Chem 1224

Chemical Qualitative Analysis - Anions

Spring 2003 Page 1

Anions
This group includes CO3 2, S 2, SO3 2, SO4 2, NO2 , NO3 , PO4 3, C2O4 2, F , Cl , Br , and I . Instead of a flow chart such as you have used in Groups B E, the analysis of anions will consist of tests that first eliminate certain anions by running classification tests and then secondly, confirmation tests for the presence of individual anions. Because certain of anions have limited stability in solution, both your known and unknown samples are the sodium or potassium salts of that anion. For example, the chloride is as sodium chloride.

Classification and Elimination Tests

1 Elimination of the Volatile Anions The anions CO3 2, S 2, SO3 2 and NO2 are anions of the weak acids H2CO3, H2S, H2SO3 and HNO2 respectively. These weak acids are unstable in solution and decompose to produce the gases CO2, H2S, SO2 and NO2. If no volatile gases are produced from the acidic solution, then these 4 gases are absent. Place approximately 25 mg of the solid salt in a small test tube and treat with 2 drops of 1.5 M H2SO4. Examine the mixture for evidence of the evolution of gases. If no gases are observed to be formed, carefully heat the mixture in the hot water bath. If no gases are evolved, then CO3 2, S 2, SO3 2 and NO2 ions are absent. If a gas is evolved, note its odor and color. CO2 (carbon dioxide) is colorless and odorless H2S (hydrogen sulfide) is colorless and smells like rotten eggs SO2 (sulfur dioxide) is colorless and smells like burning sulfur, and NO2 (nitrogen dioxide) has a reddish-brown color and a characteristic odor. 2 Preparation of Sample for additional analysis If your tests are for only the anions, you can ignore this step because for all these anions the sodium and potassium salts are soluble in water. If this is a general unknown (Number G-xx) you may need to remove the heavy metal cation before continuing. This is done by adding Na2CO3 which forms the insoluble carbonate with all of the heavy metals. Place ~ 100 mg of the unknown in a small test tube and add 30 drops of 1.5 M Na2CO3 solution. Heat the mixture for 10 minutes in the hot water bath. Carefully smell the vapors above the heated test tube; if the odor of ammonia is detected, heat until no smell is evident. Separate any precipitate that forms and retain the solution for the subsequent tests; it will be referred to as the prepared solution in subsequent steps. 3 Elimination of the Oxidizing Anions - The second classification tests depends on the ability of the NO2 and NO3 ions to oxidize Mn+2 to Mn+3. Place 4 drops of the prepared solution in a small test tube and add 6 drops of the saturated solution of MnCl2 in 12 M HCl. Carefully heat the mixture to boiling. The formation of a dark brown or black color of the manganese(III) chloride complex (MnCl4 ) indicates the presence of either NO2 and NO3 .

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Chemical Qualitative Analysis - Anions

