Overview of Synthesis and Preparation Experiments

Overview of Synthesis and Preparation ExperimentsIntroductionAs we know, Manganese is open up in the first row of transition metal with the electron configuration Ar 3d5 4s2. Besides that, Manganese has different type of oxidization states when it appears as a fuse and the oxidation state is from Mn(-III) until Mn(VII). So, we know that the compounds of manganese range in the oxidation number have a different of 10 electrons. In the taste 1, we found tris(acetylacetonato)manganese(III), Mn(acac)3 by using manganese(II) chloride tetrahydrate and potassium permanganate act as oxidation agent to oxidise manganese(II) chloride to acetylacetonemanganese(III).Manganese(III) acetylacetonate is an one- electron oxidant. Manganese(III) acetylacetonateis high spin. It has also a distorted octahedral structure. This distortion is callable to the Jahn-Teller effect. (Absolute Astronomy, 2009). The structure of Manganese(III) acetylacetonate is shown as below-(Source Tcieurope.com)The equat ion is as follow-MnCl2 + 4 pee Mn(H2O)4Cl2Mn(H2O)4 Cl + 2HC5H7O2 + NaC2H3O2 Mn(C5H7O2)2 + NaCl + HC2H2O24Mn(C5H7O2)2 + KMnO4 + 7HC5H7O2 + HC2H3O2 5Mn(C5H7O2)3 + KC2H3O2 + 4H2OFurthermore, bis(acetylacetonato)oxovanadium(IV) is also known as Vanadyl acetylacetonate, VO(acac)2. As we know, it is a blue green complex. bis(acetylacetonato)oxovanadium(IV) has a vanadyl group, VO2+. The vanadyl group is holded to 2 acetylacetonate anions and the structure of the compound is as follow-This complex lowlife be made from vanadium(IV) or vanadium(V). In our experiment, bis(acetylacetonato)oxovanadium(IV) was prep ard from vanadium(V) oxide and the equation is as follow-V2O5 + 2H2SO4 + EtOH 2VOSO4 + 3H2O + CH3CHOVOSO4 + 2HC5H7O2 + Na2CO3 VO(C5H7O2)2 + Na2So4 + H2O + CO2(Absolute Astronomy, 2009)Besides that, both of the acetylacetonato (acac) groups of bis(acetylacetonato)oxovanadium(IV) atomic number 18 able to be exchanged with primitive ligands having coordinating atoms of different pote ntialities. (Maurya, 2003)Both Manganese(III) acetylacetonate and bis(acetylacetonato)oxovanadium(IV) are bond with acetylacetonate which known as ligand. The precursor for acetylacetonate is acetylacetone with formula C5H8O2. However, acetylacetonate is an anion. It can bind to corresponding cation but it very hard to exist as a plain ion in solution.In addition, Cobalt is a hard, gray metal. It has a proton number 27. Besided that, there are two types of cobalt ions namely carbonic acid gas+ and Co3+. First, Co3+ ion is more weaker than the Co2+ ion. However, the complex ion formed with higher oxidation state is more stable. ( zmir Institute of Technology, n.d.). So that, Cobalt(III) complexes are kinetically inert.Co3+ can undergo a process known as ligand exchange reactions lento which examined to Co2+ complexes. The cobalt(III) complexes are usually in octahedral shape. In the experiment, chloropentaamminecobalt(III) chloride is being synthesized. The structure is as follow- (Source Chemicalbook.com)The complex is prepared by the oxidation of ammoniacal solution of cobalt(II) salts by using hydrogen peroxide. The formula is as follow-Co2+ + NH4+ + 1/2H202 Co(NH3)5H203+Co(NH3)5H203+ + 3Cl- Co(NH3)5ClCl2 + H20( zmir Institute of Technology, n.d.)Materials and MethodsExperiment one,5g of MnCl2.4H201.3g of NaC2H3O2.3H2O NaC2H3O2.3H2ODissolved in 200cm3 of distilled water.21cm3 of 2HC5H7O2 slowly added1g of KMnO4Present of two-phase layerSolution A added in with stirringDissolved in 50cm3 of distilled water.13g of NaC2H3O2.3H2OSolution B added inSolution ASolution BDissolved in 50cm3 of distilled water.Heated with 60oC for 30 minutesComplex washed with acetoneSolid complex filtered by suctionResultant