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استخلاص نقطة الغيمة بالازدواج مع طريقة طيفية لاستخلاص وتقدير النيكل (??) والكوبلت (??) والبزموث (?I?) في نماذج مختلفة باستعمال مشتقي ازو مناسبين == Cloud point extraction coupled with spectroscopic method for separation, extraction and determination of Nickel( ?? ) , Cobalt( ?? ) and Bismuth ( I?? ) in different samples by use of suitable Azo - derivatives
Author name:
احمد صادق عبد هاشم الحمادي
Supervisor name:
شوكت كاظم جواد
General topic:
Chemistry
Specific topic:
Analytical Biochemistry
Degree:
Master
University:
University of Kufa - College Of Education For Girls - Chemistry Department
Language:
Arabic
University location:
Najaf
First pages:
25T1570 - p.pdf
Abstract:
Cloud point extraction methodology was used for separation, preconcentration and extraction cations for Bismuth(III) , Nickel(II) , Cobalt(II) as ion association complexes by two new laboratory prepared azo derivatives as complexing agents which are MIBSHA and AADAD as well as these new organic complexing agents studied spectrophotometricaly by UV - Vis spectroscopy and IR specrtrophotometry to confirm their structures and for the separation, preconcentration and extraction of the elements in this study which was performed as follows : 1 - Bismuth(III) Studies : At the beginning an experiment was conducted to determine the wave length of ion association complex of bismuth ion Bi(III) with new laboratory prepared complexing agent MIBSHA by UV - Vis, spectroscopy and the spectrum showed λmax=550nm. Under optimum conditions of extraction Bi(III), the study showed that pHex=9 was more stable for extraction and gave higher efficiency because at this acidic function, there exists the best coordination bounding between Bi(III) and MIBSHA in presence of 40 μg of Bi(III) as optimum concentration giving favorites thermodynamic equilibrium for complex formation and this method of extraction depends on using Non - ionic surfactant 1% Tritonx - 100. And experimental study showed that 0.5ml of this surfactant suitable for forming Cloud point layer (CPL) with higher density and smaller volume to give the best extraction efficiency for Bi(III) with high absorbance and distribution ratio (D). The extraction efficiency also increased with increasing MIBSHA concentration as linear relation because any increasing in MIBSHA concentration is mean increasing in ion pair complex concentration and suitability so increasing in the thermodynamic equilibrium partition to the CPL. And this reflects the sensitivity of new complexing agent MIBSHA in coordination binding and ion pair complex formation in addition to extraction CPE methodology which depends on heating. The experimental study shows that the optimum temperature of heating was (90°C) that gives higher extraction efficiency because it allow to reached the best thermodynamic equilibrium in Cloud point layer formation with good dehydration, as well thermodynamic data was ΔHex=0.145KJ mol - 1, ΔGex= - 73.786KJmol - 1and ΔSex=203.669Jmol - 1K - 1 whereas the low value of enthalpy for Demonstrate extraction to approach another ion of ion pair association complex, also the extraction method is entropic region, and the experimental study about the effect heating time was 20min was the optimum heating time which gives the higher extraction efficiency with high absorbance and distribution ratio D, as this time of heating helps to reach the optimum thermodynamic equilibrium of Cloud point layer formation CPLwith higher dehydration from other hand time of heating indicate the quantity of heat which162is help to dominate on the moving of micelles inside formation cloud point layer CPL with good properties of extraction. Stoichiometric study by using four spectrophotometric methods and the study revealed that the more probable structure of ion pair complex of Bismuth ion Bi(III) extracted was [1 : 1]+ anion [Bi(MIBSHA)]2+;2No3 - experimented study about synergism effect by using Tri butyl phosphate (TBP) and methyl isobutyl ketone (MIBK) show that the extraction efficiency for bismuth ion Bi(III) increased with the presence of TBP or MIBK in aqueous solution by the effect of TBP and MIBK participation in the complex formation of Bi(III) also the experiments showed that there is one molecule of TBP or MIBK enters in the structure of ion pair complex of Bi(III) as [Bi(MIBSHA)(TBP)]2+;2NO3 - ; [Bi(MIBSHA)(MIBK)]2+;2NO3 - and TBP or MIBK enter in the complex instead of water molecule in the hydration shell of Bi(III) and increase hydrophobicity of ion pair complex and increased rate of partitioning to the CPL. As well as this study involved experiments about interferences effects as well as electrolytes effect and these experiments illustrated interferences effect to decline extraction efficiency because these ions form ion pair complex with complexing agent MIBSHA , that means a decrease in complexing agent MIBSHA concentration to form ion pair complex with Bi(III) so that electrolytes affect by increasing extraction efficiency of Bi(III) by effect of increasing Dehydration and destroyed hydration shell of bismuth ion to increase the chances of binding with MIBSHA for more stable ion pair complex. Later, this method was used coupled with suitable spectrophotometric application in the separation and determination of bismuth (III) in different samples.2 - Studies about Nickel (II)For nickel ion Ni(II) extraction from aqueous solution as ion pair complex used new laboratory prepared complexing agent AADAD , the spectrophotometric study for ion pair complex on Ni(II extracted into CPL showed maximum absorbance peak at wave length λmax=585nm and through the experimental study to limit optimum conditions and effective parameters. The study demonstrated that the optimum pHex was (9) which gives the highest extraction efficiency for nickel ion Ni(II by use complexing agent AADAD, whereas at this pHex favorable