Experiment 3: The Preparation and reactivity of coordination compounds Jim Hartley U4223210 Thursday, group 3 Dan Beck 20/10/05

AIM: To prepare an inorganic complex, K3[Fe(ox)3].3H2O, and study its reactivity. INTRODUCTION: Coordination compounds consist of a central metal ion surrounded by some number of donor atoms. The species that donate these atoms are referred to as ligands. The number of donor atoms of a given compound is known as its coordination number. The tris(oxalato)ferrate(III) compound prepared has three oxalate ions as ligands, and since each oxalate ion donates 2 atoms to the compound, the coordination number of six. In the first part of this experiment, the tris(oxalato)ferrate(III) anion is isolated, than the hydrated potassium salt, a green crystalline compound, is isolated (eqn 1) Eqn 1: FeCl3.6H20 +3K2C2O4.H20 K3[Fe(ox)3].3H2O + other products The second part of the experiment was to examine the reactivity difference between the tris(oxalato)ferrate(III) compound and an aquo compound, [Fe(H20)6]3+. Essentially, different ligands attached to a metal change the reactivity of the compound in question. Specifically, the reactivities of a metal ion and water ligands, as compared to a metal ion and non-water ligands, differ significantly. In the third part of the experiment, the photosensitivity of the [Fe(ox)3]3- is studied, particularly in utilization through a blueprinting procedure. Light of wavelength 450 nm or lower causes an intramolecular redox reaction (eqn 2 below) in the [Fe(ox)3]3- in which the Fe(III) ion is reduced to Fe(II), which can then be detected by adding potassium ferricyanide, K3[Fe(CN)6] which reacts with the Fe(II) to form a dark blue substance, ferriferrocyanide, Fe4[Fe(CN)6]3.H20. (eqn 3 below) Eqn 2: [Fe(ox)3]3- + e- [Fe(ox)2]2- + 2CO2 Eqn 3: [Fe(ox)2]2- + K3[Fe(CN)6] Fe4[Fe(CN)6]3.H20 + other products Procedure: No changes were made to the procedure specified in the lab manual for any of the three parts of the experiment. All relevant equations and reaction schemes are found in the Introduction section of this report. RESULTS AND OBSERVATIONS: (a) Mass of potassium oxalate, K2C2O4.H20 Molecular weight of K2C2O4.H20 Moles of K2C2O4.H20 Mass of Iron(III) chloride hexahydrate, FeCl3.6H20 4.49 184.231 0.024 2.03

Molecular weight of FeCl3.6H20 270.297 Moles of FeCl3.6H20 0.0075 Equation FeCl3.6H20 +3K2C2O4.H20 K3[Fe(ox)3].3H2O + other products Molecular Weight of K3[Fe(ox)3].3H2O 491.246 Theoretical yield of K3[Fe(ox)3].3H2O 3.68 Mass of prepared, dried product 3.42 g Percentage yield 92.83% Appearance of Product: Lime-Green Crystals Calculations for yield:

(b) Observations: K3[Fe(ox)3].3H2O water solution is light green, remaining this colour after KI added, but with addition of DCM, the solution separates into two layers, green top layer, clear bottom with a top to bottom ration of about 5:1. [Fe(H20)6]3+ with water turns light brown/yellow, remaining this colour with addition of KI, but addition of DCM causes separation into 2 layers, burgundy on top, purple on bottom. Interpretation: That the organic layer is clear for the [Fe(ox)3]3- solution is due to the reduction reaction that takes place, [Fe(ox)3]3- + e- [Fe(ox)2]2- + C2O42-only providing 0.02 volts. Thus, the 2I- 2e- +I2 reaction cannot take place, as it requires 0.54 V. Thus, no iodine is present in the organic layer. In the aquo compound, however, the reaction Fe(H2O)63+ + e- Fe(H20)62+ produces 0.77 volts, which is more than enough to cause the 2I- 2e- +I2 reaction to take place, meaning iodine will be present in the iodine layer, which is indicated by the purple colour of that layer. (c) Observations: Irradiated sample turns dark blue with addition of ferricyanide. Unirradiated sample turns slightly blue with addition of ferricyanide, but for the most part, still green.

FeSO4 turns dark blue with addition of ferricyanide. Interpretation: The [Fe(ox)3]3- anion is photosensitive, subject to internal redox when subjected to radiation of wavelength 450 nm or lower. [Fe(ox)3]3- + e- [Fe(ox)2]2- + 2CO2 Thus, the test tube placed under the spot lamp undergoes significant redox reaction, whereas the one placed in the cupboard (to prevent exposure to light), does not. When ferricyanide is added to the test tube, the [Fe(ox)2]2- reacts with the ferricyanide, K3[Fe(CN)6], forming a Prussian blue complex known as ferriferrocyanide, Fe4[Fe(CN)6]3.H20. [Fe(ox)2]2- + K3[Fe(CN)6] Fe4[Fe(CN)6]3.H20 + other products. Thus, the tube subjected to a lot of light has significant [Fe(ox)2]2-, which can then react with the ferricyanide. This means the product will be coloured a dark blue. The tube which is kept away from direct light, on the other hand, will not have very much [Fe(ox)2]2-, and as a result, the reaction with ferricyanide does not produce as much ferriferrocyanide, and very little blue colour appears. (ii) Blueprinting Interpretation: When the absorbent paper is dipped in the photosensitive liquid, were it to be placed under direct light, it would turn Prussian blue. After the paper is dried in the oven, a negative is placed over the paper, meaning that while parts of the paper are still subjected to direct sunlight through the clear parts of plastic, meaning they will turn Prussian blue, other parts, covered by opaque plastic, are not subjected to light, and as a result, will remain the green colour of the photosensitive liquid. Once reaction has occurred to a suitable extent, the paper is washed, so that all remaining photosensitive material is flushed from the paper, thereby fixing the print. DISCUSSION: There are two apparent discrepancies. The first is that the yield for the first part of the experiment, the making of the coordination compound, is very high. This could be due to insufficient drying, meaning some water still remains with the crystals, producing an incorrectly high yield. Were the crystals to have been dried in the oven in addition to the acetone wash, perhaps this would not have been an issue. The second discrepancy is that the supposedly non-exposed sections of the blueprint turned a light blue, whereas in theory they should have remained white. The most obvious explanation for this is that the photosensitive paper was subjected to enough light before the negative was placed on it, or once the negative was removed, white areas were subjected to light before fixing. Furthermore, the blueprint appears somewhat smudged, which can be attributed, perhaps, to insufficient drying in the oven before the paper was exposed to light. This would perhaps allow the blue dye to run through the paper somewhat, creating a blurry, smudged effect. However, the

blueprint is still clear enough to suggest that some drying did occur. CONCLUSION: The inorganic compound was prepared and its reactivity studied.

POST-LAB QUESTIONS: 1) Suggest a possible structure for the copper(II)oxalate complex.

2) Design an experiment that uses the blueprinting process to assess the effectiveness of sunscreen creams. The easiest way to do this would be to prepare the same K3[Fe(ox)3].3H2O complex, prepare the same blueprinting solution as detailed in the procedure for part c. Once again, dip absorbent paper in the blueprinting solution, dry it in an oven, but instead of overlaying a negative, divide the paper into a number of segments, appropriate to the number of sunscreens being tested, and cover each segment with similar amounts of different sun creams. Leave one section without sun cream as a control. This is shown in the diagram below.

Then, place this paper in direct sunlight. The section that turns blue the slowest, was

the section covered in the most effective sun cream. The section that turns blue the quickest, disregarding the control, has the least effective sun cream.