Identification of an Unknown Organic Acid

Ansley Barfield Chem 1211 Lab Summer 2012

Abstract The purpose of the following experiments is to identify an unknown organic acid (335031-CS12). After recrystallization of the unknown, various parameters were determined to aid in characterization of the acid. The melting point range was determined to be 159-162C. Equivalent weight calculated by the pKa titration was 236.91 3.4 g/mol and equivalent weight determined by the titration with an indicator was 238.6 3.3 g/mol. The average equivalent weight was 237.76 g/mol. The molarity of NaOH was computed to be .1102 M. The sodium fusion test indicated that cyanide ions were present in the acid; therefore, the unknown organic acid was identified to be 4methyl-3,5-dinitrobenzoic acid.

I. Introduction The purpose of this experiment is to identify an unknown organic acid by conducting several experiments to determine the acids unique properties. By determining various properties of the unknown acid and then comparing these to the constant properties of known substances found in the computer search, it is possible to identify an unknown organic substance. Examples of constants that can be determined in lab include: melting or boiling point, titration and calculation of equivalent weight, sodium fusion, an amide experiment, and solubility tests (GSU Chemistry Faculty 5). An organic acid is an organic compound with acidic properties that contains carbon, hydrogen, and at least one carboxyl group COOH (GSU Chemistry Faculty 83). They have a low molecular weight and are water-soluble acids that produce H+ ions in an aqueous solution (Hannan 34). They generally have simple structures and a smaller mass or molecular size (Theron and Lues 21-22). Common organic acids include: citric acid, acetic acid, glycolic acid, sulfamic acid, stearic acid, and malic acid. Acetic acid, or ethanoic acid, is used as vinegar. In the household, diluted acetic acid is most often used in descaling products, which reduce the buildup of limescale that can affect plumbing. Citric Acid is a weaker organic acid that is found in all citrus fruits. Its a natural preservative that adds a sour taste to softs drinks and food. Malic acid is another acid that is various foods, such as fruit, sour candy, and potato chips. Glycolic acid, a smaller organic acid, is used in many skin care products that improve skins texture and appearance. Sulfamic acid is a commonly used organic acid and is found in many household detergents, bleaches, and rust removers. Last, stearic acid is a higher fatty organic acid that is used to make soaps (Hannan 35-37).

II. Experiments: In the first step towards identifying the unknown organic acid, it was important that the acid was purified via recrystallization. This was done by using a solvent (deionized H2O and ethanol) to dissolve the unknown acid and then promptly cooling the solvent. The unknown organic acid recrystallizes, but the impurities stayed dissolved in the solvent. Next, the pure crystals were filtered out of the impure solvent via suction filtration. These purified crystals were used to determine the unknowns constant properties. The melting point range of the purified unknown was determined using capillary tubes and the Bibby Sterlin device. Another property that aided in the identification of the unknown was equivalent weight, the weight in grams of the acid that has precisely one mole acidic hydrogens (GSU Chemistry Faculty 38). Equivalent weight was determined through the process of titration. Before the titration of the unknown, there were numerous practice titrations to determine the molarity of HCl and NaOH by titrating KHP with NaOH and HCl with NaoH. The molarity of NaOH was an essential component of future equations used to determine equivalent weight of the unknown organic acid. Three titrations were performed using a buret filled with NaOH and an indicator (phenolphthalein). Equivalence point was reached when the solution of HCl and NaOH reached a light pink color. Three titrations of KHP were also performed using the same process above. Next, the unknown organic acid was titrated with NaOH. This allowed for the determination of equivalent weight. Once again, three titrations were performed using the indicator to aid in determining the equivalence point, or when the solution of the unknown organic acid and NaOH reached a light pink color. The volume of NaOH (in liters) used to reach this equivalence point is known as the volume

of NaOH at neutralization, and it is used in the equation for equivalent weight in addition to the weight of the unknown (about .30 grams) and the molarity of NaOH. Next, pKA titrations of the unknown organic acid were performed. These titrations were done using about .20 grams of the organic acid dissolved in three different combinations of deionized water and ethanol The combinations of solvent include: 75 mL ethanol and 25 mL deionized water, 80 mL ethanol and 20 mL deionized water, and 85 mL ethanol and 15 mL deionized water. Instead of using an indicator, a pH meter was used to determine the equivalent weight and pKa. The pH was taken at specific intervals during the titration of the unknown with NaOH. The volume of NaOH at neutralization was obtained from the graphs made on excel, as it was the volume at half the equivalence point. Last, a sodium fusion test was performed to determine if the compound contains Cl, Bri, I, or N. After filtration of the stock solution, drops of ferrous sulfate, potassium fluoride, ferric chloride, and dilute sulfuric acid were added. The substance turned blue, concluding that cyanide ions were present in the organic acid. Therefore, this confirmed that the unknown organic acid contained nitrogen.

