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EXPERIMENT 3 SYNTHESIS, CHARACTERIZATION AND LIGAND EXCHANGE EQUILIBRIA OF POTASSIUM TRIS(OXALATO)FERRATE(III) PURPOSE This three-part laboratory exercise will

expose students to their first synthesis of inorganic compound, in this case a coordination compound. It offers an integrative approach in laboratory chemistry, where in addition to gaining skills in synthesis, you will see how basic characterization of a compound is carried out using already familiar techniques of titrimetry and spectrophotometry (colorimetry) to help elucidate the structure and further to explore some aspects of the ligand exchange chemical equilibria. OBJECTIVES During and by completing this experiment, you (student) will: 1. Synthesize and purify by recrystallization the coordination compound, potassium tris(oxalato)ferrate(III). 2. Determine the oxalate content of the coordination compound via titrimetric analysis using standardized potassium permanganate. 3. Prepare and standardize a solution of potassium permanganate. 4. Explore the redox chemistry of the reaction between the oxalate and manganate ions. 5. Determine the iron content of the coordination compound via colorimetric analysis. 6. Calculate the number of water of crystallization in the coordination compound. 7. Determine the molecular formula of the complex synthesized. 8. Explore some ligand exchange reactions of the synthesized compound. INTRODUCTION Coordination chemistry is an important aspect of chemistry and the synthesis of these compounds is very exciting due to the variation in colours that these complexes display due to the interesting electronic and coordination properties by the metal ions and ligands. One of the easiest coordination complexes to prepare is potassium tris(oxalato)ferrate(III). Its interesting

chemistry and versatility sees it being used as a starting material in the synthesis of many other industrial compounds. This experiment will be done over the course of two lab sessions. In the first, you will synthesize the compound and carry out ligand exchange reactions and in the second you will analyze it to determine its molecular formula. As you have learnt in CHEM 1067, inorganic compounds may contain a variety of species, including ions, ligands, metal centres, and independent molecules. In this lab, you will synthesize a coordination compound (complex iron salt) with the formula KxFey(C2O4)zH2O, where C2O42- is the oxalato ligand. The "" before H2O indicates the number of "water of hydration/crystallization", which means number of water molecules are loosely bound in the crystal. In inorganic synthesis, the desired product is frequently formed and isolated by crystallization from a reaction mixture. Because the reaction mixture may contain excess reactants and other products, the crystals are likely to be relatively impure. The crystals can be separated from the impure solution (often called the "mother liquor") by filtration or decantation and then washed. However, washing will not remove impurities occluded within the crystals. A standard method for purifying the product is recrystallization. The product is redissolved in a minimal amount of an appropriate solvent, generally while heating. Slow cooling of the solution results in slow crystal growth, producing pure crystalline product. An important factor in syntheses is the actual quantity of desired product obtained compared to the theoretical amount predicted on the basis of the stoichiometry of the reaction. The ratio of the mass of the actual product to the theoretical amount is the percent yield. There are many reasons why the actual yield is not 100 %; you will be expected to suggest some reasons based on the chemistry of the method used. The oxalate ion in the compound will be determined by titration with potassium permanganate (KMnO4) according to the reaction: 5 C2O42- (aq) + 2 MnO4- (aq) + 16 H+ (aq) 10 CO2 (g) + 2 Mn2+ (aq) + 8 H2O (l)

Before you can perform the titration, you will need to standardize the potassium permanganate using sodium oxalate (Na2C2O4), according to the same reaction. The amount of iron in the complex will be determined spectrophotometrically. First, the compound is to form ferrous ions, then a reagent, bipyridine, another chelating ligand is added which will exchange the oxalate and bind to the metal ion. The intensity of the red colour is a measure of the concentration and the iron content is determined from a calibration curve of standards. An important aspect of the [Fe(C2O4)3]3 complex anion is that it is a very useful product for exploring chemical equilibria, offering an overall picture of how ligand coordination, displacement/exchange and precipitation equilibria are interrelated. The sufficient quantity of complex obtained in the synthesis permits utilization of the substance to show students a practical example of the chemistry of complexes in solution. The anion presents an ideal balance between stability and lability such that a number of reactions can be displaced in one direction or the other, depending on the quantity and properties of the reagents involved. APPARATUS AND CHEMICALS Fe(NH4)2(SO4)26H2O (5 g) 20 volume H2O2 (9 mL) 1 M H2SO4 (50 mL) 0.005 M FeSO4 (15 mL) 10 % aqueous hydroxylamine 6 M HCl (few drops) Buchner setup 250 mL volumetric flask 50 mL burette Bunsen/hotplate SAFETY PRECAUTIONS Remember your PPE: lab coat, gloves and safety glasses should be worn at all times. H2C2O42H2O (4.5 g) 95 % ethanol (50 mL) 0.02 M KMnO4 K2C2O4.H2O (3.5 g) Acetone (20 mL) Na2C2O4 (0.4-0.6 g)

