Preparation and Titration of Potassium Tris(Oxalato)Aluminate(III)

Introduction Aluminum, like many of the transition metals, forms octahedral complex ions. In this lab you will synthesize potassium tris(oxalato)aluminate(III), K3[Al(C2O4)3]3H2O and determine the mass percent of oxalate in the sample. Is it really this compound that is produced, which has three moles of oxalate ion for every mole of aluminum? Or is it simple aluminum oxalate, Al2(C2O4)3, which has three moles of oxalate for every two moles of aluminum? This will be determined by titration, employing potassium permanganate as a titrant. This is very similar to the previous lab in which we used an acid-base titration to determine the mass percent of ammonia in a copper compound, in this case employing an oxidation-reduction titration rather than an acid-base titration. First, lets cover some background on aluminum. Like several other metals, aluminum is reactive enough to displace hydrogen from water. However, this does not occur because aluminum develops a layer of aluminum oxide that protects the metal surface. This oxide coating can be dissolved by acid, according to the equation shown below. Al2O3 + 3HCl 6Cl- + 2Al3+ + 3H2O The oxide coating can also be dissolved by excess hydroxide, forming the [Al(OH)4]- ion. Al2O3 + 2OH- + 3H2O 2[Al(OH)4]Once the oxide coating is removed, the aluminum will react with water to produce hydrogen gas, just like some of the alkali and alkaline earth metals. Al + 4H2O [Al(OH)4]- + 2H2 In the first part of this experiment you will synthesize K3[Al(C2O4)3]3H2O. First, aluminum metal is reacted with potassium hydroxide to produce the [Al(OH)4]- ion. Next, oxalic acid (H2C2O4) is added, which neutralizes the excess hydroxide and provides a source of the oxalate ion. Last, the [Al(C2O4)]3- ion that is produced is precipitated as the potassium salt by the addition of ethanol. The overall reaction is represented by the equation shown below. Al + 3KOH + 3H2C2O42H2O K3[Al(C2O4)3]3H2O + 6H2O + 3/2 H2 In the second part of the experiment you will employ an oxidation-reduction titration to determine the mass percent of oxalate in the sample. In this reaction, the C2O42- ion is oxidized to CO2. In C2O42- carbon is in the +3 oxidation state and in CO2 carbon is in the +4 oxidation state; since two CO2 molecules are produced from one C2O42- this a two-electron oxidation. C2O42- 2CO2 + 2e1

The oxidant that will be employed is the permanganate (MnO4-) ion, which will itself be reduced to the Mn2+ ion. Since MnO4- has manganese in the +7 oxidation state, this is a five-electron reduction. 5e- + MnO4- Mn+2 In any oxidation-reduction process the electrons must balance. The only way to balance the equation is to multiply the oxidation reaction by five and the reduction reaction by two, giving the following equation. 5C2O42- + 2MnO4- 10CO2 + 2Mn+2 Adding H2O to balance the oxygen atoms and H+ to balance the hydrogen atoms give the massbalanced equation shown below. 16H+ + 5C2O42- + 2MnO4- 10CO2 + 2Mn+2 + 8H2O Every titration must employ an indicator of some kind to signal the completion of the reaction. In this case, the intense purple color of the permanganate ion serves as a built-in indicator. As long as C2O42- is present, the MnO4- is reduced to Mn2+, which is very nearly colorless. Once the supply of C2O42- is exhausted, one additional drop of MnO4- is enough to turn the entire solution pink, signaling the end of the titration. A Sample Calculation Lets work an example calculation. Suppose a 0.110-gram sample of a compound believed to be K3[Al(C2O4)3]3H2O is titrated with 0.02 M of KMnO4. If 14.28 mL of KMnO4 are required, determine the mass percent of oxalate in the sample. First, use the molarity and volume of KMnO4 to determine the number of moles used. (14.28 mL) x (1 L/1000 mL) x 0.02 mol/L = 2.856 x 10-4 moles Next, consider the stoichiometry of the reaction. Two moles of permanganate react with five moles of oxalate; therefore moles of C2O42- = 5/2 the moles MnO4-. (2.856 x 10-4 mol MnO4-) x (5 mol C2O42-/ 2 mol MnO4-) = 7.140 x 10-4 mol C2O42This is then multiplied the mass of C2O42- to get the mass of oxalate in the sample: 7.140 x 10-4 mol x 88.04 g/mol = 0.06283 grams Finally, this is divided by the total mass of the sample to get the mass percent of oxalate in the sample. 0.006283 gram of oxalate / 0.110 grams of sample = 57.1 % oxalate Note that the mass of sample limited the final answer to three significant figures. 2

