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Calculation of magnetic moments of CoL2X2 complexes. Objectives. * To explain how the mass susceptibility can be calculated.?. * To explain how the molar susceptibility can be calculated from the mass susceptibility.?.
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Objectives * To explain how the mass susceptibility can be calculated.? * To explain how the molar susceptibility can be calculated from the mass susceptibility.? * To explain how the diamagnetic correction is carried out on xM to calculate xpara..? * To explain how the magnetic moment can be calculated.? * To predict the geometries and the spin state of the Co(II) complexes using magnetic moments.?
Co(2-Me-py)2(SCN)2 1 2 3
Co(2-Me-py)2(SCN)2 4.2439 4 6 7 5 4.2825
(m)- (0.029 10-6 )V = (- ) Where m = tube filled with solid – empty tube • = empty tube field on – empty tube field off • = tube filled with solid, field on – tube filled with solid, field off V = (tube filled with water – empty tube) / density of water gof standard = 16.44E-6 cgs
Calibration Constant we calculate (calibration constant) by using m, and Xg(mass susceptiblity )of the standard : (m)- (0.029 10-6 )V = (- ) X(g)= 16.44x10-6 cm3/g(emu/g)
(m)- (0.029 10-6 )V = (- ) By using the value of we calculate X(g) of the sample :
Diamagnetic correction of magnetic susceptibility para= M - dia
Total= -1.9058x10-4 cm3/mol. AND Remember that this unit = emu/mol
From this value. How can you determine the geometry and the spin state of the complex..?
Octahedral Co2+ (d7) High Spin Co2+ (d7) Low Spin eg eg t2g t2g
Tetrahedral Co2+ (d7) only High Spin t2 e
The magnetic moment of tetrahedral geometry is in range(4.30 – 4.74 B.M.) and absorb light strongly at range (580-780) nm.
The magnetic moment of octahedral geometry is in range(4.90 – 5.40 B.M.) and absorb light weakly in the range (640-600 nm)
Co(2-Me-py)2(SCN)2 High λ Low ∆0 HS. ueff= 4.95 BM Tetrahedral (4.30-4.74 ) BM
Summary 1.Magnetic moments are used to determine the spin state (high spin or low spin). 2.Octahdral complexes can be either high spin or low spin. 3.Tetrahedral complexes can only be high spin. 4.Experimental magnetic moments for Co(II) Complexes are always higher than the spin-only magnetic moments because of the significant Orbital contribution .
5.The magnitude of the orbital contribution differ for tetrahedral and octahedral ,it is greater for octahedral than for tetrahedral. Therefore ,we can distinguish between tetrahedral and octahedral. Tetrahedral; 4.30 – 4.72 B.M. Octahedral; 4.90 – 5.40 B.M.
References 1- Gary L.Miessler, Donald A. Tarr, “Inorganic Chemistry”,3rd Edition, 2- D.P.Graddon ,E.C.Watton,auet.J.Chem, 1965,pp 507-520.