Experiment 6: Elemental Analysis Nuez, Noemi Angela D. Solis, Christian Marie Araceli P.

Abstract

AB2, Group 6, Mr. Kevin Sison May 4, 2010

Identification and classification of a compound can be achieved through quantitative and qualitative analyses. However, in the experiment, only qualitative elemental analysis was used on the compounds to be tested, which were p-chloroaniline and thioacetamide. Before such analysis could be done, the compounds were fused with sodium through intense heating. The fused compound was then mixed in water, allowing the excess sodium to react. The solution was boiled and filtrated, resulting to a colorless solution. This solution was tested for sulfur, nitrogen and, halogens by mixing certain compounds. The reaction of these compounds resulted to defined changes in color and formation of precipitates which determined the elements present. After the tests had been conducted, it was concluded that p-chloroaniline had the elements nitrogen and chlorine, while thioacetamide had the elements sulfur and nitrogen. Keywords: sodium fusion, qualitative analysis, compounds Introduction In order to characterize and classify unknown organic compounds, analyses of elements other than carbon, hydrogen, and oxygen are essential. These elements include nitrogen, sulfur, and the halogens (chlorine, bromine, and iodine), which are covalently bonded to the organic compounds. In order to detect their presence, they have to be converted into their ionic forms. One of the ways in which this can be carried out is by the sodium fusion experiment. This process involves the fusion of an unknown organic compound with sodium at high temperature. They will then be converted into water-soluble inorganic sodium salts sodium cyanide (NaCN), sodium sulfur (Na2S) and sodium halides (NaX, where X=Cl, Br, and I). These ionic compounds are extracted in aqueous solution and can be detected by qualitative analysis. The alkaline aqueous solution obtained is called sodium extract or Lassaigne's extract. Experimental A. Sodium Fusion Prior to heating procedures, 0.3 g pchloroaniline, 10 mL cold distilled water in 50 mL beaker, and wire gauze were prepared for convenience and better results. A small piece of sodium was placed in a small and dry 5 mL test tube and heated over a Bunsen burner until sodium vapor was observed to condense on the walls of the tube. The pcholoroaniline was added and the tube was hovered back into the flame. After a while, the bottom of the test tube was heated to redness for about 3 minutes. It was then dropped into the beaker containing cold distilled water which was Chem 31.1, Experimental Analysis also covered with wire gauze. As the test tube shattered, unreacted sodium was released and allowed to react before the solution on the beaker was boiled for two minutes. It was then filtered and the filtrate was kept for the succeeding qualitative tests. The abovementioned procedures were also done with thioacetamide as replacement for pchloroaniline. B. Qualitative Tests B.1. Sulfur Test Five (5) drops of fusion solution and 3 drops of water were combined in a 5 mL test tube. Two (2) drops of 2% aqueous sodium nitroprusside solution was then added. The formation of a deep blue-violet color was observed. B.2. Nitrogen Test A pinch of FeSO4 was added to 1 mL of fusion solution in a test tube. Five (5) drops of 10% KF was also added before the mixture was boiled for 5 seconds and was added with 2 drops of 5% ferric chloride solution. A sufficient amount of 6 M H2SO4 was then dropped to dissolve insoluble iron hydroxides and make the solution acid to litmus. Deep blue precipitate indicated the presence of nitrogen. If it had been inconspicuous, the mixture was filtered and the filter paper was washed with distilled H2O to see blue coloration in the residue. B.3. Halogen Test Ten (10) drops of fusion solution was placed into a small test tube. If it had been positive for nitrogen or sulfur, the solution was acidified by adding 2 M HNO3. It was then boiled gently for 1 minute (to remove possible HCN or H2S) and Page 1 of 3

