Experiment 55: Qualitative Analysis

Karly Childress

Organic Chemistry Lab, CHEM 369 The University of Tennessee, Knoxville Yundi Dr. Laureta Smith Date Performed: 27 July 2011 Due Date: 1 August 2011

Introduction The purpose of this experiment is to identify an unknown compound through chemical and spectroscopic methods. The unknown was characterized by the Infrared Spectroscopy (IR), 1H and 13C Nuclear Magnetic Resonance Spectroscopy (NMR). H-NMR is a technique that examines the nuclear magnetic moments of atoms based on their spin properties. It determines the number of different types of hydrogens present in the molecule, the relative number of different types of hydrogens, the electronic environment of the different types of hydrogens, and the number of hydrogen neighbor a hydrogen has. Similar to H-NMR, C-NMR is also a technique in determining the structure of the unknown compound. C-NMR provides information concerning the number of different types of carbons atoms present in the molecule, the electronic environment of the different types of carbons, and the number of neighbors a carbon has (also known as splitting). Infrared Spectroscopy is a technique used to determine the chemical functional groups in the unknown. In this experiment, several classification tests were run to determine the physical properties and functional group of the unknown compound. The compound had the possibility of containing any of the major functional groups (alcohol, aldehyde, ketone, carboxylic acid, phenol) and one or more of the secondary functional groups (alkene, aromatic). All aqueous solutions were disposed of in the container designated for aqueous waste and all the organic compounds were disposed of in the appropriate organic waste container.

Procedures and Observations The unknown compound was a white, powdery solid. On the first lab session, the objective was to identify the functional group(s) present. First, the melting point was run via Mel-Temp showing that the unknown had a melting point of 150-154oC. Solubility of the unknown was then determined by adding one milliliter of the solvent to 0.1 grams of the unknown. The solubility chart on page 454 of the Organic Laboratory Techniques book was followed to determine the functional group. The first solvent on the chart was water, when mixed with the compound showed that it was fairly soluble in water. The next step was to determine whether the compound was basic, acidic, or neutral by spotting red and blue litmus paper. The blue litmus paper turned red indicating it was an acid but also that it was a carboxylic acid. On the second lab session, the objective was run various tests to confirm functional group and to specifically identify the unknown compound. The test for unsaturation was the first test run using potassium permanganate and bromine in methylene chloride. In the potassium permanganate test, twenty-five milligrams of the unknown was dissolved in two milliliters of 95% ethanol then %1 aqueous solution of potassium permanganate was slowly added. The purple color of the reagent was discharged and a brown precipitate of manganese dioxide formed indicating a positive test. In the methylene chloride test, fifty milliliters of the unknown compound was dissolved in one milliliter of methylene chloride. A 2% solution of bromine in methylene chloride was then added to find if the red color disappears. More than five drops of the bromine solution were added with discharge of the red color of bromine indicating a positive test. The test for an aldehyde or ketone was skipped because as previously stated

the functional group was a carboxylic acid therefore the next test that was run was to check for aromaticity. This test was simply preformed by looking at the IR Spectrum. The IR did not show an aromaticity therefore this test was negative. The test for a carboxylic acid was run next by checking the pH with pH paper. The compound had a low pH of around 3-4 signifying an acid. The last step of the carboxylic acid was to test for solubility in sodium bicarbonate. A small amount of the compound was dissolved in a 5% aqueous sodium bicarbonate solution. Bubbles of carbon dioxide were produced showing an acid therefore proving the unknown compound was a carboxylic acid. Once the functional group was identified, a list of possibilities was made based on the physical properties and results of the classification tests by referring to the Table of Unknowns in Appendix 1 of the laboratory book. There were six possibilities in the carboxylic acid table based on the melting point taking on the first lab session. Only one of the compounds did not have a halide (previously stated by TA that none of the compounds contained) and a benzene ring, which was Hexanedioic acid (adipic acid). The compound was verified by the H-NMR and C-NMR that it was indeed hexanedioic acid. Data Reagent Water Potassium Permanganate Methylene Chloride Bromine 95% Ethanol Sodium Bicarbonate Formula H2O KMnO4 CH2Cl2 Br2 C2H5OH NaHCO3 Role Solvent Solvent Solvent Solute Solvent Solvent Amount Used 1 mL 5 drops 100 mL 2 mL 2 mL Small amount Hazards none Harmful with skin contact Harmful with skin contact Toxic Flammable Harmful with eye contact

