تحضير ودراسة تحليلية - طيفية لبعض اصباغ الازو غير المتجانسة واستخدام احدها في استخلاص النحاس الثنائي من المحاليل المائية == Preparation and Analytical Study of Some Heterogeneous Azo Dyes and Using One of Them in Extraction of Cu(II) From Aqueous Solutions
Author name:
لمياء عبد اللطيف رسن
Supervisor name:
اسعد عبود علي
General topic:
Chemistry
Specific topic:
Chemistry
Degree:
Doctorate
University:
University Of Basrah - College Of Education For Pure Sciences
Language:
Arabic
University location:
Basrah
First pages:
25T1598 - p.pdf
Abstract:
The thesis involves three parts : The first part included synthesis eight new Azo dyes,derived of Procaine and Metoclpramide : LR1R = 3 - [ ( Procaine ) azo ] - 2 - hydroxyl indoleLR2R = 2 - [ ( Procaine ) azo ] - 4,5 - diphenyl ImidazolLR3R = 2 - [ ( Procaine ) azo ] - 3 - PhenylephrineLR4R = 2 - [ ( Procaine ) azo ] Imidazol, L5 = 2 - [ ( Metoclopramide ) azo ] Imidazol,LR6R = 2 - [ ( Metocopramide ) azo ] 3 - PhenylephrineLR7R = 3 - [( Metoclopramide ) azo ] 2 - hydroxyl indoleLR8R= 2 - [( Metoclopramide ) azo ] - 4,5 - diphenyl ImidazolThey have been described by C.H.N. and Visible spectroscopic spectra and the functional groups were characterized by I.R technique like azo group of (1558.48 , 1512.19 ,1581.63 , 1508.12 , 1521.84 , 1529.55 , 1517.98 , 1533.14 ) cm - P 1 P for azo dyes (LR1R LR2R , LR3R , LR4R , LR5R , LR6R , LR7R , LR8R) respectively The Acid - Base properties were also studied spectrophotometric using buffer solutions of pH values of (0.67 - 12) in the visible region, From the spectra obtained the protonation an ionization constants of azo dyes were determined by using Half - Height method ,the isopiestic point were also established ,which indicated the suggested mechanism for the ionization and protonation steps.The effect of solvents of different polarities was also studied on the spectra shift in the visible region. It was found that linearity relation between the dielectric constants of solvents and λRmaxR this denotes the dielectric constants at the mediumis the main factor governing the band shift, except for (LR6R) azo dye which give little deviation from linearity . The second part concerns with the ability of azo dye (LR8R) for forming complex with Cu(II) , The optimum conditions for forming stable azo dye - complex were studied like pH effect , kind of buffer solution , time effect and sequence of addition of reagents by aid molar ratios method and Continuous variation method It was found that stable complex was obtained with stoichiometry of 1 : 2 ( M : L ) From calibration curve of (L8) complex , : Sandell sensitivity 2.492× 10 - 3 μg cm - 2, Detection limit 0.00977 μg ml - 1, Standard deviation 0.00193, Correlation coefficient 0.994 , molar absorbitivity coefficient 2.547×104 L mol - 1cm - 1 , specific absorbtivity 0.4012 ml g - 1cm - 1 and obeyness of Beer's law linearity up to 3.20 ppm The effect the interference of some important cations and anions of concentration (1 - fold, 5 - fold and 10 - fold ), the stability of this complex was showed through determination of their conformation constants (stability constants) by use the corresponding solution method ,by aid of using half value method .this complex had been characterized by (FT - IR) according to the different of shift relativity abundance of same active groups bundle complex comparison with privately dyes ; the azo group ( - N=N - ) and (C=N) groups.,the percentage to metal (Cu) in the complex determine by using of result Atomic Absorption Spectroscopy where found approximate the same between theoretical and measurement.The third part : involved solvent extraction of Copper(II) ions from its aqueous solution by using L8 to organic solution. This study include limitation of optimum conditions for complex formation of highest observed absorbance of λmax at complex : such as (pHex=7) ,ions concentration Copper(II) 15μg effect shaking time of two immiscible phase 15 min .the distribution ratio (D*).and extraction percentage (%E) were determination.Organic solvent effect study appeared there is not any linear relation between dielectric constant (D) of organic solvents and distribution ratio (D*) that’s mean there is not any effect for polarity of organic solvent on extraction method but there is an effect for organic solvent structure which is participate in the structure of ion pair complex extracted by formation tight ion pair or loose ion pair as well experiment result illustrate chloroform organic solvent it was the best organic solvent in extraction .Thermodynamic study include Temperature effect on extraction efficiency the experimental results demonstrate the reaction was exothermic for Copper(II) with organic reagent (LR8R) endothermic reaction , after calculation thermodynamic data ΔHRexR , ΔGRexR , ΔSRex Rshow entropy values was high that is mean complexion reaction is entropic in region
