Experiment No. 8A: Qualitative Analysis (Experiments A to D) Rempillo, James Earl R.; Talusan, Michelle Katherine Chem 31.

1, CD2, Group 8, Jayson DR. Vedad May 02, 2012 Qualitative analysis is the process of determining the nature of a compound. In this experiment, a number of organic compounds were subjected to four chemical tests which were the Tests for unsaturation, Tests for Aromaticity, Tests for Acidity and Basicity, and Tests for Alkylhalides, to determine their possible functional groups. The visible results displayed by the organic compounds, once subjected to the tests, were recorded then compared to other organic compounds. Then the structure and formulae responsible for the visible results were known. It can be concluded that identification of the functional groups gives the grounds for establishing the nature and full-identity of an organic compound, though not the full identity of the sample. Keywords: qualitative analysis, unsaturation, aromaticity, acidity and basicity, alkylhalides Introduction Organic compounds are defined as substances that contain the carbon atom. However, other elements are usually incorporated with these carbon atoms to form various types of organic mixtures. A method to determine these non-carbon particles is through qualitative analysis. Qualitative analysis aims to determine which elements are present in a particular substance. The aim of this experiment was to determine which functional groups were present through methods that involved wet chemistry. Wet chemistry entailed manipulating the properties of substances in its liquid phase. In this experiment, different organic test samples were reacted with various reagents. These reagents were aimed at producing a particular reaction with a specific substance. The presence of specific element/s in the mixture produced the expected, specific physical manifestations while the non-presence of an element generated different results. Experimental Part A. Tests for Unsaturation The first test to be performed was the Test for Unsaturation. This was divided into two parts: reaction with Bromine in Methylene Chloride and the Baeyer Test. The Bromine Methylene Chloride test was not done because the reagent needed for it was unavailable. The Bayer Test was performed by placing 3 drops of 1% aqueous solution of potassium permanganate in a test tube containing acetylene. Observations were subsequently noted. This test was then repeated with the test samples being benzene, styrene, and hexane. Part B. Tests for Aromaticity Second, Tests for Aromaticity were performed. Aromaticity was tested using a Nitration Test. This was done by mixing 10 drops of concentrated nitric acid and 10 drops of concentrated sulfuric acid in a test tube. This was then placed in a beaker with cold water. The mixtures were then heated in a water bath at 50 degrees Celsius for 5 minutes. After the heating process, the mixture was shook, and then poured into a beaker of 5mL ice-cold water. Presence of color change and product odor were then observed. Part C. Tests for Acidity and Basicity Next to be done were the Tests for Acidity and Basicity. These tests were further divided into the Silver Nitrate test and the Silver Acetylide test. For the Silver Nitrate test, 2 drops of acetic acid, 20 drops of ethanol, and 20 drops of 2% ethanolic acid solution were placed in a 5mL test tube. Precipitate was expected to form, so the group applied 5% nitric acid to the mixture. The group then repeated this test using phenol, aniline, and benzoic acid as a test sample. After this, the Silver Acetylide Test was done. Tollens reagent was prepared by adding 1M NH3 drop wise to 20 drops of 2% silver nitrate solution until no precipitate was present. This mixture was then poured into the test tube containing acetylene gas. This was then stoppered and shook. The color change and the formation of precipitate was then recorded. Part D. Tests for Alkylhalides Lastly, the Alkylhalide Test, was achieved by doing the Alcoholic silver nitrate test. This was performed by placing 20 drops of 2% alcoholic silver nitrate and 2 drops of ethylchloride in a 5mL test tube. This was then shaken and subsequently heated in a water bath for 1 minute. After retrieving the mixture from the hot bath, observations were recorded. This test was repeated but with page 1

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ethylbromide, ethyliodide, benzylchloride, tertbutylchloride, sec-butylchrloide and chlorobenzene as test samples. *20 drops silver acetate with 5 drops ethanol were used as a replacement for silver nitrates unavailability. Results and Discussion The decoloration of Bromine solution test and Baeyer test differentiate saturated from unsaturated hydrocarbons. In decoloration of bromine solution test, if the test compound is unsaturated, the orange-brown color of the aqueous bromine solution rapidly disappears. Bromine adds to each of carbon of the bond then the pi bond converts into a sigma bond and thus become saturated. As a result of this reaction, an OH group is added to each carbon at each end of a multiple bond. When this happens, the multiple bond becomes saturated. Potassium Permanganate (KMNO4) is an oxidizing agent. Following the oxidation of an unsaturated compound, the Permanganate ion is reduced to Manganese Dioxide (MnO4), a brown precipitate. The reaction is important because it doesnt work on alkanes (compounds with carbon-carbon single bonds) or aromatic compounds.
Table 1: Baeyer Test

positive charge being spread over two secondary carbons and one tertiary carbon atom (the one bearing the CH3 group). When reaction of toluene occurs at the meta position, then the resonance forms of the sigma complex put positive charge over 3 secondary carbons - the same as for benzene.
Table 2: Nitration