0.1 % aqueous bipyridine (30 mL) sodium acetate pH buffer 5 (30 mL) 0.5 M KSCN (few drops) Filter paper 20 mL Vol. Flasks (3) Foil sheet Spectrophotometer 3 M KF (few drops) 250 mL beaker 250 mL conical flasks (6) Cuvettes

Potassium permanganate and sulphuric acid and hydrogen peroxide can cause chemical burns. The KMnO4 solution is a powerful oxidant and the dilute solution is a disinfectant will stain skin and clothing. Oxalic acid and oxalates are toxic and must not be ingested. Avoid skin contact with these chemicals, but if you spill them on yourself, simply wash with cold water. Clean up all spills immediately. Be cautious when using glassware. Should breakage occur, inform your demonstrator, clean up broken glass and place in the broken glass bin, NOT the regular trash (glass in regular trash can injure our custodial staff). Please follow all laboratory safety guidelines. Please review current Material Safety Data Sheets for additional safety, handling, and disposal information.

EXPERIMENTAL Part A: Preparation of the Complex (Week 1) Mark the level of 45 mL water in a 250 mL beaker. To a well-stirred solution of 5 g of ferrous ammonium sulphate in 20 mL of warm water containing 1 mL of dilute sulphuric acid in the beaker, add a solution of 2.5 g of oxalic acid dihydrate in 25 mL of water. Slowly heat the mixture to boiling (beware of bumping) then allow the yellow precipitate to settle. Decant the supernatant through a Buchner funnel making sure it has a properly fitted filter paper. Add 15 mL of hot water to the solid precipitate then stir and filter. Drain well and then transfer all the precipitate from the paper, back into the beaker with 10 mL hot water. Add 3.5 g solid potassium oxalate monohydrate and heat to approximately 40 oC. Add slowly, using a dropper, 9 mL of 20 volume hydrogen peroxide. (If the precipitate looks yellowish, not brown and settles readily, decant the supernatant, add a solution of 0.2 0.4 g potassium oxalate monohydrate in 1 2 mL water and then hydrogen peroxide dropwise until the precipitate dissolves. Then add the previously decanted supernatant) and heat to boiling. Add a solution of 2 g of oxalic acid dihydrate in 30 mL of water in portions, add 20 mL initially, then, if the brown precipitate still remains, add more solution little by little until it all dissolves. Boil the clear solution down to a volume of 40 50 mL,

filter through a Buchner funnel with well fitting paper and add 95 % ethanol slowly until a precipitate starts to form (~ 30 mL). Redissolve any crystals by heating (beware of fire assuming...using a flame) and leave to crystallise until next lab session. On your return to the lab filter and wash the crystals on the Buchner with a 1:1 ethanol/water mixture and finally with acetone, (beware fire again). Dry in the air and weigh. The complex is photosensitive and should not be exposed to light unnecessarily. Store in a sample bottle wrapped in foil. Part B: Chemical Equilibria - Ligand Exchange Reactions (Week 1) Approximately 0.1 M stock solution of potassium tris(oxalate)ferrate(III) is available to the class for use. Place 1 mL of the green stock solution 1 in a test tube and add 3 drops of 6 M HCl. Note the colour change of this solution 2; To 2 add 3 drops of 0.5 M KSCN and note the colour of this new solution 3. To 3 add 10 drops of 3 M KF and note the change of this new solution 4. Finally, add to 4 15 drops of 2 M K2C2O4, and record the change. Write reaction equilibria for each step and give a rationale for the changes taking place. Part C-1: Determination of Oxalate Content by Titrimetry (Week 2) a. Standardization The permanganate solution should be standardized accordingly: Weigh accurately two portions of about 0.2 g AnalaR sodium oxalate into conical flasks. Dissolve each in water, acidify with 50 mL of 1 M sulphuric acid and titrate slowly with permanganate at 60 oC until the solution retains a pin colouration after standing for about 30 seconds. b. Titration of Sample In duplicate, weigh accurately about 0.2 g of the potassium tris(oxalate)ferrate(III) complex previously prepared. Boil the sample with 50 mL of 1 M sulphuric acid in a conical flask.

