Experiment 2: Qualitative Analysis of Metal Cations
INTRODUCTION You have performed a separation of a mixture earlier. Do you remember? You have separated a heterogeneous mixture of sand, calcium carbonate, and sodium chloride. You have used both physical and chemical properties of compounds to separate the mixture. In this experiment, you used only chemical changes, called reactions, to separate three cations in an aqueous homogeneous mixture, called a solution. It is the technique used in water analyses of various metal ion content. As it is your first time, lets use non-toxic metal ion mixture of three cations: aluminum ion, iron(III) ion, and nickel(II) ion. The first step in the analysis involves treating the solution with sodium hydroxide. When sodium hydroxide is added to the solution, white precipitate forms if the solution contains aluminum ion, green precipitate forms if nickel(II) ion presents, and red precipitate forms if iron(III) ion present. However, it is very difficult to separate a mixture of different colored solid, as it is hard to separate sugar from salt, or baking soda from flour. And if all three colored precipitate present as a suspension in the solution (heterogeneous mixture), the precipitate looks greenish, redish brown. How do you separate them??? When you add excess sodium hydroxide to aluminum hydroxide, the precipitate disappears (dissolves) because of a formation of a hydroxo-complex ion, Al(OH)4-: Al3+ (aq) + 4 OH- (aq) Al(OH)4- (aq)
2+ 3+ 3+
[Equation 1]
The Ni and Fe ions, unlike Al do not readily form hydroxo-complexes. Therefore, it is easy to separate aluminum from the other two ions. In order to confirm the presentence of aluminum ion in the solution, you can just test by treating the solution with aqueous ammonia. If only aluminum ion present in the solution, a white gelatinous precipitate of aluminum hydroxide forms back. Al3+ (aq) + 3 NH3 (aq) + 3 H2O (l) Al(OH)3 (s) + 3 NH4+ (aq) [Equation 2]
Because of the low concentration of OH- in dilute NH3, Al(OH)4- complex ion by equation 1 does not form. After you separate aluminum ions from the other two cations, you need to separate nickel from iron. The mixed precipitate of nickel(II) hydroxide and iron(III) hydroxide is dissolved by adding a strong acid, for example, nitric acid. Acid-base reaction results to separate hydroxide ions and form water; as a result, nickel and iron ions go back to the solution as a suspension. At this point, the Ni2+ and Fe3+ ions can be separated by adding ammonia. The Ni2+ ion is converted to the deep-blue hyrdoxo-complex ion, Ni(NH3)62+, which stays in solution: Ni2+ (aq) + 6 NH3 (aq) Ni(NH3)62+ (aq) [Equation 3]
while the Fe3+ ion, which does not readily form a hydroxo-complex with ammonia, re-precipitate as iron(III) hydroxide. Fe3+ (aq) + 3 NH3 (aq) + 3 H2O (l) Fe(OH)3 (s) + 3 NH4+ (aq) [Equation 4]
The confirmatory test for nickel in the solution is made by adding an organic reagent, dimethylglyoxime (DMG), C4H8N2O2. The reaction between nickel ion and DMG gives a deep rose-colored precipitate, Ni(C4H8N2O2) with nickel: Ni2+ (aq) + 2 DMG (aq) Ni(DMG)2 (s) + 2 H+ (aq) [Equation 5]
In this experiment, you will separate three metal cations, aluminum, nickel(II), and iron(III) ions in a solution. Then, you will analyze your own unknown solution to determine which ions present in the solution. Keep in mind that you do not have to measure the volume that you need for this experiment. It is qualitative analysis. THEORY: Complete the following flow chart for the separation of three cations: Al3+, Fe3+, and Ni2+ in a solution based on the procedures (next page).
Solution: Al , Fe , Ni Add Precipitate formula Add
3+ 3+ 2+
Ion Al
3+ 3+
Fe Ni
2+
Solution Ion formula Ion
Precipitate formula
Add Add Precipitate formula Solution Ion formula Ion Precipitate formula Add
Ion
PROCEDURE 1. Take 1 mL of solution which contains all three metal ions (0.1 M each ion) into a medium test tube (#1). 2. Add 1 mL of 6 M sodium hydroxide. Swirl gently. Observe what happens. CAUTION! 6 M sodium hydroxide solution must be handled with care! If you spill on your skin, rinse under running water for at least 5 minutes. Follow the first aid. 3. Add another 1 mL of 6 M sodium hydroxide. Swirl gently. Observe. 4. Leave the test tube in the test tube rack. Wait until precipitate settles down at the bottom of the test tube. 5. Slowly transfer the solution to another test tube (#2). Hint: Think about the way that you transfer only the solution, not the precipitates. 6. Slowly (drop-by-drop) add 6 M HCl to acidify the mixture. You need ~ 2mL. Swirl and test the acidity of the solution using litmus paper. 7. Add 6 M NH3 to test tube #2 drop by drop. Observe. 8. If catechol violet reagent is available, add a few drops and you will observe the color change of the solution (it will turn blue) to confirm the existence of aluminum. 9. Returning to the precipitate left in test tube #1, add HCl to dissolve the solid. If necessary, warm the test tube in the water bath to complete the solution process. 10. Add 6 M NH3 until the solution is basic to litmus paper. Observe. 11. Add 1 mL more of the NH3, and gently swirl to bring the nickel into solution as Ni(NH3)62+ complex ion. 12. Leave the test tube in a test tube rack until much solid settles down to the bottom of the test tube. 13. Slowly and carefully pour the solution to another test tube (#3). The solution may be blue if nickel ion present. To confirm the presence of nickel ion in solution, add few drops of dimethylglyoxime (DMG) reagent. Observe. 14. Obtain an unknown solution. 15. Repeat the steps 1-12 and determine which metal cations exist in your unknown solution. 16. Discard all solutions into the waste container and clean your work area. NOTE: When you observe, compare with a control test tube. A control to compare solutions is often just water!
DATA 1. Mixture of all three ions (known mixture) Observation Addition of 1 mL NaOH to test tube #1 Addition of 2 mL NaOH to test tube #1 Addition of NH3 to test tube #2 Addition of NH3 to test tube #1 Addition of DMG to test tube #3 Analysis
2. Unknown mixture Observation Addition of 1 mL NaOH to test tube #1 Addition of 2 mL NaOH to test tube #1 Addition of NH3 to test tube #2 Addition of NH3 to test tube #1 Addition of DMG to test tube #3 Analysis
3. Determination of metal cation present in your unknown Write the cation(s) that present in your unknown solution
Pre-Laboratory Assignment I. II. Complete a flow chart in the page 2 by following the experimental procedure. Copy the flow chart in your lab notebook. Write answers in a separate sheet of paper and submit at the beginning of the class. You dont have to copy questions. 1. Write net ionic equations for the initial precipitation of three ions with sodium hydroxide in this experiment. Answer is NOT in this manual. If you dont remember how to write the equations, you need to consult your textbook. a) Aluminum ion b) Nickel ion c) Iron ion 2. Name the mixture which contains a solution with aluminum and precipitates of nickel and iron. 3. Name the general separation method to separate the mixture of solution and precipitate in question #2. 4. Write net ionic equations for dissolving solids by addition of nitric acid. Again, answer is NOT in this manual. a) Nickel(II) hydroxide precipitates b) Iron(III) hydroxide precipitates 5. Describe the difference between quantitative analysis and qualitative analysis.