solution was cooled with cold waterExperiment 2Experiment 35 cm3 distilled water4 cm3 concentrated H2SO410 cm3 ethanolWere added in.RecrystalliseResults For experiment 1,from the equation below, I can get the theoretical mass of the Mn(acac)3 solid state com plex by Mn(H2O)4 Cl + 2HC5H7O2 + NaC2H3O2 Mn(C5H7O2)2 + NaCl + HC2H2O24Mn(C5H7O2)2 + KMnO4 + 7HC5H7O2 + HC2H3O2 5Mn(C5H7O2)3 + KC2H3O2 + 4H2OFrom the equation, we know that 1 seawall of Mn(H2O)4 Cl = 1 gram molecule of Mn(C5H7O2)2.So, 5 g of Mn(H2O)4 Cl = 0.0308 mol is also = 0.0308 mol of Mn(C5H7O2)2.From the second equation, 4 mol of Mn(C5H7O2)2 = 5 mol of Mn(acac)30.0308 mol of Mn(C5H7O2)2 = 0.0385 mol.So, theoretical weight of Mn(acac)3 = 0.0385 mol X 252.938 g/moltheoretical weight of Mn(acac)3 = 9.7381 gThe following shows the method to get our experimental weightWeight of have tube14. 8180 gWeight of try tube + solid complex , Mn(acac)318.7785 gSo, the experimental weight of Mn(acac)3complexes were 3.9605 gPercentage yield of Mn(acac)3complexes we get was = 3.9605 g / 9.7381 g X 100 %= 40.67 %Next, charismatic trice of Mn(acac)3complexes were calculated as follow m = 0.9278g- 0.8193g= 0.1085gRo= -33L = 2.4cmR= 1165 (para magnetised)CBal = 1X(g) = CBal X L X (R-Ro) / 1 09 X mX(g) of Mn(acac)3complexes = 2.65 X 10-5So, Mn(acac)3complexes are paramagnetic rendering of IR spectrum for complexes will be written in discussion.For experiment 2,from the equation below, I can get the theoretical mass of the Co(NH3)5ClCl2 solid complex by Co2+ + NH4+ + 1/2H202 Co(NH3)5H203+Co(NH3)5H203+ + 3Cl- Co(NH3)5ClCl2 + H20From the above equation, 1 mol of Co2+ = 1 mol of Co(NH3)5H2O3+12g of Co2+ = 0.0504 molSo 0.0504 mol of Co(NH3)5H203+= 0.0504 mol of Co(NH3)5ClCl2Theoretical weight of Co(NH3)5ClCl2 solid complexes = 0.0504 mol X 250.433 g/mol= 12.6218 gThe following shows the method to get our experimental weightWeight of ingest tube14. 9285 gWeight of Sample tube + solid complex , Mn(acac)322.3723 gSo, the experimental weight of Co(NH3)5ClCl2 solid complexes = 7.4438 gPercentage yield of Co(NH3)5ClCl2complexes = 7.4438 g / 12.6218 g X 100 %= 58.98 %Next, charismatic moment of Co(NH3)5ClCl2complexes were calculated as follow m = 0.9264g- 0.8207g= 0.1057gRo= -36 L = 2.1cmR= -41 (dimagnetic)CBal = 1X(g) = CBal X L X (R-Ro) / 109 X mX(g) of Co(NH3)5ClCl2complexes = -9.9338 X 10-8So, Co(NH3)5ClCl2complexes are dimagneticFor experiment 3,from the equation below, I can get the theoretical mass of the Vo(acac)2(H2O) solid complex by V2O5 + 2H2SO4 + EtOH 2VOSO4 + 3H2O + CH3CHOVOSO4 + 2HC5H7O2 + Na2CO3 VO(C5H7O2)2 + Na2So4 + H2O + CO2From the above equation, 1 mol of V2O5 = 2 mol of VOSO42g 0f V2O5 = 0.011 mol = 0.022 mol of VOSO42 mol of VOSO4 = 2 mol of VO(C5H7O2)2Theoretical weight of VO(C5H7O2)2= 0.022 mol X 264.94 g/mol= 5.8287 gThe following shows the method to get our experimental weightWeight of Sample tube14.8445 gWeight of Sample tube + solid complex , Mn(acac)318.5818 gSo, the experimental weight of VO(C5H7O2)2= 3.7373 gPercentage yield of VO(C5H7O2)2= 3.7373 g / 5.8287 g X 100%= 64.12%Next, Magnetic moment of impure VO(C5H7O2)2 complexes were calculated as follow m = 0.8880g 0.8244 g= 0.0636gRo= -34L = 2.5cmR= 72 (paramagnetic)CBal = 1X(g) = CBal X L X (R-Ro) / 109 X mX(g) of impure VO(C5H7O2)2complexes = 4.17 X 10-6So, VO(C5H7O2)2complexes are paramagneticMagnetic moment of pure VO(C5H7O2)2 complexes were calculated as follow m = 0.8947g -0.8211= 0.0736gRo= -33L = 2.3cmR= 144 (paramagnetic)CBal = 1X(g) of pure VO(C5H7O2)2complexes = 5.53 X 10-6Discussion Interpretation of IR spectrum for tris(acetylacetonato)manganese(III)Wavenumber (cm-1)Description of bands2921.1 2959.7-relative military capability weakCH stretchiness of CH31593.91508.0-relative