Mandal Bhabatosh, Barman Milan K, Srivastava Bhavya
Department of Chemistry, Visva-Bharati, Santiniketan, West Bengal 731235, India
Department of Chemistry, Visva-Bharati, Santiniketan, West Bengal 731235, India.
J Chromatogr Sci. 2014 Oct;52(9):1135-44. doi: 10.1093/chromsci/bmt160. Epub 2013 Nov 4.
A selective method has been developed for the extraction chromatographic separation of V(IV) with SSG-V-10 composite. V(IV) was quantitatively extracted at pH 5.0-6.0, and its loading has been confirmed by EDAX. XRD studies indicate that the SSG network does not get influenced by impregnation with V-10 or by the sorption of V(IV) on the surface of SSG-V-10 composite. The binding between SSG and V-10 is a hydrophobic interaction only, and it takes place at the surface of the hydrophobic SSG. TGA-DTA analysis indicates its thermal stability up to 45°C. The exchange capacity (1.65 meq of H(+) g(-1)), break-through capacity (34.5 mg g(-1)) and column efficiency (360) of the extractor have been rationalized by Brunauer-Emmett-Teller analysis (SA = 149.46 m(2) g(-1) and PV = 0.2001 mL g(-1) at a relative pressure of 0.9-1.0). The sorption process was endothermic (ΔH = 12.63 kJ mol(-1)), entropy gaining (ΔS = 0.271 kJ mol(-1) K(-1)) and spontaneous (ΔG = -68.241 kJ mol(-1)) in nature. Preconcentration factor has been optimized at 182.3 ± 0.2. Formation constants (Kf) of the metal centers [Zn(II) (0.6 × 10(3)), Cd(II) (0.9 × 10(4)), Pb(II) (0.6 × 10(5)), Cu(II) (0.2 × 10(5)), Al(III) (6.2 × 10(5)), Ga(III) (4.2 × 10(5)), Hg(II) (2.2 × 10(6)), Bi(III) (6.2 × 10(6)), Tl(III) (8.9 × 10(6)), Zr(IV) (6.8 × 10(9)), Fe(III) (0.9 × 10(9)) and V(IV) (0.8 × 10(6))] have been determined. The desorption constants Kdesorption (1.9 × 10(-2)) and [Formula: see text] have been determined. Rf values and selectivity factors for diverse metal ions have been determined. V(IV) has been separated from the synthetic and real samples containing its congeners. A plausible mechanism for the extraction of V(IV) has been suggested.
已开发出一种用SSG-V-10复合材料进行萃取色谱分离V(IV)的选择性方法。V(IV)在pH 5.0 - 6.0时被定量萃取，其负载情况已通过能谱分析（EDAX）得到证实。X射线衍射（XRD）研究表明，SSG网络不受V-10浸渍或V(IV)在SSG-V-10复合材料表面吸附的影响。SSG与V-10之间的结合仅是疏水相互作用，且发生在疏水SSG的表面。热重-差热分析（TGA-DTA）表明其热稳定性可达45°C。通过布鲁诺尔-埃米特-泰勒（Brunauer-Emmett-Teller）分析（在相对压力0.9 - 1.0时，比表面积SA = 149.46 m² g⁻¹，孔容PV = 0.2001 mL g⁻¹）对萃取器的交换容量（1.65 meq的H⁺ g⁻¹）、穿透容量（34.5 mg g⁻¹）和柱效（360）进行了合理说明。吸附过程是吸热的（ΔH = 12.63 kJ mol⁻¹）、熵增的（ΔS = 0.271 kJ mol⁻¹ K⁻¹）且是自发的（ΔG = -68.241 kJ mol⁻¹）。预富集因子已优化至182.3 ± 0.2。已测定了金属中心[锌(II)（0.6 × 10³）、镉(II)（0.9 × ¹⁰⁴）、铅(II)（0.6 × 10⁵）、铜(II)（0.2 × 10⁵）、铝(III)（6.2 × 10⁵）、镓(III)（4.2 × 10⁵）、汞(II)（2.2 × 10⁶）、铋(III)（6.2 × 10⁶）、铊(III)（8.9 × 10⁶）、锆(IV)（6.8 × 10⁹）、铁(III)（0.9 × 10⁹）和V(IV)（0.8 × 10⁶）]的形成常数（Kf）。已测定了解吸常数Kdesorption（1.9 × 10⁻²）和[公式：见原文]。已测定了不同金属离子的比移值（Rf）和选择性因子。V(IV)已从含有其同系物的合成样品和实际样品中分离出来。已提出了一种合理的V(IV)萃取机制。