Test Samples

Visible Result

Structure/Formula of Compound Responsible for Visible Result

Toluene (Styrene)

Colorless; strong odor

Acidity, from the Bronsted-Lowry concept, is correlated with the ability of an organic compound to be a proton donor. Acidity of organic compounds is usually associated with functional groups containing OH alcohols, phenols, and carboxyls. Basicity, from the Lewis Concept of Acids and Bases, is the ability or availability of a compound to donate its electron pair. Basicity is commonly associated with amines since nitrogen has a lone pair that can be shared with Lewis acids.
Table 3: AgNO3 Test

Test Samples

Visible Result Violet-brown solution with precipitate Top layer: clear Bottom layer: brown Top: cloudy white Bottom: brown Top: clear Bottom: purple

Structure/Formula of Compound Responsible for Visible Result

Test Samples Acetic Acid Phenol Aniline Benzoic Acid

Observation Cloudy white with precipitate No sample available Light brown with precipitate Clear with white precipitate

Acetylene Benzene

MnO2 for the brown precipitate MnO2 for the brown precipitate

Styrene Hexane

MnO2 for the brown precipitate No visible result

Aromaticity is a chemical property in which a conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibit a stabilization stronger than would be expected by the stabilization of conjugation alone. It can also be considered a manifestation of cyclic delocalization and of resonance. Nitration is a general chemical process for the introduction of a nitro group into a chemical compound. Nitration of toluene generates a mixture of products. The major products are those with substitution at the ortho and para positions. In the case of toluene, ortho (and para) attack result in the Chem 31.1. Qualitative Analysis 8A

Only acids will react to form the precipitate due to the departure of H from the molecule and replacing it with a silver ion. The ammoniacal silver ion reacts with acetylene to form C2Ag2 (Silver acetylide), which is the solid precipitate. The presence of an acid is detected by the presence of + replaceable H atoms and the formation of precipitates. The essence of this test is the reaction between carboxylic acids and silver nitrate. Silver nitrate reacts with carboxylic acids to form salts of the carboxylic acid. To verify the presence of the silver salt, dilute nitric acid should be added. Silver salts should dissolve in nitric acid.
Table 4: Silver Acetylide Test

Test Samples

Visible Result

Structure/Formula of Compound Responsible for Visible Result

Acetylene

Cloudy white with formation of yello crystals that settled at the bottom

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Silver acetylide is formed when acetylene is passed into an ammoniacal solution of silver nitrate. These substitution reactions which ethynes undergo to form compounds with metals are not occur with the alknes. These reactions can be used as tests to distinguish between acetylene and ethylene. When acetylene is passed through an ammonical solution of silver nitrate or cuprous chloride, at room temperature, precipitates of silver acetylide (white) or cuprous acetylide (red) are formed. In the Test for Alkylhalides, the Alcoholic AgNO3 Test was conducted. This test can be used to differentiate aromatic halides from aliphatic halides. The reaction of an alkyl halide with silver nitrate in ethanol will result in the formation of a white or yellow silver halide precipitate that is insoluble in nitric acid. This reaction quite often proceeds slowly, and occasionally slight warming is necessary. Different rate if silver halide precipitation would be expected from halogen in each of these environments, namely, primary<secondary<tertiary. Alkyl bromides and iodides react more rapidly than chlorides. Aryl Halides are unreactive toward the test reagent.
Table 5: Alcoholic AgNO3 Test

assumed to be aromatic. This happens because the multiple carbon bonds do not all combust. If it does not produce a dark, smoky flame, it is aliphatic. 2. Do alkynes give all tests which alkenes exhibit? What tests could be used to differentiate them? No, only terminal alkynes can be differentiated with alkenes. A mercury test can e used to differentiate these two. A (terminal) alkyne is present if a gray precipitate can be observed when the substance is added to mercuric iodine. 3. Illustrate with equation the reaction of Br2 in methylene chloride with acetylene.

