Chemistry 212 The Preparation of Common Alum from Scrap Aluminum

LEARNING OBJECTIVES To demonstrate the principle of recycling by conversion of waste materials into valuable pure substances. To provide experience in filtration methods and in melting point determinations.

BACKGROUND In this experiment, you will prepare a common alum, KAl(SO4)2@12H2O (potassium aluminum sulfate dodecahydrate), from an aluminum beverage can. Alums can be described as a class of compounds that contain the sulfate ion, SO42-, a trivalent (3+) cation such as Al3+ , Cr3+ , Fe3+ , and a monovalent (1+) cation such as K+ ,Na+ , and NH4+ . Alums have many purposes, as shown in the table below. The alum that you will prepare forms white crystals similar to fine salt. The @12H2 O indicates that 12 molecules of water are present in the crystals for each KAl(SO4)2 formula unit.

Aluminum is the most abundant metal in the earth's crust (8.3% by weight) and is the third most abundant element after oxygen (45.5%) and silicon (25.7%). Pure aluminum is a silvery-white metal and has many desirable physical and chemical properties: it is light-weight, non-toxic, corrosion-resistant, nonmagnetic, and malleable. Aluminum is commonly combined with other metals such as copper, manganese, silicon, magnesium, and zinc, which produces alloys with high mechanical and tensile strength. You are probably familiar with many uses of aluminum and its alloys. The first post-lab question asks you to list some examples. When metallic aluminum comes into contact with aqueous solutions of strong bases like potassium hydroxide, KOH, it reacts to form hydrogen gas (FLAMMABLE!) and a salt containing both aluminum and potassium ions. 2 Al (s) + 2 KOH (aq) + 6 H2O (l) 2 K[Al(OH)4] (aq) + 3 H2 (g) This salt, K[Al(OH)4], is soluble in solutions of strong acids, such as sulfuric acid, H2SO4, and reacts to form aluminum hydroxide, Al(OH)3, and potassium sulfate, K2SO4. 1

2 K[Al(OH)4] (aq) + H2SO4 (aq) 2 Al(OH)3 (s) + K2SO4 (aq) + 2 H2O (l)
Excess sulfuric acid is required to dissolve the Al(OH)3, and to form aluminum sulfate, Al 2 (SO4) 3. 2 Al(OH)3 (s) + 3 H2SO4 (aq) Al 2 (SO4)3 (aq) + 6 H2O (l) As this solution is cooled, the aluminum and potassium sulfate salts crystallize out of the solution as the alum. The equation below shows only the ions and the water involved in the crystallization process. K+ (aq) + Al3+ (aq) + 2 SO42- (aq) + 12 H2O (l) KAl(SO4)2@12H2O (s) You will determine both the percent yield and the melting point of your alum crystals. Please see The Determination of Melting Point at the end of this lab procedure.

Type of Alum (common name) Ammonium aluminum sulfate dodecahydrate (ammonium alum) Ammonium ferric sulfate dodecahydrate (ferric alum) Potassium aluminum sulfate dodecahydrate (alum or potassium alum) Potassium chromium(III) sulfate dodecahydrate (chrome alum) Sodium aluminum sulfate dodecahydrate (sodium alum)

Formula NH4 Al(SO4 )2@12H2O NH4Fe(SO4)2@12H2O KAl(SO4)2@12H2O KCr(SO4)2@12H2O NaAl(SO4)2@12H2O

Uses Pickling cucumbers

Mordant in dyeing and printing textiles Water purification, sewage treatment, and fire extinguishers Tanning leather and waterproofing fabrics Baking powders: hydrolysis of Al3+ releases H+ in water to react with the HCO3- in baking soda to produce CO2 , causing the dough to rise.

SAFETY PRECAUTIONS CAUTION!! Excess care must be used in handling potassium hydroxide (KOH) and sulfuric acid (H2 SO4 ). KOH is corrosive and will dissolve clothing and skin! Sulfuric acid will also burn and dissolve clothing. Wash your hands thoroughly after using either of these solutions!

EXPERIMENTAL PROCEDURE 1. A piece of scrap aluminum will be provided. Use steel wool to remove as much paint as

possible. The inside of the can is protected with a plastic coating and you should remove 2