Procedure Week 1 Cut aluminum foil into roughly one-centimeter squares and measure approximately 0.50 grams (this should require 12-14 squares of foil). Record the exact mass used. Transfer the foil to a 250-mL beaker. Using a graduated cylinder, add 30 mL of water and 15 mL of 4.0 M KOH. If necessary use a stirring rod to be sure the aluminum foil is submerged. When the reaction has subsided, heat the solution to boiling on a hotplate to dissolve any unreacted aluminum. Next, add 8.0 grams of oxalic acid dihydrate, in small portions, to the hot solution. Filter the hot solution through a Buchner funnel and transfer the filtrate back to the 250ml beaker. Place the beaker an ice bath and cool it to 10oC. Add approximately 20 mL of ethanol and leave the beaker in the ice bath until crystallization appears complete (this could take up to 15-20 minutes). Recover the product by suction filtration, rinse with 10mL of acetone, and allow it to air dry. Transfer the solid to a sample vial, label it with your name, and store it in your drawer until the following period.

Procedure Week 2 Caution: Wear gloves when working with the 0.02 M KMnO4 solution. It is a powerful oxidant and will stain both skin and clothing. Clean and rinse a 250-mL beaker and obtain approximately 150 mL of 0.02 M KMnO4 solution. This should be enough for all three titrations. Clean and rinse your buret first with water and then with a few mL of the KMnO4 solution. Drain a few mL of titrant from the buret to be sure the tip is filled and there are no air bubbles. Weigh three 0.10 0.35 gram samples of the compound you made the previous week and add to three 125-mL Erlenmeyer flasks. It is a good idea to use a different mass each time. Dissolve each sample in approximately 35 ml of 3M H2SO4. Place the first flask on a hotplate and heat to 70-80oC (use a thermometer to monitor the temperature; you cannot rely on the hotplate reading). Once the solution has been heated, turn off the heat, remove the thermometer, and add a magnetic stir bar. Begin slowly adding the KMnO4 titrant; a good initial rate is 1-2 drops per second. You will see local color changes around each drop of titrant that disappear as the solution is stirred. As you approach the endpoint it will take longer for the color to disappear; this is a sign that you should slow the titration. There should be a precise endpoint; the KMnO4 is so intensely colored that one drop excess should be should be enough to impart a permanent pink color to the entire solution. Repeat this procedure for the remaining two flasks. Based upon the volumes of titrant used, determine the mass percent of oxalate in each sample. When finished be sure to rinse your buret thoroughly with water as the KMNO4 solution will stain and ruin the buret. 3

Preparation and Titration of Tris(Oxalato)Aluminate(III) Pre-Laboratory Week 1

Name:

1. List the chemical formula, physical and chemical properties, and any hazards or special precautions, associated with each of the following reagents: a. Oxalic acid dihydrate

b. Potassium permanganate

2. Calculate the amount of K3[Al(C2O4)3]3H2O that could be obtained from 0.50 grams of aluminum.

3. Calculate the mass percent of C2O42- in (a) Al2(C2O4)3 and K3[Al(C2O4)3]3H2O.

Preparation and Titration of Tris(Oxalato)Aluminate(III) Report Page Week 1

Name:

1. Record your observations during the synthesis of K3[Al(C2O4)3]3H2O.

2. What mass of aluminum did you use? Calculate the theoretical yield of K3[Al(C2O4)3]3H2O based upon this mass of aluminum. You must show your calculations to receive credit.

3. How much K3[Al(C2O4)3]3H2O was obtained? Calculate your percent yield. You must show your calculations to receive credit.

Preparation and Titration of Tris(Oxalato)Aluminate(III) Pre-Laboratory Week 2

Name:

1. Calculate the volume of 0.20 M KMnO4 that would be required to completely react with 0.75 grams of K3[Al(C2O4)3]3H2O.

2. Suppose that a 0.65-gram sample of K3[Al(C2O4)3]3H2O requires 8.50 mL of 0.20 M KMnO4 to reach the endpoint. Determine the mass percent of oxalate in the sample.

3. Suppose that the sample of K3[Al(C2O4)3]3H2O you titrated was wet. Do you think this would cause your mass percent of oxalate to be erroneously high or low? Explain your answer.

Preparation and Titration of Tris(Oxalato)Aluminate(III) Report Page Week 2

Name:

Mass of sample

Starting buret volume (mL)

Final buret volume (mL)

Volume of titrant dispensed (mL)

Volume of titrant dispensed (L) Moles of MnO4dispensed Moles of C2O42- in sample Mass of C2O42- in sample

Mass percent of C2O42-