cooled to room temperature. Four (4) drops of 0.1 M AgNO3 was then added. A heavy curdy-type precipitate indicated presence of halogens white, AgCl; pale yellow, AgBr; and yellow, AgI while a faint turbidity was a negative test. To further differentiate AgBr from AgI, 0.5 mL of 2 M NH4OH was added to the precipitate and stirred to determine solubility of the solid. AgI is insoluble in the solution while AgBr is slightly soluble. A preliminary test (Beilstein test) for halogen was also available. A 3mm diameter-loop was made on one end of a six (6) inch-copper wire while the other end was inserted into a cork to serve as a holder. The coiled part was then heated on a Bunsen burner until it imparted no color to the flame. As the wire cooled, it was dipped into a small portion of the original sample. The sample was then heated and a green color indicated the presence of halogen. Results A. Sodium Fusion The resulting solution was a colorless liquid with insoluble black particles that were eventually removed through filtration. B. Qualitative Tests
Table 1: Results of Qualitative Tests

sodium, resulting to an inorganic salt such as NaCNS, Na2S, NaCN or NaX. Accordingly, the fusion of p-chloroaniline with sodium formed sodium chloride and sodium cyanide, while the fusion of thioacetamide with sodium formed sodium thiocyanate. However, in the presence of excess sodium, sodium thiocyanate formed sodium sulfide and sodium cyanide. When the fusion solution of pchloroaniline was tested with sulfur by putting 2% sodium nitroprusside, it turned yellow. There was no sulfur present. It is only thioacetamide that turned to a deep blue-violet color, which indicated the presence of sulfur. The deep blue- violet color was caused by Na4[Fe(CN)5NOS]. The reaction is illustrated in the following formula: Na2S+Na2Fe(CN)5NO->Na4[Fe(CN)5NOS] The second test was the nitrogen test or Prussian blue test. Both compounds were positive for the presence of nitrogen because of the formation of a deep blue precipitate. Ferrous sulfate reacted with sodium cyanide forming sodium ferrocyanide, Na4[Fe(CN)6]. Potassium fluoride was added to intensify the deep blue color that was to be formed. When the solution was boiled, some of the ferrous salt oxidized to ferric salt and this reacted with the sodium ferrocyanide to form ferric ferrocyanide or Fe4 [Fe(CN)6]3. Ferric ferrocyanide caused the deep blue color. The formation of this precipitate is illustrated in the following formula: 6NaCN + FeSO4 -> Na4[Fe(CN)6] + Na2SO4
3Na4[Fe(CN)6]+2Fe2(SO4)3 -> Fe4[Fe(CN)6]3 + 6Na2SO4

Compounds P-chloroaniline Thioacetamide

Sulfur test +

Nitrogen test + +

Halogen test + -

P-chloroaniline fusion solution didnt turn deep blue-violet when placed in a sulfur test. Therefore, there was no sulfur present. It instead was positive for the presence of nitrogen and chlorine, since the solution formed a deep blue precipitate when placed in nitrogen test and a white precipitate when placed in halogen test. Thioacetamide fusion solution had both the presence of sulfur and nitrogen since the solution turned to a deep blue-violet color and formed a deep blue precipitate when placed in sulfur test and nitrogen test, respectively. There were no halogens present in the solution because a faint turbidity was produced rather than precipitate when placed in halogen test. Discussion Sodium fusion involves the strong heating of a sample with sodium metal. Sulfur, nitrogen or halogens present in the sample will fuse with Chem 31.1, Experimental Analysis

The final test was the halogen test. Beilsteins test and silver nitrate test are two ways to test a compound for the presence of halogens. The Beilsteins test is an extremely sensitive test because minute traces of impurities containing halogen and certain nitrogen compounds without halogen may produce a green flame. That is why the Beilsteins test should always be cross-checked by the silver nitrate test. In the silver nitrate test, nitric acid, HNO3, reacts with cyanide or sulfide that could be present in the filtrate. It results to the formation of hydrogen cyanide or hydrogen sulfide, and sodium nitrate. Boiling the sodium fusion filtrate is important in order to expel hydrogen cyanide or hydrogen sulfide that was formed. Between the tested compounds, p-chloroaniline had a presence of halogens, specifically chlorine. The formation of white precipitate indicated the presence of chlorine. The formation of the precipitate is illustrated in the following formula: Page 2 of 3

