Analysis of Hydrocarbons

Manalansan, Hazel Ann, Manapat, Gracy Anne Lou, *Maranan, Bianca Hannah, Montemayor, Trisha Mae Department of Psychology College of Science University of Santo Tomas Espaa, Manila 1015
Abstract : Hydrocarbons hexane, cyclohexene, naphthalene (in hexane), and toluene were subjected to three different kinds of tests, namely Nitration Test, Bromine Test, and Basic Oxidation Test. The tests aid in differentiation of physical and chemical properties of the hydrocarbons of each type. The tests help in characterization of each unknown hydrocarbon through the use of parallel chemical test.

Introduction: Hydrocarbons are generally characterized by utilizing chemical reactions that are either classified as addition or bond rupture reactions. The noticeable structural simplicity of this group significantly simplified chemical characterization. (Garcia & Manansala, 2008). Hydrocarbons are compounds that contain only carbon and hydrogen atoms. (Stoker, 2010) Hydrocarbons may be divided into two classes: aliphatic and aromatic. Under aliphatic are saturated and unsaturated hydrocarbons, which can both have acyclic and cyclic atom arrangement. Saturated hydrocarbon (Alkane group) is a hydrocarbon in which all carbon-carbon bonds are single bonds. One type of a saturated hydrocarbon is hexane. Its molecular formula is C6H14. It has acyclic atom arrangement with six carbons bonded by single bonds. Unsaturated hydrocarbon (Alkene/Alkyne) is a hydrocarbon in which one or more carbon-carbon multiple bonds (double or triple) are present. One type of an unsaturated hydrocarbon is cyclohexene. Its molecular formula is C6H10. It has a cyclic atom arrangement with six carbons bonded by single bonds with the presence of one double bond. The greater the chemical reactivity of the double bonds in unsaturated hydrocarbons can be used to distinguish alkenes from alkanes. Even when both classes of compounds can react with the same chemical reagents, the processes and products are often different. (Johnson, Miller, & Pasto, 1998).

Aromatic hydrocarbons refer to the class of compounds that contain six-membered benzene-like rings with three alternating double bonds. It has known to be less reactive than typical alkenes and fail to undergo typical addition reactions. (McMurry, 2011) One type of aromatic hydrocarbon is naphthalene. Its molecular formula is C10H8. Toluene is also a type of aromatic hydrocarbon that has a substituent of one methyl group. Nitration Test is a test use to predict presence of aromatic ring. Aromatic ring are nitrated by reaction with a mixture of concentrated nitric acids. The nitronium ion (NO 2+) which is formed from nitric acid by adding proton and loss of water reacts with benzene. Bromine Test is a test use to predict unsaturation. Addition of Br 2 acts as a simple and rapid laboratory test for unsaturation. Immediate disappearance of reddish Br 2 color signals a positive test and indicates that the sample contains a double bond. (McMurry, 2011). Bromine test for alkenes work via the mechanism of making alkenes or hydrocarbons having a minimum of one double bond undergo addition reactions. A bromine test for unsaturation makes the alkenes and the aforementioned hydrocarbons combine with the bromine to impart a colorless appearance to the otherwise reddishbrown bromine. Since alkenes contain double bonds, they are capable of undergoing addition reactions. As for the change in bromine's color, alkenes are colorless and therefore, their combination with bromine causes the latter to lose color as well as it gets consumed in the process of reaction. (Shukla, 2011). Alkanes and alkenes react with halogens such as bromine. Alkanes react to produce alkyl halides. The net result is substitution of a halide for hydrogen on the starting alkane. In contrast, alkenes undergo a net addition of halogens to the double bond by way of polar mechanism. In either case, the characteristic brown color of bromine dissipates during reactions. This color change serves as the visual tests for the reactions. (Johnson, Miller, & Pasto, 1998). Basic Oxidation Test was tested using potassium permanganate (KMnO4 ), it a strong oxidizing agent. Alkenes can easily be oxidized by potassium permanganate and other oxidizing agents. Potassium permanganate, which is purple, is reduced to manganese dioxide, which is a brown precipitate; any water-soluble compound that produces this color change when added to cold potassium permanganate must possess double or triple bonds. (http://www.cliffsnotes.com, n.d.)

