التقدير الطيفي لايونات الكوبلت والنيكل والنحاس ثنائية التكافؤ في محاليلها المائية باستخدام كاشف ازو- شف جديد مشتق من -4امينوانتي بايرين

Spectrophotometric Determination of Divalent Cobalt and Nickel and Copper Ions in aqueous Solutions Using a New Azo-Schiff reagent Derived from 4-Aminoantipyrene

The study in this thesis included the preparation and diagnosis of a new azo ligand type (4-ASNA). Two steps were taken to prepare the new azo ligand .The first step involved preparing a Schiff base by reacting -4 aminoantipyrine with Salicyaldehyde and then reacting the reaction product with P-nitroaniline as a second step to give the reagent 4-(2-hydroxy-5-((4- nitrophenyl)diazenyl)benzylideneamino)-1,5-dimethyl-2-phenyl-1H- pyrazol-3 (2H)-one(4ASNA) and the detector was identified using UV spectroscopy, infrared spectroscopy (FT-IR), and proton nuclear magnetic resonance spectroscopy (1H-NMR), and then its complexes were prepared with metal ions (Cu(II), Ni(II). Co(II), and these complexes were studied using the same previous techniques, while studying some of their physical properties such as melting point, solubility, electrical conductivity, an magnetic susceptibility.
The ideal circumstances for formation of the three complex were also determined, such as the concentration of the reagent, pH effect, the period for the stability of the formed complexes, the effect of temperature, and the order of addition were studied. The obeyed of the Beer-Lambert law were al determined through calibration curves and were within the range (0.1 7.5)µg/ml, (1.5-8) µg/ml, (0.1-12.5) for Co (II), Ni (II), and Cu (II) complexs respectively.
For Co (II), Ni (II), and Cu (II) complexes, the Sandel sensitivity, molar absorption coefficient, and correlation coefficient were determined within the ranges of 4.533×10-4µg/cm², 14.971 x10-3ug/cm², and 9.012×10-4 μg/cm²) (1.30×105, L\MoL.cm 3.29×10³, L\MoL.cm 7.05×104 L\MoL.cm)
The stoichiometry of the prepared complexes was also studied by determining the ratio of metal ions to the reagent using, Continuous variation method, the Mole ratio method (M:L), and the slope analysis. The results showed that the ratio was (1:2) for all complexes. The stability constants were also calculated (L\moL). 1.65×108, 6.41×108 L\moL, 3.94×108 L\moL) for (II) Co, (II) Ni, and (II) Cu complexes, respectively.
The thermodynamic functions (∆G, ∆H, ∆S) were also calculated for the formation of the prepared complexes under study at temperatures K (338-288). It was found that the stability constants of the complexes decrease with increasing temperature because they are heat-emitting reactions and all complex formation reactions occur spontaneously, and this What was observed through the values of the change in the free compression energy, and the charge of the dissolved complexes was determined using the electrical conductivity and magnetic susceptibility device. The result was that Cobalt and Copper complexes were uncharged but Nickel complex was charged , and from this we conclude that the complexes formed are octahedral for Cobalt and Copper complexes and squar planer for Nickel complex .
The extent of compatibility, accuracy and sensitivity of the spectroscopic analysis method used was determined using standard solutions of the selected ions with standard solutions of the detector, and through it the standard deviation, the percentage relative standard deviation, and the percentage relative error were calculated, the limits of which did not exceed (±1), and the recovery rate was calculated by three Different concentrations, from which we conclude that the spectroscopic method used has good accuracy, precision, and sensitivity.