this also. Weigh the cleaned strip of aluminum to the nearest 0.001 grams. 2. Cut the Al sample into small squares and place the squares in a clean 100-mL or 150-mL beaker. Perform the following either in the hood or close to the bench-top hood!! Carefully add 20 mL of 4 M potassium hydroxide, KOH. Bubbles of hydrogen gas should evolve. Place your beaker on a hot plate (close by the bench-hood-screen) to speed up the reaction. When hydrogen bubbles are no longer formed, the reaction is complete. This should take 10-15 minutes. Remove the beaker from the hot plate and allow it to cool at your bench. The resulting grayish mixture should be filtered to remove unwanted impurities. If the solution is still warm, cool it by placing the beaker in an ice bath. Set up a 250-mL filter flask and Gooch filter crucible or Bchner funnel as demonstrated. Don't forget to clamp the filter flask to some kind of support. Filter the solution slowly. Rinse the beaker two times with small portions (<5 mL) of distilled water, pouring each rinse through the filter. Transfer the clear colorless filtrate to a clean 250-mL beaker. To the cool solution, slowly and carefully, with stirring, add 15 mL of 6 M sulfuric acid. White lumps of Al(OH)3 should form in the solution. Again working by the bench-hood, heat and stir the mixture to dissolve the white lumps. Excess sulfuric acid may be added dropwise, but no more than 30 mL total, in order to totally dissolve the Al(OH)3, and give a clear solution. Cool the clear solution in an ice bath for at least 20 minutes. Crystals of alum should fall to the bottom of the beaker. If no crystals form, scratch the bottom of the beaker with your stirring rod. If that fails, add a "seed" crystal of alum to facilitate crystallization. While the solution is cooling, reassemble the filtration apparatus. Be sure to weigh the filter paper at this point. Slowly filter the solution containing the crystals. Rinse the beaker once with 5 mL of cool distilled water and once with 5 mL of isopropyl (rubbing) alcohol, pouring each rinse through the filter. Allow the aspirator to pull air through the crystals until they appear dry, at least 5 minutes. Remove the filter from the flask. More crystals may form in the filtered solution (filtrate). If you have time, filter these crystals as just described, and add these to the first crystal crop. Remove the damp crystals and filter paper from the filter and place them into a weighed beaker. Place the beaker containing your crystals in your locker until next week. After drying, weigh the filter and crystals, and determine the mass of the alum produced. Calculate the percent yield. Determine the melting point of the alum crystals using the following procedure. Carefully, push the open end of a capillary tube into your crystals, forcing some of the solid into the tube. Turn the tube over and tap it gently to move the crystals to the sealed 3

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end of the tube. Repeat this process until you have about 5 mm of solid in the capillary tube. Carefully, insert the tube into the melting point apparatus. The apparatus will be HOT if others have been using it! Note the temperatures at which the alum first appears to melt (i.e., when liquid first becomes visible) and at which it is completely melted (all liquid). Discard the capillary tube in the glass bin.

9.

Obtain the literature value for the melting point of alum. Compare your experimental melting point to the literature value. Calculate the percent error.

DETERMINATION OF MELTING POINT (SUPPLEMENTARY EXPERIMENTAL PROCEDURE)

1.

The melting point of a pure substance is a characteristic property for a given substance. That is, under the same laboratory conditions, a given substance will always have the same melting point. Characteristic physical properties (such as the melting point or boiling point of a pure substance) are of immense help in the identification of unknown substances. Such properties are routinely reported in scientific papers when new substances are isolated or synthesized, and are compiled in tables in the various handbooks of chemical data that are available in science libraries. When an unknown substance is isolated from a chemical system, its melting point may be measured (along with certain other characteristic properties) and then compared with tabulated data. If the experimentally determined physical properties of the unknown match those found in the literature, you can typically assume that you have identified the unknown substance.

2.

When a pure solid substance melts during heating, the melting usually occurs quickly at one specific, characteristic temperature. For certain substances, especially more complicated organic substances or biological substances that tend to decompose slightly when heated, the melting may occur over a span of a few degrees, called the melting range. Melting ranges are also commonly observed if the substance being determined is not completely pure. The presence of an impurity will broaden the melting point of the major component and will also lower the temperature at which melting begins. Melting points of solid substances are routinely reported in the scientific literature and are tabulated in handbooks for use in identification of unknown substances. Melting point determinations are very common and will be used as an aid in the identification of solid products and as an indication of their purity.

THE PREPARATION OF COMMON ALUM FROM SCRAP ALUMINUM

Name _________________________________ Lab Instructor ___________________________ Section/Day_____________________________ Date __________________________________ DATA & RESULTS Alum Preparation Mass of aluminum sample Mass of filter paper (second time) Mass of beaker Mass of beaker, filter paper & alum crystals Mass of alum crystals Theoretical Yield of alum (based on Al) Percent Yield ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________ ________________________________

Melting Point Determination Temperature at which melting begins Temperature at which melting ends Literature value for the melting point of alum ________________________________ ________________________________ ________________________________

Please show calculations below.

POST LABORATORY QUESTIONS 1. List some common uses of aluminum and/or aluminum alloys.

2.

What are some specific things that affected your yield? How could you have improved your yield?

3.

How does the experimental melting point of the alum produced compare to the literature value? List possible reasons for any differences.

THE PREPARATION OF COMMON ALUM FROM SCRAP ALUMINUM

Name _________________________________ Lab Instructor ___________________________ Section/Day_____________________________ Date __________________________________ PRE LABORATORY ASSIGNMENT 1. Calculate the molar mass of alum. (The formula is given in the introduction.)

2.

Calculate the mass percentage of aluminum in alum.

3.

If you begin with 0.50 g of aluminum metal and 5.0 g of alum are obtained at the end of the experiment, what percent of the original aluminum was actually recovered? Be sure to take into account that only a small fraction (see Question #2 above) of the alum mass is actually aluminum.