intensity material-(C=C) stretching-(C=CH) deformation1387.2-relative intensity unanimous-(CH3)- symmetric C-H deformation1253.5-relative intensity substantive-(C=C) stretching-(C-CH3) stretching1016.8-relative intensity strong-(CH3) out-of plane bending923.2-relative intensity strong-(C-CH3) stretching777.0-relative intensity strong-(C-H)deformation678.1-relative intensity medium/ strong-(C-CH3)stretching,(O=C-CH3) deformation-(Mn-O) stretching indicat es metal-ligand bond460.1 relative intensity weak (C=C) stretching,(C-CH3) stretching-(Mn-O) stretching that also indicates metal-ligand bondInterpretation of IR spectrum for chloropentaamminecobalt(III) chlorideWavenumber (cm-1)Description of bands3258.0-relative intensity strongNH3 stretch1576.2-relative intensity medium-degenerate asymmetric NH3 stretching1307.8-relative intensity strong-symmetric NH3 angle deformation844.9-relative intensity strong-NH3 rocking487.6-(Co-Cl) stretching indicates metal-ligand bondInterpretation of IR spectrum for impure bis(acetylacetonato)oxovanadium(IV)Wavenumber (cm-1)Description of bands1556.81521.0-relative intensity medium (C=O) stretching-( C=C),(C=CH) stretching1418.7-relative intensity medium-(CH3) deformation1374.01357.6-relative intensity strong-(C=O) stretching-(CH3) deformation mode1286.6-relative intensity strong-(C=C=C) stretching998.2-relative intensity strong and sharp-stretching of V=O bond-it also indicates the metal-li gand bond.1018.6-relative intensity strong-(CH3) rocking936.1-relative intensity strong-(C-CH3) stretching-(C=O) stretching798.6-relative intensity medium-(C-H) out-of-plane bending685.9657.2-relative intensity medium/ weak-(ring) deformation out-of-plane bending for609.2-(ring) deformationInterpretation of IR spectrum for pure bis(acetylacetonato)oxovanadium(IV)FTIR is known as Fourier Transform Infrared Spectroscopy. This FTIR can be used to identify different types of chemical bond which is either organic compound or inorganic compound. So no two different compounds will have same spectrum. However, FTIR may cause destructive to our sample compare to magnetic strength which is non-destructive. Besides that, magnetic susceptibility can be group by paramagnetic, diamagnetic and ferromagnetic. Paramagnetic substance is those attracted by strong magnetic field but those repelled by magnetic field are diamagnetic substances.Besides that, we can also confirm the shape by using ma gnetic susceptibility. The Cobalt ion to form Chloropentaamminecobalt(III) chloride has 6 electron in d orbital.Magnetic Susceptibility for chloropentaamminecobalt(III) chloride is -9.9338 X 10-8 and it is diamagnetic. Only the low-spin octahedral shape shows diamagnetic properties, so the shape of chloropentaamminecobalt(III) chloride is octahedral.Magnetic Susceptibility for tris(acetylacetonato)manganese(III) is 2.65 X 10-5 and it is paramagnetic. So the shape of tris(acetylacetonato)manganese(III) is octahedral. However we cannot determine whether is low-spin or high-spin in this situation because we are not calculating the p porting energy for the complex.In addition, there is only one electron in d orbital for vanadium ion of bis(acetylacetonato)oxovanadium(IV). Magnetic susceptibility for it is 4.17 X 10-6 and it is paramagnetic.Moreover, oxovanadium complexes act as insulin representationals, nucleolytic and anticancer.To recognize insulin- mimetic complexes, a simple and f ast in-vitro assay is developed. Besides that, an accurate assessment of the cells taken up of glucose, in-vitro assay with Ehrlich can be used. The oxovanadium complexes can cleave deoxyribonucleic acid without the present of hydrogen peroxide. Then, its nucleolytic efficiency is also greater but it is affected