Spring 2003 Page 2

4 Elimination of Reducing Anions This test depends on the ability of S 2, SO3 2, NO2 , and I to reduce the iron (III) in K3Fe(CN)6 to iron (II); this is shown by the formation of a blue color. Prepare a test solution by mixing together 2 drops of freshly prepared saturated solution of K3Fe(CN)6 with 1 drop of FeCl3 and 2 drops of 6 M HCl. Add 2 drops of the prepared solution from step 2 and let the mixture set for a few minutes. The development of a blue color or the formation of a blue precipitate indicates the presence of a reducing agent (S 2, SO3 2, NO2 , or I ). Run a blank by observing a mixture of the reagents which has not had the sample solution added. 5 - Elimination of Fluoride and Oxalate - C2O4 2 and F form calcium salts that are not soluble in 4 M acetic acid. Place 20 drops of the prepared solution from step 2 into a small test tube and add 4 M HC2H3O2 dropwise (noting the number of drops) until the solution is just acid to litmus. Add additional acetic acid equal to the number of drops originally added. Stir the contents of the test tube until all carbon dioxide has been expelled. Add 8 drops of 0.1 M CaCl2 and stir the contents of the test tube. Allow the test tube to set for a few minutes. The formation of a white precipitate suggests the presence of C2O4 2 or F . Separate the precipitate and retain the solution for the test for sulfate. Retain the precipitate for confirmatory tests for C2O4 2 and F. 6 - Elimination of Sulfate - To the solution from step 5, add 1 drop of 0.1 M CaCl2 to assure complete precipitation. Next add 8 drops of 0.1 M BaCl2. Stir the mixture well and allow it to stand for approximately 5 minutes. If sulfate (SO4 2 ) is present, a white precipitate of BaSO4 will form. Separate the mixture and retain the solution for the following test for the phosphate ion. If sulfite (SO3 2 ) is present in the original solution, you may obtain a positive test because sulfite is oxidized by the oxygen in the air to sulfate. 7 - Elimination of Phosphate Transfer the solution from step 6 to your evaporating dish, add 6 drops of 12 M HCl and carefully heat on the hot plate to release CO2 and SO2. Remove the evaporating dish from the hot plate and allow it to cool. Use 6 M ammonia to make the solution basic to litmus paper, and then add 5 drops in excess. The formation of a with precipitate of Ba3(PO4)2 indicates the presence of phosphate. 8 - Elimination of Sulfide - Prepare lead acetate paper by wetting a strip of filter paper with lead acetate solution. Place the prepared damp lead acetate paper on the bottom side of a small watch glass. Place 8 drops of the prepared solution in a small beaker and add 1.5 M sulfuric acid drop-wise to make the solution acidic to litmus paper. Use the watch glass with the lead acetate paper to cover the beaker. A darkening of the lead acetate paper indicates the presence of the sulfide (S 2) ion.

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Chemical Qualitative Analysis - Anions

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9 - Elimination of Chloride, Bromide and and Iodide If the sulfide ion was found in the above step, treat 10 drops of the prepared solution with 4 M acetic acid until the solution is acidic to litmus paper. Add 10 drops of 0.1 M AgNO3 . Separate the precipitate. Wash the precipitate with 10 drops of water. Discard the solution. Add 10 drops of 0.1 M AgNO3 , 4 drops of 4 M ammonia and 4 mL of deionized water to the precipitate. Stir this mixture well. If the precipitate dissolves completely, Br and I are absent and the presence of Cl is indicated. Acidify the solution with 4 M HNO3. The reformation of a white precipitate confirms chloride.

Confirmatory Tests for the Anions

10 Confirmatory Test for Carbonate Add 25 mg (portion ca. size of capital O) of the original unknown to a small test tube. Add 10 drops of hydrogen peroxide and heat the mixture in the hot water bath. Suspend a drop of Ba(OH)2 in the loop of your Nichrome test wire. Add 3 drops of 4 M H2SO4 to the test tube and then hold the loop with the barium hydroxide over the reaction mixture in the test tube. The formation of turbidity in the drop of Ba(OH)2 confirms the presence of the carbonate ion. Chemical equations for the confirmatory step CO3 2 + 2 H+ H2O + CO2 (g) CO2 (g) + Ba(OH)2 (aq) BaCO3 (s) 11 Confirmatory Test for Sulfate Transfer 5 drops of the prepared solution from step 2 to a small test tube. Make acidic to litmus paper with 6 M HCl and add 2 drops in excess. Heat the mixture in a hot water bath for 2 or 3 minutes. Add 0.1 M BaCl2 until precipitation is complete. The formation of a finely divided white precipitate confirms the presence of the sulfate ion. Separate the mixture and retain the solution for the test for the sulfite ion. Chemical equations for the confirmatory step SO4 2 (aq) + Ba(OH)2 (aq) BaSO4 (s) 12 Confirmatory Test for Sulfite To the solution from the proceeding step, add 5 drops of bromine water and 2 drops of 0.1 M BaCl2. Heat the mixture in the hot water bath and allow to set for 5 minutes. The formation of a finely divided white precipitate confirms the presence of the sulfate ion. Chemical equations for the confirmatory step SO3 2 (aq) + Br2(aq) SO4 2 (aq) SO4 2 (aq) + Ba(OH)2 (aq) BaSO4 (s) 13 Confirmatory Test for Sulfide The confirmatory test for sulfide was done in the elimination test, step 8 earlier. Chemical equations for the confirmatory step H2S (g) + Pb+2(aq) PbS (s)

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Chemical Qualitative Analysis - Anions