4. Does toluene behave in the same way like the other unsaturated hydrocarbons? Why? Toluene reacts differently because of its structure. It is very much like benzene: planar, very stable, with equal C-C bonds, cyclic, conjugated, and both following Huckels rule for pi electrons. Its benzene ring allows fewer interactions with other molecules due to its already complete and fully paired molecular orbitals, making toluene very stable. Also, when it reacts, its conjugated structure is not destroyed. Instead of addition to the pi bonds, substitution reactions happen, resulting in the preservation of the double bonds. 5. What is the role of concentrated sulfuric acid in the nitration of toluene? Concentrated sulfuric acid turns toluene into trinitrotoluene. The addition of this produces electriophilic areas and forms NO2+ (the active ion in the nitration of aromatics). 6. Show the mechanism for the nitration reaction.

Test Sample Ethylchloride Ethylbromide Ethyliodide

Tert-butylchloride

Visible Result N/A Slightly cloudy N/A

White, cloudy

Sturcture/Formula of Compound Responsible for Visible Result

N/A

N/A

Sec-butylchloride

2 clear layers
Partly cloudy; 2 layers formed White, cloudy with precipitate

Chlorobenzene Benzyl chloride

Guide Questions and Answers 1. What test/s could be used to differentiate saturated and unsaturated hydrocarbons? Explain how the test could differentiate them. A Bromine test could be used. When bromine is dropped onto an alkane, its color does not change; it stays orange. When Br is dropped onto an alkene, the orange color lessens. This is because the Bromine reacts with the carbons in the pi bonds and turns these bonds into sigma ones. An ignition test can also be used. When one heats a sample on a spatula and produces a smoky flame, the sample is Chem 31.1. Qualitative Analysis 8A

7. Give the equation involved in the reaction of

acetylene with alcoholic silver nitrate.

C2H2 + Ag(NH3)NO3 C2Ag2 + HNO3

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8. Tollens reagent for the silver acetylide test should always be freshly prepared. Why? It should be freshly prepared because it spontaneously decomposes and its precipitate becomes explosive. 9. Explain why the terminal hydrogen in acetylene is acidic when in fact the electronegativity values of hydrogen and carbon are almost the same. The terminal hydrogen in acetylene is acidic because terminal alkynes can be easily deprotonized and can produce a carbanion. Since its hybridization is sp, its H is closer to the nucleus of C, making it more stable. When the H+ atom is cleaved, the molecule becomes acidic. 10. What test could be used to differentiate carboxylic acids from phenol. Explain how the test/s could differentiate them. An ether test could be performed. The sample would be warmed with ethyl alcohol and concentrated sulfuric acid. Esters would be formed if carboxylic acid is present and the physical manifestation of this would be a fruity smell. Also, a sodium bicarbonate test can be done. When a sample is mixed with NaHCO3, and effervescence is produced, carboxylic acid is present. Other substances usually would not react the same way. 11. Why is the order of reactivity of the alkyl halides toward alcoholic silver nitrate 3>2>1? This is due to hyperconjugation. Tertiary alkyl groups help stabilize energies by spreading the charge over larger distances compared to secondary alkyl groups; subsequently, since secondary alkyl groups cover a bigger area, it has more stabilizing powers than primary alkyl groups which cover less space. 12. In the silver nitrate test for halides, explain why alcohol is used as the solvent for silver nitrate and not water. The presence of alkyl halides are determined by observing their solubitlities. This is only possible if there is dissolution of the polar nitrate and the non-polar alkyl chain to expose the halide portion. Water is only polar, so it cannot achieve this. Ethanol has both polar and non-polar properties, so it can dissolve what is needed to expose the halides. Chem 31.1. Qualitative Analysis 8A

Conclusion and Recommendations Identification of the functional groups gives the grounds for establishing the nature and fullidentity of an organic compound. Positive results from the tests confirm the presence of a specific functional group. The limitations of the experiments are the fact that the true identity of the compound cannot be determined through the tests conducted. Only the functional groups present in the organic compound can be determined. It is recommended that Further investigations can be conducted to find out the real nature and components of the organic compound.

References Klein, D. (2012). Organic Chemistry. United States of America: John Wiley & Sons, Inc. Chang, Raymond. Chemistry, 8th Edition. New York: McGraw-Hill, 2005. Qualitative chemical analysis. (2012). In Encyclopdia Britannica. Retrieved from: http://www.britannica.com/EBchecked/topic/486045/ qualitative-chemical-analysis Furniss et. al. Vogels Textbook of Practical Organic th Chemistry, 5 ed. Great Britain: Longman Scientific & Technical, 1989. McMurry, John. Fundamentals of Organic th Chemistry 5 ed. The University of the Philippines Manila. College of Arts and Sciences. Department of Physical Sciences and Mathematics. Learning Guide In Organic Chemistry.

I hereby certify that I have given substantial contribution to this report.

_______________ James Earl Rempillo

____________________ Michelle Katherine Talusan

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