Solvent Extraction and Separation of Gallium(III) using Hexaacetato Calix(6)Arene

Abstract

Gallium(III) was extracted at pH 3.5 by equilibrating eight min with 10 mL of 0.0001 M acetyl derivative of calix(6)arene in xylene. Gallium(III) was stripped quantitatively with 0.1 N hydrochloric acid and determined spectrophotometrically with 0.01% PAR at 510 nm. The nature of the extracted species was determined from the log-log plots and its stoichiometry was confirmed by numerical treatment to experimental data. The IR analysis of Ga(III) loaded organic phase was also studied. The conformational change of reagent during complex formation was studied from the 1 H NMR treatment. The temperature dependence of the extraction equilibrium and metal loading capacity of the reagent was also evaluated. The proposed method was successfully applied for the extraction and separation of multicomponent mixtures, synthetic mixtures, and binary and ternary separation of gallium from the associated elements. The results obtained were reproducible and accurate.

Extraction of Cu(II) From Acidic Sulfate Media by Palm Kernel Fatty Acid Distillate: Stoichiometry and Thermodynamic Studies

“…These negative ΔH o (favorable) and ΔS o (unfavorable) attained also imply that the binding of Cu(II) to FFAs was primarily driven by enthalpy (Arisaka and Kimura, 2011) and FFAs acted as non-chelating or monodentate ligands. Several researchers have reported the similar findings for the enthalpydriven complexation reaction (Arisaka and Kimura, 2011;Mishra and Devi, 2011;Thakare and Malkhede, 2014;Wang et al, 2018) and the outer-sphere metal-extractant complexes (Bell et al, 2008;El-Sweify et al, 2008) as this work, while others have recorded the entropy-driven reaction (Mishra and Devi, 2018;Yin et al, 2015) and the inner-sphere complexes (Arisaka and Kimura, 2011;Hu et al, 2017;Mishra and Devi, 2018). Fig.…”

“…The stoichiometry provides the precise number of moles of each substance required to form one mole of metal-extractant complexes under favorable thermodynamic conditions, while the thermodynamics explains the extraction behavior of a metal ion by the extractant (Choppin and Morgenstern, 2000;Wahab et al, 2016). The stoichiometry of various metal-extractant complexes in different diluents have been reported, for instance, 1:4 and 1:2 for Cu(II)-di-2-ethylhexylphosphoric acid (D2EHPA) complexes in soybean oil (Chang et al, 2011) and waste palm cooking oil (Wahab et al, 2016), respectively; 1:2 for Cu(II)-2-hydroxy-5-nonylacetophenone oxime (active component of LIX 84) complexes in toluene (Elizalde et al, 2019); 1:6 for Nd(III)-D2EHPA complexes in sulfonated kerosene (Yin et al, 2015); 1:3 for Ga(III)-hexaacetato calix(6)arene in xylene (Thakare and Malkhede, 2014); and 1:2 for hydrated Ni(II)-dinonylnaphthalene disulfonic acid and 2-ethylhexyl 4-pyridinecarboxylate ester complexes in sulfonated kerosene (Hu et al, 2018). The majority of these works used either the equilibrium slope or numerical analysis, or both, to determine the stoichiometry of metal-extractant complexes (Chang et al, 2011;Elizalde et al, 2019;Thakare and Malkhede, 2014;Wahab et al, 2016;Yin et al, 2015).…”

“…The stoichiometry of various metal-extractant complexes in different diluents have been reported, for instance, 1:4 and 1:2 for Cu(II)-di-2-ethylhexylphosphoric acid (D2EHPA) complexes in soybean oil (Chang et al, 2011) and waste palm cooking oil (Wahab et al, 2016), respectively; 1:2 for Cu(II)-2-hydroxy-5-nonylacetophenone oxime (active component of LIX 84) complexes in toluene (Elizalde et al, 2019); 1:6 for Nd(III)-D2EHPA complexes in sulfonated kerosene (Yin et al, 2015); 1:3 for Ga(III)-hexaacetato calix(6)arene in xylene (Thakare and Malkhede, 2014); and 1:2 for hydrated Ni(II)-dinonylnaphthalene disulfonic acid and 2-ethylhexyl 4-pyridinecarboxylate ester complexes in sulfonated kerosene (Hu et al, 2018). The majority of these works used either the equilibrium slope or numerical analysis, or both, to determine the stoichiometry of metal-extractant complexes (Chang et al, 2011;Elizalde et al, 2019;Thakare and Malkhede, 2014;Wahab et al, 2016;Yin et al, 2015). Other methods like the Job plot (Wahab et al, 2016) and quantitative analysis with FTIR (Chang et al, 2011) (Aidi and Barkat, 2018) and Cu(II)-N-(2 hydroxybenzylidene) aniline (Aidi and Barkat, 2010) complexes, respectively, in cyclohexane; ∆H o of 25.65 kJ•mol -1 , ∆S o of 0.079 kJ•mol -1 •K -1 , and ∆G o of 0.86 kJ•mol -1 for Zn(II)-D2EHPA complexes in kerosene (Jafari et al, 2018); and ∆H o of 17.32 kJ•mol -1 , ∆S o of 0.041 kJ•mol -1 •K -1 , and ∆G o of 5.09 kJ•mol -1 for vanadium(V)-D2EHPA complexes in kerosene (Razavi et al, 2018).…”

Extraction of Gallium(III) with a New Azo Dye in The Presence or Absence of Xylometazoline Hydrochloride

“…[4,[6][7][8][9][10][11][12] Gallium(III) forms intensely colored chelate species with azo dyes, such as 4-(2-pyridylazo)resorcinol (PAR) and 4-(2thiazolylazo)resorcinol (TAR). [13][14][15][16][17][18] Cationic ion-association reagents have been used in our laboratory to improve the hydrophobicity and extraction characteristics of such chelates: tetrazolium salts, [19,20] nitron [21] and xylometazoline hydrochloride (XMH). [22] Extraction systems containing both Ga(III) and 6-hexyl-4-(2-thiazolylazo)resorcinol (HTAR) have not been studied so far.…”

Partitioning Equilibria and Thermodynamics of Gallium, Indium, and Thallium in Aqueous Two-Phase Systems

“…For the treatment of metals ions or organic materials, most of the technologies include adsorption, , flotation, , membrane processes, , and ion exchange, and also a promising alternative way, liquid–liquid extraction. Unfortunately, the published work on liquid–liquid extraction usually involves volatile organic compounds (VOCs) as solvents, − such as toluene, benzene, nitrobenzene, n -hexane, xylene, ethanol, 2-propanol, kerosene and so on, which largely limits the application of this method. So a new extraction system for the extraction of gallium, indium, and thallium without VOCs is urgently needed.…”