IR cm
-1

Stretch O-H C=O C-H

~3000 ~1710 ~1200-1500

H-NMR Chemical Integration Splitting shift 12 2H Singlet 2.2 1.7 4H 2H Triplet Quintet

C-NMR Chemical Splitting shift (if given) 173 Singlet 32 23 Triplet Triplet

13

Results and Discussion This experiment qualitative organic analysis by performing the appropriate methods for establishing the identity of a compound. An unknown compound was issued and asked to identify it through chemical and spectroscopic methods. In the solubility test, it was determined that the unknown was soluble in water. Compounds that contain five or six carbons are often insoluble or in this case have borderline solubility. When the ratio of oxygen in a compound to the carbon atoms is increased, the solubility of the compound in water often increases. This is due to the increased number of polar functional groups. When the blue litmus paper was test and it turned red showed that the compound was a carboxylic acid. In the unsaturation test, the compound was positive for unsaturation in potassium permanganate and methylene chloride. The test is typically positive for double and triple bonds but not for aromatic rings. The conversion of the purple ion MnO4- to a brown precipitate of MnO2 following the oxidation depends on the unsaturation of the

compound.

This

reaction shows the unsaturation of the double bonds. By observing the IR Spectra it was discovered that the compound was not positive for the aromaticity test. As previously states the test of unsaturation also provided this observation as well. The compound did not have any C=C but also did not have C-H stretch, aromatic ring which would occur at a higher frequency than 3000 cm-1. Since the compound was soluble in water, in the carboxylic acid test the pH level was checked with pH paper and was predicted to have a low pH for an acid. When this step was completed it resulted in a pH level of ~3-4, confirming our prediction. When the compound was dissolved in 5% aqueous sodium bicarbonate it was also predicted that bubbles may appear of carbon dioxide. This also confirmed that the compound was an acid. The following reactions show the confirmation of the acid forming carbon dioxide bubbles: RCOOH + NaHCO3 RCOO-Na+ + H2CO3 (unstable) H2CO3 CO3 + H2O If the compound was indeed a carboxylic acid, the infrared spectroscopy would have a C=O stretch that was very strong and often broad in the region between 1725 cm-1 and 1690cm-1. When looking at the IR spectra one can clearly see the C=O stretch around 1710cm-1. The carboxylic acid was predicted to also have an O-H stretch that has a very broad absorption in the region between 3300cm-1 and 2500cm-1; it usually overlaps the CH stretch region. The IR spectra of the unknown shows the O-H stretch around 3000cm-1.

All of the tests performed in this experiment lead to the conclusion that the compound was a carboxylic acid. Looking at the 1H-NMR and 13C-NMR determines the number of hydrogen and carbons and where they are located in the compound. The O-H is a singlet indicating that they are located on the ends of the carbon straight chain. The C=O has a triplet splitting indicating that there are so bonds attached to the carbon. After observing the IR Spectra, 1H-NMR, and 13C-NMR and referring back to the melting point of 150-154oC it was determined that the unknown compound was Hexanedioic acid, typically called adipic acid. Conclusion The unknown compound was determined by performing the experiment of qualitative analysis by classification tests. This experiment is very good practice if one is studying to become a professional chemist, a scientist, or a pharmacist. These professions use these tests daily to determine certain compounds. The ultimate goal for this experiment was to reject every compound but the correct one, not to prove whether the compound was this or that. By having this task previously set, the classification tests were simply easy to perform to determine the specific name of the unknown compound. The 1H-NMR and 13C-NMR were used to characterize the compound respectively by where the hydrogens and carbons were located. The IR Spectrum was used to analysis the specific functional groups. As a result, the compound was discovered to be have a carboxylic functional group and the specific name of the unknown compound was hexanedioic acid.

References Pavia, Donald L. A Small Scale Approach to Organic Laboratory Techniques. Belmont, CA: Brooks/Cole ; Cengage Learning, 2011. Print.