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14 Confirmatory Test for Oxalate Wash the precipitate from the classification tests in step 5 twice, using 10 drops of deionized water for each washing. Discard the washings. Add 10 drops of deionized water and 10 drops of 4 M sulfuric acid and stir the mixture. Add 0.002 M KMnO4 drop-wise until a faint pink color occurs in the solution. If oxalate is present, several drops of potassium permanganate will be required. (Note: in the absence of oxalate, the solution will be purple colored, the color of the permanganate.) Chemical equations for the confirmatory step 5 C2O4 2 (aq) + 2 MnO4 (aq) + 8 H+ (aq) 10 CO2 (g) + 2 Mn+2(aq) + 4 H2O 15 Confirmatory Test for Phosphate Transfer 4 drops of the prepared solution from step 2 to a small test tube. Add 10 drops of deionized water. Make the solution acidic with 4 M HNO3 and add 10 drops of the magnesia mixture. Allow the mixture to set. The formation of a white precipitate confirms the presence of the phosphate ion. Chemical equations for the confirmatory step Mg+2 (aq) + NH4+(aq) + HPO4 2(aq) MgNH4PO4 (s) + H+(aq) 16 Confirmatory Test for Iodide Transfer 6 drops of the prepared solution to a small test tube and add 12 drops of deionized water. Make the solution acidic to litmus with 4 M HNO3 and then add 2 additional drops. Treat the solution with 20 drops of 0.1 M Fe(NO3)3 and 10 drops of methylene chloride (CH2Cl2) and shake the test tube. The development of a violet color in the organic layer confirms the presence of the iodide ion. Extract the solution with portions of methylene chloride until the organic layer is colorless and then remove the aqueous layer for the test for bromide. Chemical equations for the confirmatory step 2 I (aq) + 2 Fe+3(aq) I2 (org) + 2 Fe+2(aq) 17 Confirmatory Test for Bromide Transfer the aqueous solution from the proceeding step to a small test tube and add 2 drops of 4 M HNO3 and 0.1 M KMnO4 until the solution remains pink. Treat the solution with 10 drops of methylene chloride (CH2Cl2) and shake the test tube. The development of a yellow or orange color in the organic layer confirms the presence of the bromide ion. Chemical equations for the confirmatory step 10 Br (aq) + 2 MnO4 (aq) + 16 H+(aq) 5 Br2 (org) + 2 Mn+2(aq) + 8 H2O 18 Confirmatory Test for Chloride The confirmatory test for chloride was done in the classification test for chloride, bromide and iodide, step 9. Chemical equations for the confirmatory step Cl (aq) + Ag+(aq) AgCl(s) AgCl(s) + 2 NH3 (aq) [Ag(NH3)2]+ (aq) + Cl (aq) [Ag(NH3)2]+ (aq) + Cl (aq) + 2 H+ AgCl(s) + 2 NH4+ (aq)

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Chemical Qualitative Analysis - Anions