Allow the solution to cool to about 60 C and titrate slowly with the standardized potassium permanganate solution. Continue until the warm solution retains a slight pink colouration after standing for about 30 seconds. Calculate the percentage by weight of oxalate in the complex, compare this with the theoretical value and thus obtain the percentage purity of the complex.

Part C-2: Determination of Iron Content by Spectrophotometry (Week 2) a. Preparing Sample and Standards Accurately weigh a portion of about 0.15 g of the potassium tris(oxalate)ferrate(III) compound and dissolve it in distilled water and make up 100 mL in a volumetric flask. Label this solution A1. Prepare solution B1 by accurately transferring using a pipette 1 mL of solution A1 to a 50 mL volumetric flask and dilute to the mark with deionised water. To this add 10 mL of 0.1 % aqueous bipyridine solution, 2 mL 10 % aqueous hydroxylamine solution (to reduce Fe(III) to Fe(II)) and 5 mL of 2 M sodium acetate buffer (pH range 5 7) and finally dilute to the mark with deionized water and mix thoroughly. Prepare a duplicate by repeating the first two steps, labelling the solutions A2 and B2 accordingly. Prepare the five ferrous standards as follows. To a 50 mL volumetric flask add 2 mL of 0.0005 M FeSO4, 10 mL of 0.1 % aqueous bipyridine solution, 2 mL 10 % aqueous hydroxylamine solution (to reduce Fe(III) to Fe(II)) and 5 mL of 2 M sodium acetate buffer (pH range 5 7) and finally dilute to the mark with deionized water and mix thoroughly. b. Repeat this using 3, 4, 5, and 6 mL of 0.0005 M FeSO4 and label these solutions appropriately. Colorimetric Analysis Compare the colour intensities of all the solutions using the spectrophotometer. At the selected wavelength (522 nm) measure the absorbance of the solutions at least three times and tabulate the results and calculate the average of the absorbance. Plot a graph of absorbance, A, against iron concentration, [Fe], using values from the five standard solutions. Determine the equation of the line and use it to determine the

concentration of the unknown samples. Certainly, one will have to work back to determine the actual amount of iron based on the mass of sample used. Ensure proper use of instrument with respect to zeroing during the measurement; please consult the instrument manual on myelearning prior the lab session. Part C-3: Determination of Water of Crystallization (Week 2) Weigh 0.5 0.7 g ( 0.0001g) of the complex salt into a pre-weighed evaporating dish. Label or mark the dish so you can identify it and place the evaporating dish and complex salt in an oven set at 110 oC for approximately 45 minutes. Cool the dish and contents and weigh to the nearest 0.1 mg. Calculate the % H2O in the crystals. EXCERCISES a. Pre-Lab 1. Using examples, explain the difference between complex, complex ion and a coordination compound. 2. Identify the type of and draw the structure of the oxalato and bipyridine ligands. 3. Draw the structure of tris(oxalato) ferrate(III) and tris(bipyridine) ferrate(III) complex ions and identify any isomerism in each. 4. In the synthesis of the coordination compound, identify the purpose of the hydrogen peroxide and write a balanced equation of this reaction step in the synthesis. 5. Identify and draw the structure of another ligand that has similar coordination to the bipyridine ligand forming a similar complex. b. Post-Lab 1. From the percentages of oxalato ligand, Fe3+ ion and water of crystallization, propose a formula for the complex ion and coordination compound. 2. Using crystal field theory (crystal field splitting energy), give an account of the colour changes in the ligand exchange reactions in part B.