Ligand/Metal Ratio
How to calculate the ligand/metal ratio, graph plotted is absorbance against CL/CM values. After plotting the graph, a trend line equation for the two plots is set equal to one another and the value of X is calculated.
X represents the ligand
MA = 0.2882/392.2/0.1000
= 0.00734
MB = MAVA/VB
7.34 (25)/2.50 = 7.34*10-4Y =0.2467x 0.0265
Y=4E-16x+0.699
0.2476x-0.0265 = 4E-16X+ 0.699
X = b/a
2.93/0.9 = 3
Slope Ration Method
Slope Ratio Method: Absorbance versus Fe (11) ions
VL (mL) VM (mL) CL (M) CM (M) Transmittance (%) Absorbance
10.0 0.5 0.5 8.40E-04 1.40E-05 65.0 0.1871
10.0 1.0 1.0 8.40E-04 2.80E-05 43.0 0.3665
10.0 1.5 1.5 8.40E-04 4.20E-05 28.1 0.5513
10.0 2.0 2.0 8.40E-04 5.60E-05 19.0 0.7212
1.0 2.5 2.5 8.40E-04 7.00E-05 13.0 0.8861
Slope Ratio Method: Absorbance versus Ligand
VL (mL) VM (mL) CL (M) CM (M) Transmittance (%) Absorbance
1.0 5.0 2.80E-05 1.40E-04 78.0 0.1079
2.0 5.0 5.60E-05 1.40E-04 60.0 0.2218
3.0 5.0 8.40E-05 1.40E-04 46.0 0.3372
4.0 5.0 1.12E-04 1.40E-04 34.6 0.4609
5.0 5.0 1.40E-04 1.40E-04 26.0 0.5850
From the two tables shown above and using that data, two graphs are plotted: Absorbance versus Fe (11) ions and Absorbance versus Ligand
The calculation will be as follows:
Absorbance versus Ligand: y= 4261.8x 0.0154
M1 = 4261.8 M -1
Absorbance versus Fe (11) ions: y = 12519x + 0.0166
M2= 12519 M 1
The ligand/metal ratio is therefore calculated from the Beers Law equation.
Using the Slope Ratio Method together with the equation of the Beer Law, the molar absorptivity is thus calculated.
Mean = 12652 mol/cm
Jobs Method of Continuous Variations
A graph of absorbance versus volume (Fe (111)) is plotted. It is important to note that the tangents of the curve when the volume is 0 ml and 10 ml are calculated using the derivative of the equation.
Y = 0.0072*2 + 0.0713x + 0.0129
Y = 0.0144x + 0.0713
Using Jobs Technique
Fe (111) y * The Equations intercept
0.0y (0)=0.071318 y (x) = 0.071318x
10y (10) = 0.072867 0.728672 y2 (x) = -0.072867x + 0.72867
The ligand mole ratio is established though the intersection of the tangent lines.
0.0713x + 0 = -0.0729x + 0.729
x = 5.055 ml
Fraction of the mole = 0.5055
The value of X calculated in the above equation is used to calculate the value of y.
Y = 0.0713X + 0
Y = 0.0713 (5.055) + 0
Y= 0.360
The values of A (x) and A max are therefore
A (X) 0.071318X = -0.072867X + 0.72867
0.144186X = 0.728672
X= 5.055
A(X)= 0.07131 (5.055) = 0.36042
Amax y = -0.007209*2 + 0.07318x + 0.01294
Y = 0.01441X + 0.07131 = 0
X = 4.94638
Determination for the value of Kf
V (Fe 11) ml V (Ligand) ml Amax A CM CL A/Amax*Clim
4..6 0.28527 0.19033 3.20E-04 4.80E-04 2.14E-04
4.5 0.32093 0.19629 3.60E-04 4.40E-04 2.20E-04
5.5 0.35659 0.19864 4.00E-04 4.00E-04 2.23E-04
5.54.5 0.39228 0.19738 4.40E-04 3.60E-04 1.81E-04
6.4 0.42791 0.19252 4.80E-04 3.20E-04 1.44E-04
Through the application of the formula below, the value of Kf is thus calculated
CM (A/Amax)*Clim
CL- (A/Amax)* Clim Kf pKf
1.06E-04 2.66E-04 7.52E+03 3.88E+00
1.40E-04 2.20E-04 7.16E+03 3.86E+00
1.77E-04 1.77E-04 7.10E+03 3.85E+00
2.59E-04 1.79E-04 3.91E+03 3.59E+00
3.36E-04 1.76E-04 2.43E+03 3.39E+00
The mean is therefore 5.63 E+03, 3.75E +00
Therefore
Ligand/Metal Ratio from the three methods
Jobs method 1.01940/1 3.75
Slope Ration Method 2.9375/3 1265. 2
Mole Ratio Method 2.99 = 3
As can be seen from the above, the ratio is about 3. This figure, three, represents the stoichiometric ratio between the ligand and the metal in the solution.
Percentage ratio in the Mole Ratio Method = 1/3
Ligand/Metal Ratio (Slope Ratio Method) = 3
Percentage error 2.08%
Ligand/Metal Ratio (Jobs method) 1
Percentage error 1.9%
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