III. Results % yield of recrystallized compound: 75.2% Melting point range of recrystallized compound: 159-162C [HCl] = .1951 .00073 M [NaOH] = .1102 .0014 M Equivalent Weight: from NaOH titration with indicator: 236.91 3.4 g/mol from pKa titration: 238.6 3.3 g/mol average equivalent weight: 237.76 g/mol

pKa = 4.17 IV. Discussion: In the recrystallization of the unknown organic acid, there was a high percent yield of 75.2 percent. There was a sufficient amount of the recrystallized purified substance obtained; therefore, it was unnecessary to repeat the process to acquire more crystals. On the third trial, the melting point determined (159-162C) appeared to be the most accurate when the computer search was performed. Errors occured on the first two trials of determining the melting point, which could possibly be attributed to mixing up the unknown organic acids that were drying in the oven. Additionally, the sample size of the unknown used in the capillary tube could have been a source of error because if it was too small, visibility could have been impaired. There seemed to be error in the equivalent weight found in both titration experiments. According to the computer search, the unknown organic acid should have had an equivalent weight of 226 g/mol. In the pKa titration, the equivalent weight was determined to be 236.91 g/mol. The pH meter was

properly calibrated; therefore, there was not an error in the readings of the pH. A very likely source of error was that the volume of NaOH was misread from the buret when determining the pH at various intervals. Additionally, the equivalent weight calculated from the titration of the unknown using the indicator phenolphthalein, 236.91 g/mol, was erred. This could also be attributed to the misreading of the volume of NaOH on the buret when taking the IBR and FBR. Moreover, the volume recorded at which the unknown organic acid reached neutralization could have been incorrect, as the shade of pink reached could have been too light or dark. The pKa of 4.17 found in the experiment was also very different from the value given in the computer search, 2.97. This could be a result of not titrating in smaller intervals. If the pH was taken more frequently, perhaps every .2 mL instead of every .5 mL, at the 5-9 pH range, the values on the graph might have been more precise at the jump, allowing for a more accurate reading of the volume of NaOH at the equivalence point. The sodium fusion test made the identity of the unknown clear because the nitrogen test proved that there were cyanide ions in the acid due to the blue color. The only organic acid containing nitrogen amongst the choices from the computer search was 4-methyl-3,5-dinitrobenzoic acid. V. Conclusion: The unknown organic acid was determined to be 4-methyl-3,5-dinitrobenzoic acid. Although, there was a great deal of error in the experiments in terms of the equivalent weight and pKa, other properties assisted in the identification of the unknown. The melting point found in the experiment was on par with that of the acids melting point on the computer search (159-160C). Therefore, based on melting point only, the most likely compound was 4-methyl-3,5-dinitrobenzoic acid. However, the equivalent

weight found from the titration experiment was approximately 11 g/mol off from the equivalent weight of this organic acid in the computer search. So, based on equivalent weight only, the most likely compound identified at that time was hydroxydiphenylacetic acid. It was necessary to complete other experiments to narrow the organic acid down to one choice. Unfortunately, the pKa titrations of the unknown organic acid yielded a pKa value that was also very different from the pKa value on the computer search. Therefore, a sodium fusion test had to be done to determine if the unknown was 4-methyl-3,5dinitrobenzoic acid, a nitrogen containing compound. As a result of the cyanide ions present, the unknown did in fact turn blue during the nitrogen test, signifying that the only possible organic acid that it could be amongst the three choices was 4-methyl-3,5dinitrobenzoic acid.

Works Cited GSU Chemistry Faculty, First. The Identification of an Organic Acid. 3rd ed. 2011. 83. Print. Hannan, Henry. Technician's Formulation Handbook for Industrial and Household Cleaning Products . Lulu.com, 2007. 33-37. <http://books.google.com/books?id=s3Ru9fvsGh4C&dq=household organic acids&source=gbs_navlinks_s>. Theron, Maria, and Jan Lues. Organic Acids and Food Preservation. illustrated. CRC Press, 2009. 21-22. Web. <http://books.google.com/books?id=7IrGwQTt1aMC&dq=what is an organic acid&source=gbs_navlinks_s>.