Abstract

         This study involves  synthesis and identification of two new ligands.   The first ligand was synthesized  by reacting of para-aminoacetophenone with 2-naphthol  as first step via diazotization reaction,  then reaction with 2-aminophenol as a second step to give the ligand 1-((4-(1(2-hydroxyphenylimino)ethyl) phenyl) diazenyl)naphthalene-2-ol (HPEDN). The second reagent was prepared via diazotization  from the reaction of sulfadiazine with imidazole to give the ligand    4 – (imidazole-2-yl) diazenyl) -N- (pyrimidin-2yl)benzenesulfonamide (IDPBS).

         These  ligands were characterized using¹H-NMR spectroscopy,¹³C-NMR spectroscopy and , Fourier transform Infrared spectroscopy (FT-IR) .

         The prepared  Complexes of these tow ligands were synthesized with metal ions, Co(II),Ni(II)and Cu(II). The ligands and their complexes were investigated  by determining some of their physical properties such as  solubility, melting point, molar electrical conductivity and Fourier transform Infrared spectroscopy (FT-IR).

         The optimal conditions for the formation of these complexes were studied such as concentration of the used reagents, pH, time  of period for the stability of the formed complexes, effect of temperature, the order of addition of the concentrations of  reaction components,  that obey Beer-Lambert’s law were determined by calibration curves within the range (1.1-7.1,0.5-7.6μg/mL) for nickel (II),(0.5-7.6,1.1-7.6μg/mL)for cobalt)II) and (0.6-8.2,1.2-8.2μg/mL) for the copper  (II) with (HPEDN),(IDPBS)ligands respectively.

         The composition of the complexes was studied by finding the ratio of metal ion to ligand)M: L) using continuous variation  method, molar ratios method and analytical slope method. The results indicate that the ratio was (1:2) )metal: ligand(for both ligand complexes. The stability constants were calculated and found (3.065×10⁹ ,4.965×10⁹ , 8.728×10⁹)for cobalt(II (,nickel)II) and copper(II) complexes with ligand )HPEDN) and (3.366×10⁹, 4.918×10⁹ , 5.827×10⁹)for cobalt)II( ,nickel(II)  and copper(II) complexes  with ligand (IDPBS).

         The correlation coefficient, Sandell sensitivity and molar absorption coefficient were determined and they were as follows(0.9996,0.0193,0.3475×10⁴ and 0.9997,0.0221,0.2648×10⁴ and 0.9998,0.0176,0.3600×10⁴).for cobalt(II), nickel(II) copper(II) complexes  with ligand )HPEDN) and(0.9996,0.0142,0.4134×10⁴ and 0.9995,0.0177,0.3317×10⁴ and 0.9994,0.0241,0.2628×10⁴)for cobalt (II) ,nickel)II( and copper(II)complexes  with ligand(IDPBS).

           In addition the, thermodynamic functions ⁰GΔ  ,ΔHº and , ΔS⁰  were calculated for the synthesized complexes  at different temperatures (308,303,298,293,288K) .The charge of the dissolved complexes was determined by using the molar electrical conductivity. The result showed that two (HPEDN ( and (IDPBS) complexes were un charged. According to this study, we can concluded that the shape of the prepared complexes were octahedral.                       

         Also, precision , accuracy and sensitivity of the spectral analytical method  were determined using standard solutions of selective ions with standard solutions of ligand, from which standard deviation, relative standard deviation and percentage error were calculated its limits did not exceed (±5) and percentage Recovery, for three concentration, it was concluded that the spectral method used is of good accuracy, precision and sensitivity.                      

         This spectrophotometric method was successfully applied in different alloys models to determine of copper and nickel using reagents and compare the obtained results  with the results of flame atomic absorption. The results were convergent and good, indicating that the  used  method in this study is rapid, economical, sensitive and highly selective.