Extraction Chromatographie Behaviors of Zirconium and Hafnium Using Sulfoxides as Stationary Phases

Wang, Qiuquan; Tsunoda, Kin-ichi; Akaiwa, Hideo

doi:10.2116/analsci.11.909

Cited by 10 publications

(4 citation statements)

References 9 publications

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“…The complex molar ratios of H + /SCNand MIBK/HSCN in the organic phase were both almost 1:1, which indicated that SCNwas extracted into the organic phase as a form of HSCN and form a complex of HSCN•MIBK. The large value of K1 indicated that the HSCN is a weak acid, which is consistent with the conclusion of the study by Wang et al [27].…”

Section: Stoichiometry and Equilibrium Constantssupporting

confidence: 92%

“…The complexing process of Zr 4+ /Hf 4+ with SCN − must go through the dissociation of HSCN. Since HSCN is a weak acid, the hydrolysis of HSCN would restrain the complexation of Zr 4+ /Hf 4+ with SCN − [27]. The effect of HCl concentration on the distribution ratio and the separation factor when NH4SCN concentration was 2.5 M was studied in detail, and the results are presented in Figure 12.…”

Section: Ft-ir Analysismentioning

confidence: 99%

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The Extraction Mechanism of Zirconium and Hafnium in the MIBK-HSCN System

Xiong,

Li,

Zhang

et al. 2024

Separations

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The extraction of zirconium (Zr) and hafnium (Hf) in methyl isobutyl ketone (MIBK)—thiocyanic acid (HSCN) system has been widely used in the production of nuclear-grade zirconium and hafnium in industry, while the extraction mechanism was not adequately studied. In this study, the extraction and stripping equilibrium of Zr and Hf in the MIBK-HSCN system was studied. The results showed that elevated HCl concentration can increase the distribution ratio of SCN− and decrease that of Zr/Hf in organic phase. In the stripping process, HCl concentration and the Organic/Aqueous (O/A) phase ratio played important roles. The mechanism of the extraction reaction was discussed by considering the stoichiometric relationship of possible reaction equations and corresponding equilibrium constants. The results indicated that SCN− could be extracted into MIBK as HSCN·MIBK. Meanwhile, SCN− could also be extracted into MIBK by complexing with metal (Zr or Hf). The molar ratios of MIBK to the complexes of Zr and Hf have been found to be 5.34 and 5.03, respectively. With the increase in the initial concentration of HCl in the aqueous phase, the complexation molar ratios of SCN− to Zr and Hf increased first and then decreased, and so do the extraction equilibrium constants, which might be due to the extraction competition of HSCN and metal complexes.

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Section: Stoichiometry and Equilibrium Constantssupporting

confidence: 92%

Section: Ft-ir Analysismentioning

confidence: 99%

The Extraction Mechanism of Zirconium and Hafnium in the MIBK-HSCN System

Xiong,

Li,

Zhang

et al. 2024

Separations

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“…The results for the determination of cadmium in its bioavailable fractions of BCR-483 and the soil samples are listed in Table 1. The results were in good agreement with the indicative values for cadmium in the bio-available fraction of BCR 483 by AAS and ICP-AES/MS determinations, as well as those in the soil samples obtained by ICP-MS determination with a pretreatment of bis(1,1,3,3-tetramethylbutyl)phosphinic acid (HMBP) extraction method [27].…”

Section: Performance Of the Micro Hplc Systemsupporting

confidence: 81%

Chromatographic behavior of cadmium in an ion-pair reversed-phase micro HPLC system and its application to the determination of bio-available cadmium in soil samples

