Spectrophotometric determination of the species

Nickel(II) complex present when water is substituted

by EN.
62%
C Stoltz*
* [email protected]

ABSTRACT

The Ni2+ 1, 2−diaminoethane (EN) system was investigated. To determine what species was present in the solution a series of
solutions with different mole fractions of EN was prepared and measured at different wavelengths using a spectrophotometer.

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1 Introduction
A coordination compound or complex consists of a central atom (metal) that acts as a Lewis acid and attached ions (ligands)
that acts as Lewis bases. If other ligands are added to the solution of aqueous metal ions, the water molecules that are weak
Lewis bases can be replaced. When formed the complex cannot be isolated as a stable compound to be determined individually.
To determine the stoichiometry of a metal-ligand complex the method of continuous variation, also known as Job’s
method, can be used. Solutions are prepared, each with a varying mole fraction of the reactants, but keeping the total
molecular concentration of the metal and the ligand reactants equal to one. Complex ions are usually coloured differently
from their component solutions thus the monochromatic light absorbed by the resulting solutions can be measured using a
spectrophotometer1 . The corrected absorbance is plotted as a function of the ligand (or metal) concentration in the flasks. The
curves gives a maximum that corresponds to the metal ligand ratio2 .
This experiment will be performed to identify what domonant complex ion is formed in the prepared solutions reacting aque-
ous Nickel(II) and diaminoethane(EN). The 11 solutions of different mole fractions ranging from 0 to 1 will be measured and the
absorbance plotted. The average of the maximum can be used to calculate the value of n for the species [Ni(H2 O)6−2n (en)n ]2+ .

2 Experimental Procedure
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3 Results

Table 1. Absorbance of different solution mole fractions at different wavelengths.

Absorbance
x 530nm 545nm 575nm 620nm 640nm
0.00 0.070 0.079 0.122 0.295 0.315
0.10 0.092 0.095 0.172 0.345 0.342
0.20 0.103 0.100 0.210 0.400 0.405
0.30 0.111 0.150 0.270 0.432 0.443
0.40 0.121 0.190 0.300 0.465 0.470
0.50 0.166 0.236 0.365 0.480 0.475
0.60 0.235 0.306 0.420 0.422 0.375
0.70 0.366 0.440 0.444 0.288 0.280
0.80 0.347 0.324 0.305 0.130 0.052
0.90 0.189 0.195 0.148 0.056 0.040
1.00 0.020 0.015 0.012 0.005 0.009

Open Rubric
Table 2. Corrected absorbance of different solution mole fractions at different wavelengths using equation
Y = Dmeasure − (1 − x)Dm .

Absorbance
x 530nm 545nm 575nm 620nm 640nm
0.00 0.000 0.000 0.000 0.000 0.000
0.10 0.029 0.024 0.062 0.080 0.059
0.20 0.047 0.037 0.112 0.164 0.153
0.30 0.062 0.095 0.185 0.226 0.223
0.40 0.079 0.143 0.227 0.288 0.281
0.50 0.131 0.197 0.304 0.333 0.318
0.60 0.207 0.274 0.371 0.304 0.249
0.70 0.345 0.416 0.407 0.200 0.136
0.80 0.333 0.308 0.281 0.071 -0.011
0.90 0.182 0.187 0.136 0.027 0.009
1.00 0.020 0.015 0.012 0.005 0.009

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Y calculation for 520nm, at mole fraction 0.01. Y = Dmeasure − (1 − x)Dm Y = 0.092 − (1 − 0.10)(0.070) Y = 0.029

Figure 1. Graph of absorbance versus mole fraction of thylenediamine at wavelenght 530nm.

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Figure 2. Graph of absorbance versus mole fraction of thylenediamine at wavelenght 545nm.

Figure 3. Graph of absorbance versus mole fraction of thylenediamine at wavelenght 575nm.

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 Figure 4. Graph of absorbance versus mole fraction of thylenediamine at wavelenght 620nm.

Figure 5. Graph of absorbance versus mole fraction of thylenediamine at wavelength 640nm.

Xmax can be determined where the slope of the points before the maximum absorbance and the slope of the points after the
maximum absorbance intersects.

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Table 3. The maximum absorbance (Xmax ) and the corresponding moles (n) for [Ni(H2 O)6−2n (en)n ]2+ calculated using the
equation n = Xmax /(1 − Xmax ).

Wavelength Xmax n
530nm 0.76 3.17
545nm 0.73 2.70
575nm 0.70 2.33
620nm 0.55 1.22
640nm 0.53 1.13

The average of n across all five wavelengths is n = 2.11 rounded to n = 2 thus making the species

[Ni(H2 O)4 (en)]2+ (aq) +en K2 [Ni(H2 O)2 (en)2 ]2+ (aq) + 2H2 O
←
→

4 Discussion
The value of n was determined to be n=2, which indicated that the Nickel (II) complex formed as shown in the results section
(3). The average of the Xmax = 0.65 which corresponds to a 2:1 ligand:metal ratio2 .
Nickel (II) can form complexes with different ligands leading to several complexes coexisting in the same solution, thus
pure reagents must be used to avoid ambiguous results. Precise measurement of reactant volumes are crucial fot the success of
Job’s method, calibrated glassware should be used.

5 Conclusion
N/A

References
1. Vosburgh, W., Cooper, G. & Am, J. Complex ions. i. the identification of complex ions in solution by spectrophotometric
measurements. SPECTROPHOTOMETRIC IDENTIFICATION OF COMPLEX IONS IN SOLUTION 63, 437 (1941).
2. MacCarthy, Z. D. H. P. Novel approach to job’s method. J. Chem. Educ. 63, 162 (1986).

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