EXPERIMENT 1: SYNTHESIS OF POTASSIUM TRIOXALATOALUMINATE(III) K3[Al(C2O4)3] Aim of the experiment: To illustrate complex formation by a non-transition metal Abstract: Potassium

trioxalatoaluminate (III) was prepared by boiling aluminium hydroxide precipitate with an aqueous solution of oxalic acid dehydrate and potassium oxalate. The percentage of oxalate ligand in the product was determined by titrating the prepared product solutions against standard 0.002M potassium tetraoxomanganate solution. Solutions were prepared as follows; 0.002M potassium tetraoxomanganate solution prepared by measuring 25cm3 of 0.02M potassium tetraoxomanganate solution stock into a 250ml volumetric flask followed by 25cm3 of 2M sulphuric acid and the volume made up to the mark with distilled water, 1% potassium trioxalatoaluminate (III) solution prepared by measuring 0.5g of the product stock into 50ml of distilled water in a volumetric flask. No indicator was necessary since in this case, the intense purple color of the permanganate ion serves as a built-in indicator. The percentage yield of potassium trioxalatoaluminate (III) as well as the percentage of oxalate ligand in the product was calculated using stoichiometry. The percentage yield of the 1.103g of product was found to be 21.47%.The percentages of oxalate ligand were found to be 40.18, 39.72, 39.49 and 39.03 in the product. Actual mean composition of oxalate ligand by percentage was found to be 39.605 0.4787%with variance of 0.2292for the product. Theory: Aluminum, like many of the transition metals, forms octahedral complex ions. In this lab experiment, potassium trioxalatoaluminate (III), K3[Al(C2O4)3]3H2O was synthesized and the mass percentage of oxalate in the sample determined by titration, employing potassium permanganate as a titrant in the oxidation-reduction titration. Potassium trioxalatoaluminate (III) is a metal complex of aluminium and three oxalate ligands all bonded to a central cation potassium ion. Each of these ligands binds to the metal atom at different places hence bi-dentate ligands. Its preparation is when its formed rapidly in alkaline solution such as aluminium hydroxide. In the first part of this experiment, K3[Al(C2O4)3]3H2O is synthesized. First, aluminum sulphate hexacahydrate solution is reacted with sodium hydroxide solution to produce the aluminium hydroxide, Al(OH)3. Al2(SO4)316H2O(aq) + 6NaOH(aq) 2Al(OH)3(s) + 3Na2SO4(aq) + 16H2O(l) Next, an oxalic acid dehydrate (H2C2O4) and potassium oxalate solution is added, which neutralizes the hydroxide and provides a source of the oxalate ion. Last, the [Al(C2O4)]3- ion is produced as the potassium salt by crystallization. The overall reaction is represented by the equation shown below. 2Al(OH)3(s) + 3H2C204(aq) + 3K2C2O4(aq) 2K3[Al(C2O4)3](aq) + 6H2O(l) In the second part of the experiment an oxidation-reduction titration is employed 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 + 2eThe oxidant employed is the permanganate (MnO4-) ion, which itself is reduced to the Mn2+ ion. Since MnO4- has manganese in the +7 oxidation state, this is a five-electron reduction. 5e- + MnO4- Mn2+ 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 + 2Mn2+ Adding H2O to balance the oxygen atoms and H+ to balance the hydrogen atoms give the mass balanced equation shown below. 16H+ + 5C2O42- + 2MnO4- 10CO2 + 2Mn2+ + 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.

Procedure: Aluminium sulphate hexacahydrate (3.5g) was dissolved in water (25cm3). To the solution (with stirring) was added sodium hydroxide solution prepared by dissolving NaOH (1.50g) in water (10cm3). The freshly precipitated aluminium hydroxide was filtered off and washed with water (3 20cm3). The precipitate was boiled with an aqueous solution of oxalic acid dehydrate (2.5g) and potassium oxalate (3.5g) first prepared by dissolving them in water (50cm3). Unreacted aluminium hydroxide was filtered off and the filtrate evaporated to a volume that could effect crystallization. The product was filtered off by suction and washed with a small volume of water. It was then dried in between filter papers and then left to completely dry in a desiccator. The dry product was later weighed and its percentage yield determined. In the second part of the experiment that involved titration, standard potassium tetraoxomanganate solution was prepared by mixing pure 0.02M potassium tetraoxomanganate (25cm3) with 2M sulphuric acid (25cm3) and water in a graduated flask (250ml) filling it to the mark. A 1% solution of the product was also prepared by dissolving the product (0.5g) in water (50cm3). This solution was later titrated against the prepared standard potassium tetraoxomanganate solution. Results: Aluminium sulphate hexacahydrate was completely soluble in water. Addition of sodium hydroxide solution to aluminium sulphate hexacahydrate solution led to formation of a white precipitate. Most of the precipitate completely dissolved in the aqueous solution of oxalic acid dehydrate and potassium oxalate leaving behind only a few impurities. The oxalic acid dehydrate and potassium oxalate crystals were fairly soluble in water at room temperature. Crystals formed during the crystallization process were white in colour. Mass of container + Aluminium sulphate hexacahydrate (g) 10.939

Mass of container after sample was removed (g) Mass of sample used (g) Mass of container + oxalic acid dehydrate (g) Mass of container after sample was removed (g) Mass of sample used (g) Mass of container + potassium oxalate (g) Mass of container after sample was removed (g) Mass of sample used (g)

7.461 3.478 11.724 9.242 2.482 15.886 12.402 3.484

Mass of crystals formed/Mass of potassium trioxalatoaluminate(III) formed Mass of container + product (g) Mass of container after product was removed (g) Mass of crystals formed (g) 6.567 5.464 1.103

Effects of reagents on aqueous 1% solutions of aluminium salt, Al2(SO4)3.XH2O and the product. Reagent aluminium salt, Al2(SO4)3.XH2O White precipitate soluble in excess reagent White precipitate soluble in excess reagent No observable change No observable change White precipitate soluble in excess reagent White precipitate soluble in excess reagent Effect/observation on; 1% solution of the product No observable change No observable change No observable change No observable change No observable change No observable change

4M Sodium hydroxide 2M Sodium Hydroxide 4M Sodium Ethanoate 2M Sodium Ethanoate 4M Sodium Carbonate 2M Sodium Carbonate