Qualitative organic analysis, the identification and characterization of unknown compounds, is an important part of organic chemistry. (Engel, Kriz, Lampman, & Pavia, 1995). The classification of a compound with respect to the functional groups present and the complete identification of the compound is the concern of Experiment no. 3. Such a task is most efficiently accomplished through systematic integration of physical and chemical methods. There are steps for identification of an unknown. Step 1 is gross examination. Here one should take note of the physical state, color, and odor of the compound. Step 2 is purification of the substance, if needed. Step 3 is classification of functional group. Step 4 is final identification. (Johnson, Miller, & Pasto, 1998). A rigid and final test for identifying an unknown can be made if an authentic sample of compound is available for comparison. There is no substitute for thorough study of the prior tests. Each section should be studied carefully until one find significance of the test. Known substances should be test. In this way, it will be easier to recognize a positive test. Test should be run on known and unknown substances at the same time. This practice makes it possible to compare directly. Each successive test will either eliminate the need for another test or dictate its use. (Engel, Kriz, Lampman, & Pavia, 1995). Results and Discussion: In Nitration Test, 5 drops of each of the four standards (hexane, cyclohexene, naphthalene in hexane, and toluene) and 5 drops of the four unknowns are placed on separate test tubes. Then, 8 drops of nitrating agent is added to each test tube. After mixing the samples and nitrating agent, hexane and unknown 21 produce a colorless solution. Cyclohexene and unknown 24 produce a brown solution. The colorless and brown solution is an indication of a negative result for nitration test. While both naphthalene (in hexane) and toluene produce yellow solution. Unknown 22 and 23 also produce a yellow solution. The yellow solution indicates a positive result for nitration test. After the addition of 20 drops of distilled water to naphthalene, toluene, unknown 22, and unknown 23; naphthalene and unknown 23 produce a yellow precipitate in water. Toluene and unknown 22 produce a yellow insoluble globule in water. This is shown in Figure 1.

Figure 1: Four standards and four unknowns subjected to Nitration Test

Nitration test predicts the presence of aromatic ring. Naphthalene and toluene are both under aromatic hydrocarbons. That is why these two reacts with the nitrating agent. It can be inferred that unknown 21 is hexane, unknown 22 is toluene, unknown 23 is naphthalene in hexane, and unknown 24 is cyclohexene. Same result in the reaction of each standards and the corresponding unknown to the nitrating agent characterizes the unknowns. In Bromine Test, 5 drops of each of the four standards (hexane, cyclohexene, naphthalene in hexane, and toluene) and 5 drops of the four unknowns are placed on separate test tubes. Then, 3 drops of Br2 in Dichloromethane (DCM) is added to each test tube. After mixing the samples and Br2 in DCM, hexane, naphthalene, and toluene produce a red-orange solution. This is an indication of a negative result to Bromine Test. Only cyclohexene undergo an immediate discoloration, which is an indication of a positive result to Bromine Test. This is shown in Figure 2.

Figure 2: Four standards and four unknowns subjected to Bromine Test

Bromine Test is a test for unsaturation. Cyclohexene is an unsaturated hydrocarbon that is why it reacts with the Br2 in DCM. As expected, hexane, naphthalene, toluene, unknown 21, unknown 22, and unknown 23 produce the same negative result. Only cyclohexene and unknown 24 produce a positive result. In Basic Oxidation Test, 5 drops of each of the four standards (hexane, cyclohexene, naphthalene in hexane, and toluene) and 5 drops of the four unknowns are placed on separate test tubes. Then, 3 drops of 2% KMnO4 and 2 drops of 10% NaOH are added to each test tube. After mixing the samples and KMnO 4 with NaOH, the test tubes are subjected to water bath for two minutes. After heating, hexane, naphthalene, and toluene produce a violet solution. This is an indication of a negative result to Basic Oxidation Test. Only cyclohexene produce a brown precipitate in a colorless solution, which is an indication of a positive result to Basic Oxidation Test. These are shown in Figures 3 and 4.