binding was given to form ion pair complex of nickel ion Ni(II with high concentration and stability as well as the method CPE for extraction Ni(II needed 0.5ml of non - ionic surfactant 1% TritonX - 100 which is affected to reach favorable thermodynamic equilibrium for aggregation of micelles in the state CMC for CPL formation with good163properties for the ion pair complex extraction of Ni(II) as well this extraction efficiency appeared with the presence of 50μg Ni(II) in aqueous solution to reach the best thermodynamic equilibrium for ion pair complex formation. Increasing AADAD concentration showed the existence of linear relation with linear increase in absorbance and distribution ratio and linear increasing in concentration stability and partitioning to CPL ion pair complex of Ni(II whereas CPE methodology depends on the temperature of heating, the experiment showed that 80°C was the optimum temperature that gives the higher extraction efficiency of Ni(II with thermodynamic data ΔHex= 0.1126KJmol - 1 , ΔGex= - 58.19KJmol - 1 and ΔSex=165.16Jmol - 1K - 1 . These values prove that the ions of ion pair complex for Ni(II) extracted into CPL approached one another with a high gegree and the method of extraction was entropic in region. The experimental study about the effect of heating time showed that 15min was the best time of heating that allows to reach a higher extraction efficiency of CPE method. Time of heating indicates the kinetic side of extraction method as heating for 15min at 80°C gave the quantity of heating that hels to reach the favorable thermodynamic equilibrium for CPL formation stoichiometry showing the more probable structure of ion pair complex extracted for Ni(II) which was [Ni(AADAD)]+;No3 - but synergism effect study showed that by using TBP and MIBK showed increasing extraction efficiency of Ni(II) with the presence of TBP or MIBK in aqueous solution because substitution water in coordination shell of Ni(II) in ion pair complex and effect to increase hydrophobicity, stability and partitioning to CPL. Also, the study revealed that adding one molecule of TBP or MIBK in the structure of ion pair complex of Ni(II) such as [Ni(AADAD)(TBP)]+;NO3 - , [Ni(AADAD)(MIBK)]+;NO3 - . So the studies tackled the effect of interferences as cations and electrolytes on extraction efficiency, later on, we used this method in the extraction and spectrophotometric determination of Nickel (II) in different samples.3 - Studies about Cobalt (II)The experimental studies concerning the separation, preconcentration and extraction of cobalt(II) as ion association complex by using the same complexing agent used with nickel (II) AADAD according to Cloud point extraction methodology. The UV - Vis spectrophotometric studies about the ion association complex extracted showed that the maximum absorbance of the complex of wave length λmax=530nm. As well as the extraction method according to CPE method showed (pH=8) was the optimum acidic function for extraction giving the highest absorbance and distribution value D because this pHex the best164coordination bonding between cobalt ion Co(II) and complexing agent AADAD so that high partitioning of stable complex to cloud point layer CPL. Moreover, the experiments showed that 0.5ml of Non - ionic surfactant, very stable for giving higher extraction efficiency because this volume of surfactant helps to reach the favorable thermodynamic equilibrium of aggregation of micelles to form CPL with high density and small volume and the micelles in case one approaches the other with the best dehydration to be in high hydrophobicity with good partitioning of complex to CPL. And in this case giving higher extraction efficiency, also, this extraction efficiency obtained when 60μg of cobalt ion Co(II was in the aqueous solution to give the best thermodynamic equilibrium to formation high stability ion pair complex extracted into CPL quantitively effect of temperature study showed that 80°C was the best temperature of extraction according to CPE method because in this temperature the best CPL was formed by aggregation and using dehydration at CMC state happen good extraction as well as thermodynamic data for extraction Co(II) was ΔHex=0.1014KJmol - 1, ΔGex= - 60.658KJmol - 1, ΔSex=171.86Jmol - 1K - 1. These data showed from the small positive value of enthalpy of extraction , the ions of ion pair complex extraction when one approach another to increase stability of this complex as well the large positive value of entropy of extraction demonstrates the dependence of extraction according to CPE and entropy. Then this procedure being entropic in region. Time of heating as the experiment study showed is 15min and was stable to give higher extraction efficiency. Because heating the solution at fixed temperature and time mean the quantity of heating help kinetically to reach thermodynamic and kinetic equilibrium for formation CPL. Then giving higher extraction efficiency. Stoichiometry study revealed that the more probable structure of ion pair complex extracted was [Co(AADAD)]+;NO3 - . Synergism study show presence TBP or MIBK in aqueous solution effect to increase extraction efficiency of Co(II) according to CPE method. Because complexing agent AADAD was not able to saturated the coordination shell of Co(II) ion in complex formation then the empty coordination position and occupy with water molecule and decline extraction efficiency , but TBP or MIBK able to coordinate instead of water in coordination shell and increase extraction efficiency, as well the study showed one molecule of TBP or MIBK able to enter in complex formed such as [Co(AADAD)(TBP)]+;NO3 - or [Co(AADAD)(MIBK)]+;NO3 - . So that the studies involved the effect of interferences as cations and electrolytes on extraction efficiency , later we used this method for the extraction and spectrophotometric determination of cobalt (II) in different samples.
