Study of roméite solubility in the fluid immiscibility region of the NaF–H2O system at 800°C, 200 MPa

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Abstract

New data on roméite (CaNa)Sb2O6F solubility in the NaF–H2O system of P–Q type in a wide range of sodium fluoride concentrations (from 0 to 25 wt. % NaF) have been obtained. The concentration of antimony, in equilibrium with roméite and fluorite, in the range of NaF concentrations from 1 to 8 mol kg−1 H2O (25 wt. % NaF), is in the interval of 0.02–0.2 mol kg−1 H2O. According to the data obtained, the concentration of antimony in the L1 and L2 phases in the fluid immiscibility region of the NaF–H2O system at 800°C, 200 MPa and f(O2) = 50 Pa, specified by the Cu2O–CuO buffer, is 0.4 and 2.1 wt. % Sb, respectively. For the first time, during these experiments, the formation of fluorite skeletal forms and an intermetallic compound Pt5Sb of a hexagonal crystal system with lattice parameters (LP): a = b = 4.56(4), c = 4.229(2) Å, α = β = 90°, γ = 120° was established. Pentaplatinum antimonide is formed on the surface of Pt ampoules at 800°C, P = 200 MPa and f(O2) ≤ 10−3.47 Pa (Cu–Cu2O buffer) in experiments on the incongruent dissolution of romeite, which causes a sharp decrease (more than 1000 times) the concentration of antimony in solution.

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A. F. Redʹkin

Korzhinskii Institute of Experimental Mineralogy RAS (IEM RAS)

Author for correspondence.
Email: redkin@iem.ac.ru
Russian Federation, Acad. Osipyan st., 4, Chernogolovka, Moscow district, 142432

N. P. Kotova

Korzhinskii Institute of Experimental Mineralogy RAS (IEM RAS)

Email: redkin@iem.ac.ru
Russian Federation, Acad. Osipyan st., 4, Chernogolovka, Moscow district, 142432

Yu. B. Shapovalov

Korzhinskii Institute of Experimental Mineralogy RAS (IEM RAS)

Email: redkin@iem.ac.ru
Russian Federation, Acad. Osipyan st., 4, Chernogolovka, Moscow district, 142432

A. N. Nekrasov

Korzhinskii Institute of Experimental Mineralogy RAS (IEM RAS)

Email: redkin@iem.ac.ru
Russian Federation, Acad. Osipyan st., 4, Chernogolovka, Moscow district, 142432

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2. Fig. 1. XRD of solid phases after experiments on the solubility of Rom in NaF solutions from 0 to 25 wt.% at 800°C, 200 MPa and fO2 specified by Cu2O-CuO buffer. Legend: R — Rom, F — Flu.

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3. Fig. 2. Effect of NaF concentration on the relative intensity of the <111> Flu and <311> Rom lines in the products of experiments on the solubility of a mixture of 15 mg Rom + 2 mg Flu at 800°C, 200 MPa and fO2, specified by Cu2O–CuO buffer.

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4. Fig. 3. SEM images of solid phases after experiments at 800°C, 200 MPa, in solutions of NaF 0 (a), 4.03 (b), 10 (c), 15 (d), 20 (d), 25 wt. % (e) and fO2 specified by Cu2O–CuO buffer.

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5. Fig. 4. SEM images of solid phases after experiments at 800°C, 200 MPa, in solutions of NaF 4.03 (a) and 10 wt.% (b) and fO2 specified by Cu–Cu2O buffer.

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6. Fig. 5. XRD patterns of solid phases after solubility experiments for Rom in 4.03 and 10 wt.% NaF solutions at 800°C, 200 MPa and fO2 specified by Cu–Cu2O buffer. Legend: Sb4 – experiment in 4.03 wt.% NaF; Sb10 – in 10 wt.% NaF; F – Flu.

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7. Fig. 6. Surface of Pt ampoule after experiment at 800°C, 200 MPa, in solution of 4.03 wt.% and fO2 specified by Cu–Cu2O buffer.

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8. Fig. 7. Dependence of CtotalSb on CtotalNaF in experiments on incongruent solubility of Rom at 800°C, 200 MPa. Based on the results of ICP-MS analysis in the laboratories of (1) – IPTM RAS; (2) – Geological Faculty of Moscow State University.

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