NaCl + AgNO3 -> AgCl (s) + NaNO3 A solubility test of halogens in ammonium hydroxide can be used to determine the difference between the halogens chlorine, bromine and iodine. Silver chloride is soluble in the mentioned solvent due to the formation of Ag(NH3)2Cl. Silver bromide is only slightly soluble because it partially forms salt, and silver iodide is insoluble because it does not undergo any reaction with the ammonium hydroxide. Guide Questions and Answers 1. Outline the procedures for detecting the presence of oxygen and phosphorus in organic compounds. For Phosphorus: a. The organic compound is fused with sodium peroxide. b. The fused mass is then extracted with water. The aqueous solution obtained is boiled with concentrated nitric acid, and ammonium molybdate is added to it. c. A yellow solution or precipitate indicates the presence of phosphorus. The yellow precipitate is of ammonium phosphomolybdate (NH4)3[PMO12O40]. For Oxygen: There is no direct method for detection of oxygen in organic compounds, but its presence is detected indirectly. For example: y If an organic compound gives out water vapor upon heating, there might be oxygen in it. If the organic compound is found to contain y any oxygen-containing functional group such as OH, -CHO, -COOH, -NO2, etc., it also contains oxygen. If the sum of the percentages of the y elements in the compound is less than a hundred, then it may also contain oxygen. 2. Discuss other methods of detecting the presence of sulphur, nitrogen and halogen in organic compounds. Another method by which we could detect the presence of sulfur, nitrogen and halogen in organic compounds is through the Schoniger oxidation method, but it is much more sensitive to explosions so it is not always used. The test is conducted in an Erlenmeyer flask or in a separatory funnel. The sample will be combusted with pure oxygen. Afterwards, the combustion products will be absorbed by a solution of sodium hydroxide. The Chem 31.1, Experimental Analysis

determination of chlorine, nitrogen and sulfur is through a quantitative method. Another method to detect the presence of sulfur is the Lead acetate test. The fusion solution will be acidified with acetic acid. Then lead sulfide will be added to it. The formation of a black precipitate, lead sulfide, indicates the presence of sulfur. Conclusion and Recommendations Qualitative elemental analysis is useful in determining certain elements that are present in an organic compound. Through sodium fusion, the element to be detected combines with sodium metal to form an inorganic salt. Different compounds will react with this salt, resulting to changes in color and formation of precipitates. This kind of analysis doesnt apply to all elements. In the sodium fusion test, it is very important that the test tube used to add the sodium metal is dry because it (sodium) is potentially explosive in water depending on quantity. Sodium residues are also neutralized by adding large volumes of ethyl alcohol. If in case a fire started, it should not be hurled with water for it would only get worse; it should instead be treated with special fire extinguishers containing Pyromet, a NaCl/(NH4)2HPO4 mix. Proper attire (including goggles and gloves) is also very much necessary. For the succeeding tests, it is recommended that a clean dropper be used for the different reagents to ensure accurate results and avoid contaminating the solutions. References Shriner, R.L., Curtin, D.Y., Fuson, R.C., Hermann, C.K.F., & Morill, T.C. (1998). The Systematic Identification of Organic th Compounds (7 Ed). New York: John Wiley & Sons, Inc. Tutor Vista. (2010). Qualitative Analysis. Retrived on May 3, 2010, from http://www.tutorvista. com/content/chemistry/chemistry-iii/organic -compounds/qualitativeanalysis.php I hereby certify that I have given substantial contribution to this report. _______________ Noemi Angela D. Nuez ______________________ Christian Marie Araceli P. Solis Page 3 of 3