Cation Qualitative Analysis

Introduction
Qualitative analysis of inorganic ions (cations) is a systematic "wet method" that proceeds by separating the ions into groups by selective precipitation reactions, isolating individual ions in the groups by an additional precipitation reaction, and confirming the identity of the ion by a test reaction that gives a specific precipitate or color.

You are strongly encouraged to read the following sections from Chemistry, 2/e or 3/e by McMurry and Fay: 16.13 Precipitation of Ionic Compounds 16.14 Separation of Ions by Selective Precipitation 16.15 Qualitative Analysis

In this experiment you will study the following cations: GROUP I: GROUP II: Ag+, Pb2+ Cu2+, Bi3+

GROUP III: Fe3+, Ni2+ GROUP IV: Ba2+, Ca2+

Flowcharts are used like road maps to provide a visual guide to the sequence of steps that are required to separate and identify individual cations. On the following page is an overall flowchart that highlights the separation of cations into their particular groups. Individual group flowcharts can be found at the beginning of each group section. They trace the necesssary steps for both cation separation and identification within each group.

Qualitative Analysis: Cations Test Solution Ag+, Pb2+, Cu2+, Bi3+, Fe3+, Ni2+, Ba2+, Ca2+ 6 M HCl

GROUP I AgCl(s), PbCl2(s)

(See GROUP I Flowchart)

, Cu2+, Bi 3+ Fe3+, Ni2+, Ba2+, Ca2+

6 M HCl (pH < 1) 1 M CH3CSNH2

GROUP II CuS(s), Bi2S3(s)

(See GROUP II Flowchart)

Fe3+, Ni2+, Ba2+, Ca2+

6 M HCl NH4+/NH3 Buffer (pH = 9) 1 M CH3CSNH2

GROUP III FeS(s), Fe2S3(s), NiS(s)

(See GROUP III Flowchart)

Ba2+, Ca2+

2 M (NH4)2CO3

GROUP I V BaCO3(s), CaCO3(s)

(See GROUP IV Flowchart)

GROUP V Soluble Cations

GROUP I Flowchart

GROUP I AgCl(s), PbCl2(s) Hot Water, Filter

AgCl(s)

Pb2+

6 M NH3 Ag(NH3)2+

6 M CH3COOH 0.1 M K2CrO4

6 M HNO3

PbCrO4(s) yellow

AgCl(s) white

Cation Qualitative Analysis

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Experimental Procedure
1. 2. 3. 4. 5. Prepare a Known solution containing 1 mL each of the eight cation solutions. You will receive an Unknown solution containing any possible combination of the eight cations. You should test your Known and Unknown solutions separately but simultaneously. You will be graded based on the number of cations that you correctly identify in your Unknown solution. There will be a 10 point grade penalty if, for any reason, you need a new Unknown solution to finish this experiment.

PART I: Cation Group I Separation of Cation Group I 1. Place 3 mL of the test solution into an empty and clean small test tube. Cool the solution in an ice-water bath for approximately 5 minutes. 2. Add 6 M HCl dropwise, with stirring, until precipitation is complete. Keep the solution cool. 3. Centrifuge this solution. 4. Test for completeness of precipitation by adding 1 extra drop of 6 M HCl. If no additional precipitate forms, go to step 5. If a precipitate forms, repeat steps 2 - 4 until precipitation is complete. (Note: Avoid adding a large excess of HCl, because the soluble [AgCl2]S complex forms and a portion of the desired AgCl precipitate dissolves.) 5. Decant the supernatant solution. Label and save the solution for Cation Group II analysis (step 19). 6. Wash the precipitate with 1 mL of cold deionized water. Add the washing to the solution from step 5. 7. Save the white precipitate for Group I analysis in the next step. Cation Group I Analysis Separation of the Ag+ and Pb2+ Cations 8. To the white precipitate, add 2 mL of deionized water. 9. With stirring, heat the test tube and its contents in a boiling water bath for approximately 5 minutes. 10. Rapidly filter the hot solution into an empty and clean small test tube. Save the solution to test for Pb2+ (step 17). 11. Place the funnel in a large test tube and wash the residue in the funnel with two 5 mL portions of boiling deionized water. Discard the washings. 12. Save the residue on the filter paper in the funnel to test for Ag+ in the next step.

Cation Qualitative Analysis

_____________________________________________________________________________ Confirmation of the Ag+ Cation 13. Place the funnel containing the white residue in an empty and clean small test tube. 14. Add, with gentle agitation, 2 mL of 6 M NH3 to dissolve some of the white residue in the funnel. 15. Remove the funnel from the test tube. Add 6 M HNO3 dropwise, with stirring, to the colorless filtrate in the test tube until the solution is acidic. Test with litmus paper. 16. Record your observations. The formation of a white precipitate of silver chloride (AgCl) from the colorless filtrate indicates the presence of the silver cation (Ag+).

Confirmation of the Pb2+ Cation 17. To the solution saved from step 10, add 2 drops of 6 M CH3COOH and then 4 drops of 0.1 M K2CrO4. Thoroughly stir the solution. 18. Record your observations. The formation of a yellow precipitate of PbCrO4 indicates the presence of the lead(II) cation (Pb2+).

Cation Qualitative Analysis Group I Name_____________________ CHEM 102L Section _____ Date ________

Unknown # _____ Cation Report:

+

Ag Pb

(circle one) Present Absent Present Absent

(15 pts) (15 pts)

2+

GRADE

80

65

50