CHEMISTRY 151 LABORATORY

04/12/2006

1. Synthesis of Hexamminecobalt (III) chloride The preparation of hexammine cobalt (III) salts is carried out most conveniently starting from cobalt (II) chloride hexahydrate, CoCl26H2O, which is both stable and inexpensive. Hexamminecobalt (III) salts can be prepared by three methods in which cobalt (II) is oxidized in a ammonia solution: (1) air oxidation, with the formation of the pentammine ion, which is converted to hexammine by heating with aqueous ammonia under pressure; (2) oxidation with an agent such as H2O2, I2, KMnO4, or PbO2; (3) oxidation in the presence of a catalyst that allows equilibrium between the pentammine and the hexammine ions to be established at room temperature and atmospheric pressure. The method devised by Bjerrum & McReynolds uses activated charcoal as the catalyst, is simple, and gives high yields of pure product. A high concentration of ammonium salt stabilizes the hexamminecobalt (III) ion and the charcoal catalyzes the ligand exchange. Activated charcoal contains finely divided carbon sheets having a large surface area that can trap molecules. The tiny holes on its surface can be used as reaction sites, allowing an intermediate complex like [Co(NH3)5H2O]2+ to stabilize itself so that the steric bulk of the five bonded ammonias will not prevent the entrance of the sixth NH3 molecule. After use, the activated charcoal can be removed by filtration. 4CoCl2 + 4NH4Cl + 20NH3 + O2 4[Co(NH3)6]Cl3 + 2H2O Add 9.6 g of CoCl26H2O and 6.4 g of NH4Cl to 40 mL of water in a 250 mL Erlenmeyer flask with a side arm (filtering flask). Shake until most of the salts are dissolved. Then add 1 g of fresh activated decolorizing charcoal and 20 mL concentrated ammonia. Next connect the flask to the aspirator or vacuum line and draw air through the mixture until the red solution becomes yellowish brown (usually 23 hours). CARE: if the bubbling is too vigorous, ammonia is lost from the solution. In such a case, the solution stays red instead of becoming yellow. Add more ammonia to finish the experiment, though your yield will be low. The air inlet tube should be of fairly large bore (~10 mm) to prevent clogging with the precipitated Co(NH3)63+ salt. Filter the crystals and charcoal on a Bchner funnel and then add a solution of 6 mL of concentrated HCl in 75 mL of water; sufficient acid should be used to give the entire mixture an acid reaction. Heat the mixture on a hot plate to effect complete solution and filter it hot. Crystallize the hexamminecobalt (III) chloride by cooling to 0 C and by slowly adding 15 mL of concentrated HCl. Filter the crystals, wash with 60% and then with 95% ethanol and dry it at 80-100 C. Analyze the product with IR and UV-Vis spectrometers, calculate the extinction coefficient of the complex, and the percent yield. Questions: 1. Determine the spectrochemical series involving the ligands used in this experiment. How does this compare with valence bond theory? Crystal field theory? 2. How do the frequencies of the free ligands compare to those when the ligands are bound to a transition metal like Co (III)? Account for any differences in these frequencies. How can these differences confirm or disprove that the ligands are actually bound to the cobalt (III) cation? 3. Is your product paramagnetic? If so, how many spins? What is the calculated magnetic moment?