Figure 3: Four standards and four unknowns subjected unknowns subjected to Basic OxidationTest

Figure 4: Four standards and four subjected to water bath for Basic Oxidation Test

Basic Oxidation Test is also a test for unsaturation, particularly to alkenes. Cycloalkene is a type of alkene, so it tests positive to the Basic Oxidation Test. As expected, hexane, naphthalene, toluene, unknown 21, unknown 22, and unknown 23 produce the same negative result. Only cyclohexene and unknown 24 produce a positive result.
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Based on the three tests that are conducted, the inference that is made from the nitration test is supported. Clearly, unknown 21 is hexane, unknown 22 is toluene, unknown 23 is naphthalene in hexane, and unknown 24 is cyclohexene. All standards have parallel results with their corresponding unknown mentioned. Summary of the whole experiment is shown on Table 1.
Table 1: four standards and four unknowns subjected to Nitration, Bromine, and Basic Oxidation Test

Nitration Test

Bromine Test

Basic Test

Oxidation

Hexane

Negative result; the Negative result; the Negative result; the solution is colorless color of the solution color of the solution is still red-orange is violet it Positive result; it

Cyclohexene

Negative result; the Positive

result;

color of the solution undergo immediate has is brown discoloration precipitate

brown in a

colorless solution Naphthalene in hexane Positive result; it has Negative result; the Negative result; the a yellow precipitate color of the solution color of the solution in water Toluene is still red-orange is violet

Positive result; it has Negative result; the Negative result; the a yellow color of the solution color of the solution is violet

insoluble globule in is still red-orange water Unknown 21

Negative result; the Negative result; the Negative result; the solution is colorless color of the solution color of the solution is still red-orange is violet

Unknown 22

Positive result; it has Negative result; the Negative result; the a yellow insoluble color of the solution color of the solution is still red-orange is violet

globule in water Unknown 23

Positive result; it has Negative result; the Negative result; the a yellow precipitate color of the solution color of the solution
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in water Unknown 24

is still red-orange result;

is violet it Positive result; it

Negative result; the Positive

color of the solution undergo immediate has is brown discoloration precipitate

brown in a

colorless solution

Methodology: The students were asked to conduct Experiment no. 3 which was about analysis of hydrocarbons. They were given four standards to test, namely hexane, cyclohexene, naphthalene and toluene. Every student was given an unknown to identify. The identification of each unknown should be done through parallel chemical tests. In Nitration Test, 5 drops of each of the four standards and each of the unknowns was put in different test tubes. Then, 8 drops of nitrating agent was added and mixed well. The results were observed. Those test tubes who reacted with the nitrating agent and produced a yellow solution were added 20 drops of distilled water. In Bromine Test, 5 drops of each of the four standards and each of the unknowns was put in different test tubes. Then, 3 drops of Br2 in DCM was added and mixed well. Careful observation was practiced by the students because there was an immediate reaction. In Basic Oxidation Test, 5 drops of each of the four standards and each of the unknowns was put in different test tubes. Then, 3 drops of 2% KMnO4 with 10% NaOH was added and subjected to water bath for 2 minutes. Changes were observed by the students. References: Engel, R., Kriz, G., Lampman, G. & Pavia, D. (1995). Organic laboratory techniques: a microscale approach. (2nd ed.). USA: Saunders College Publishing Garcia, C. & Manansala, T. (2008). Laboratory manual in organic and biochemistry. Philippines: UST Publishing House Johnson, C. Miller, M. & Pasto, D. (1998). Experiments and techniques in organic chemistry. USA: Prentice-Hall, Inc.
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McMurry, J. (2011). Fundamentals of organic chemistry. (7th ed.). USA: Brooks/Cole Stoker, H.(2010). Exploring general, organic, and biological chemistry. Philippines: Cengage Learning

Shukla, I. (2011). Bromine Test. Retrieved December 11, 2012. From http://www.buzzle.com/articles/bromine-test.html Alkenes: Oxidation and Cleavage Reactions. (n.d.). Retrieved December 13, 2012. From http://www.cliffsnotes.com/study_guide/Alkenes-Oxidation-and CleavageReactions.topicArticleId-22667,articleId-22625.html