Wang

Yan

et al. 2003

Analytical and Bioanalytical Chemistry

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A novel reversed phase ion-pair micro HPLC system with on-line fluorescence detection has been developed systematically and studied for the determination of cadmium in its bio-available fractions of soil samples. In this system, a micro ODS column of 1.0 mm i.d.x150 mm length and a mobile phase containing 6 mmol L(-1) 8-hydroxyquinoline 5-sulphonic acid (HQS), 3 mmol L(-1) cetyltrimethylammonium bromide (CTMABr), 10 mmol L(-1) acetic acid-acetate buffer (pH 5.1) as well as 50% acetonitrile at 50 microL min(-1) flow rate were employed to determine cadmium with a 2 microL flow cell through its fluorescence at 518 nm under 338 nm excitation. Furthermore, the composition of Cd-HQS chelate formed on the column was confirmed to be [Cd(HQS)(2)](2-) through a log-log plot method, and then combined with the ion-pair reagent by the electrostatic force under the chromatographic condition proposed. With such a method, the detection limit of cadmium was 8.48 ng mL(-1) (3sigma) with 1 microL sample injection, and the linear range for the determination of cadmium was 30-800 ng mL(-1) (R(2)=0.992). This method has been successfully applied to determination of cadmium in its bio-available fractions of BCR-483 and soil samples without interference from other coexistent metal ions. The RSD (n=6) was less than 7.3%. The results were in agreement with the indicative value for BCR-483 and those for the soil samples obtained by ICP-MS with a pretreatment of bis(1,1,3,3-tetramethylbutyl) phosphinic acid extraction.

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“…Reduced species like CH 3 SH only appear after the samples are acidified with 1 mL of a 1 M H 2 SO 4 solution and again heated for 3 days. This observation can be explained by the weak acidity of HOCN (pK a = 3.7) that lead to the formation of an insufficient amount of H 2 S. As for the stronger acid, HSCN (pKa � 0.9), [60] the formation of CH 4 , CH 3 SH and CS 2 already takes place upon addition of 1 mL of a 1 M H 2 SO 4 solution. This is confirmed by the expected mass shifts of + 1 for all C 1 products are observed when KS 13 CN and KO 13 CN are used in place of the natural-abundance KSCN and KOCN, respectively (Figure S7 and Figure S8).…”

Section: Further Experimental Evidencementioning

confidence: 99%

Mackinawite‐Supported Reduction of C₁ Substrates into Prebiotically Relevant Precursors

et al. 2022

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Mackinawite has unique structural properties and reactivities when compared to other iron sulfides. Herein we provide evidence for the mackinawite‐supported reduction of KCN into various reduced compounds under primordial conditions. We proposed a reaction mechanism based on the nucleophilic attack by the deprotonated mackinawite ‐SH surface groups at the carbon atom of HCN. The initial binding of the substrate and the subsequent reduction events are supported by DFT calculations and further experiments using other substrates, such as KSCN, KOCN and CS2. Until now, conversion of CN− into CH4 and NH3 has been limited to nitrogenase cofactors or molecular Fe‐CN complexes. Our study provides evidence for mackinawite‐supported cleavage of the C−N bond under ambient conditions, which opens new avenues for investigation of other substrates for mackinawite‐supported reactions while shedding light on the relevance of this type of reaction to the origin of life on Earth.

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Extraction Chromatographie Behaviors of Zirconium and Hafnium Using Sulfoxides as Stationary Phases

Cited by 10 publications

References 9 publications

The Extraction Mechanism of Zirconium and Hafnium in the MIBK-HSCN System

The Extraction Mechanism of Zirconium and Hafnium in the MIBK-HSCN System

Chromatographic behavior of cadmium in an ion-pair reversed-phase micro HPLC system and its application to the determination of bio-available cadmium in soil samples

Mackinawite‐Supported Reduction of C₁ Substrates into Prebiotically Relevant Precursors

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Extraction Chromatographie Behaviors of Zirconium and Hafnium Using Sulfoxides as Stationary Phases

Cited by 10 publications

References 9 publications

The Extraction Mechanism of Zirconium and Hafnium in the MIBK-HSCN System

The Extraction Mechanism of Zirconium and Hafnium in the MIBK-HSCN System

Chromatographic behavior of cadmium in an ion-pair reversed-phase micro HPLC system and its application to the determination of bio-available cadmium in soil samples

Mackinawite‐Supported Reduction of C1 Substrates into Prebiotically Relevant Precursors

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Mackinawite‐Supported Reduction of C₁ Substrates into Prebiotically Relevant Precursors