalsareyourfriends.com/sliders/tomato-juice-rainbow-explained/

UNIVERSITY OF ILLINOIS. 2010. Q & A: Baeyer’s Test. Retrieved October 4, 2017, from:
https://van.physics.illinois.edu/QA/listing.php?id=505

UNIVERSITY OF LIMERICK. 2007. The tomato juice rainbow. Retrieved October 15, 2017, from:
http://www.csn.ul.ie/~sarah/files/Tomato_juice_rainbow.doc.

UNIVERSITY OF MALTA. 2005. Alkanes. Retrieved October 4, 2017, from:

http://staff.um.edu.mt/ratk1/AldeKetProps.htm

WEIL A. 2017. Lycopene. Retrieved October 15, 2017, from: https://www.drweil.com/vitamins-

supplements-herbs/supplements-remedies/lycopene/