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19 Confirmatory Test for Nitrite Prepare a test reagent of iron (II) in a small test tube by dissolving a small amount of FeSO4 in deionized water. Add 5 drops of the prepared solution from step 2. Carefully add 4 M H2SO4 to the mixture until the solution is acidic. The formation of a dark brown colored complex confirms the presence of NO2 . Nitrogen dioxide gas may also be evolved from the solution. Chemical equations for the confirmatory step NO2 (aq) + Fe+2(aq) + 2 H+(aq) Fe+3(aq) + NO + 8 H2O NO (aq) + Fe+2(aq) Fe(NO)+2 (aq) 2 NO (g) + O2 (g) 2 NO2 (g) 20 Confirmatory Test for Nitrate What confirmatory test is done for nitrate depends on what else you have found out about your sample. a) Confirmatory test for Nitrate in the absence of nitrite, bromide, and iodide. Add 5 drops of the prepared solution from step 2 to a small test tube. Carefully add 4 M H2SO4 to the mixture until the solution is acidic. Prepare a test reagent of iron (II) in a small test tube by dissolving a small amount of FeSO4 in deionized water as done in step 18 above. Carefully add 5 drops of concentrated H2SO4 to the test tube held at a 30 45o angle, allowing the sulfuric acid to run down the inside of the test tube and form a separate layer at the bottom of the test tube. If nitrate is present, a brown ring will form at the interface between the two layers. The major differences between the nitrate and nitrite ions are 1) the nitrite ion would be found in the first classification test for ions forming volatile gases (step 1), and 2) the nitrite ion is among the reducing ions (step 4). Furthermore is the spontaneous production of nitrogen dioxide by the nitrite ion. Chemical equations for the confirmatory step NO2 (aq) + Fe+2(aq) + 2 H+(aq) Fe+3(aq) + NO + 8 H2O NO (aq) + Fe+2(aq) Fe(NO)+2 (aq) b) Confirmatory test for Nitrate in the presence of the Nitrite ion. If the nitrite ion was indicated by the steps mentioned above, it must be removed before doing this test. Transfer 5 drops of the prepared solution from step 2 to an evaporating dish. Add 4 M H2SO4 until the solution is acidic to litmus paper and then add 4 drops of 1 M (NH4)2SO4. Heat slowly on the hot plate until a moist reside remains; do not heat to dryness. Add 4 drops of deionized water and again evaporate to a moist residue. Dissolve the residue in 6 drops of deionized water and transfer to a small test tube. Repeat the procedure shown in the second paragraph of 19a above. c) Confirmatory test for Nitrate in the presence of bromide and/or iodide ions. Transfer 5 drops of the prepared solution from step 2 to a small test tube. Add 10 drops of water.

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Use 4 M acetic acid to acidify to litmus paper. Add about 80 mg of powdered nitrate-free Ag2SO4. Use your glass stirring rod to grind the mixture of solid silver sulfate with the solution for anount 3 minutes. Separate the mixture and transfer the solution to a clean small test tube. Repeat the procedure shown in the second paragraph of 19a above. References 1. "Qualitative Analysis and Chemical Equilibrium, 4th edition", pages 497 - 537, T.R. Hogness and W.C. Johnson, publisher Holt, Rinehart, and Winston, Inc, 1954. 2. "College Chemistry with Qualitative Analysis, 4th edition", pages 962 - 975, W. H. Nebergall, F. C. Schmidt, and H.F.Holtzclaw, publisher D.C.Health and Company, 1972. 3. " Chemistry: Principles and Reactions, 4th edition", pages 460 - 476, W. L. Masterton and C. N. Hurley, Harcourt College Publisher, 2001. Reagents Sulfuric acid, 1.5 M H2SO4 Sodium carbonate, 1.5 M Na2CO3 Manganese(II) chloride, MnCl2 saturated solution in 12 M HCl Potassium hexacyanoferrate(III), K3Fe(CN)6 Ferric chloride, 1.0 M FeCl3 Hydrochloric acid, 6 M HCl Acetic acid, 4 M HC2H3O2 Calcium chloride, 0.1 M CaCl2 Barium chloride, 0.1 M BaCl2 Hydrochloric acid, 12 M HCl Ammonia, 6 M NH3 Thin strips of filter paper Lead acetate, 0.1 M Pb(C2H3O2)2 Sulfuric acid, 1.5 M H2SO4 Silver nitrate, 0.1 M AgNO3 Ammonia, 4 M NH3 Nitric acid, 4 M HNO3 Hydrogen peroxide, 3% H2O2 Barium hydroxide, 0.1 M Ba(OH)2 Nichrome test wire Sulfuric acid, 4 M H2SO4 Hydrochloric acid, 6 M HCl Barium chloride, 0.1 M BaCl2 Bromine water, Br2(aq) Sulfuric acid, 4 M H2SO4

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Chemical Qualitative Analysis - Anions

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Potassium permanganate, 0.002 M KMnO4 Nitric acid, 4 M HNO3 Magnesia mixture Iron(III) nitrate, 0.1 M Fe(NO3)3 Methylene chloride, CH2Cl2 Potassium permanganate, 0.1 M KMnO4 Iron(II) sulfate, FeSO4 solid Sulfuric acid, concentrated H2SO4 Ammonium sulfate, 1 M (NH4)2SO4 Silver sulfate, Ag2SO4 solid

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Name _________________________ Unknown Number __________ Ion(s) found _______ _______ _______ Description of Reactions that confirmed the above identifications: ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________ ______________________________________________________________________