by the choice of buffer and pH. The oxovanadium complexes is also an anticancer agent against human ovarian cancer.Actually, I have acquired a lot of new knowledge among these three experiments. First, experiment one and two are easier to carry out compared to experiment three. This is because experiment one and two involved oxidation which Mn2+ was oxidized to Mn3+ Co2+ was oxidized to Co3+. Whereas experiment 3 involved reduction which reduced VO5+ to VO4+. At the beginning of from each one experiments, we heated up the sample in open air. It is easier to oxidize the compound than reduce the compound in the presence of oxygen. So, we need more clip to heated the V2O5. During the first time of experiment three, I failed to get a blue color solid powder. This is because I heated the sample in the open air and I failed to control the heater. So, after the filtration process, I got a white solid powder. Therefore, I learnt from the mistake and during the second time I used reflux method. This time I can control the heating process well. The ethanol was not evaporated much. After filtration, I got quite a lot of blue solid powder. So, I knew that, for reduction process, we cannot heat the sample too quickly and heat too long. If we heated too long, most of the product will evaporate.Next, from the FTIR spectrum, I can see that the spectrum from the first and third experiment are quite similar. This is because, the peak from the spectrum are for the most part from the acetylacetonato (acac). However, spectrum from experiment two is quite different from other experiment because mostly the peaks come from Cl compared to other experiments.The percentage yield of the complexes from all the three experiment that I have calculate out was not so high. This is by chance due to the washing of the product with acetone, some of the product was dissolved and washed away. However, there are other factors which cause problem to our results. First, most of the heating central office we used cannot function well. I changed many heating plate during the experiment. Next, we have kept our half way done sample for more than 7 days. The results may not be so accurate anymore. Another factor maybe due to the volume and amount of the sample and other material we measure are not accurate. Our product may contain some impurities.However, some of the precaution was taken during the experiment. In these experiments, some of the chemical was corrosive and poisonous such as concentrated HCl and H2SO4. So, we poured the chemical carefully in the fume board. Next, before using any instrument, we read through the manual to understand the steps to function the magnetic susceptibility balance. We also taken down some important steps to function the FTIR spectrophotometer. I have asked some help from lab assistant on where to get the material for experiment.ConclusionThe percentage yield for tris(acetylacetonato)manganese(III) is 40.67%, chloropentaamminecobalt(III) chloride is 58.98% and (acetylacetonato)oxovanadium(IV) is 64.12%.For tris(acetylacetonato)manganese(III), the peak for two Mn-O bond are at the region approximately 678.1 cm-1 and 458.3 cm-1. For chloropentaamminecobalt(III) chloride, the peak for Co-N bond is at 669.2 cm-1 while Co-Cl bond is at 486.2 cm-1. For bis(acetylacetonato)oxovanadium(IV), the peak for V=O bond is at 997.4 cm-1 region.Magnetic Susceptibility for tris(acetylacetonato)manganese(III) is 2.65 x 10-5 and it is paramagnetic. Besides, Magnetic Susceptibility for chloropentaamminecobalt(III) chloride is -9.93x 10-8 and is diamagnetic. For bis(acetylacetonato)oxovanadium(IV), magnetic susceptibility for imp ure complex and pure complex are 4.17X 10-6 and 5.53X 10-6 respectively. They are paramagnetic.