Mass-Spectrometric Study of the Laser-Induced Vaporization of Compounds of Arsenic and Antimony with the Elements of Group VIa

Ban, Vladimir S.; Knox, Bruce E.

doi:10.1063/1.1672673

Cited by 36 publications

(13 citation statements)

References 12 publications

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“…At 300°C and 265°C, arsenolite remained the dominant phase but exhibited traces of partial melting. As has been shown by previous spectroscopic (Ban and Knox, 1970;Beattie et al, 1970;Brumbach and Rosenblatt, 1972) and pressure or vaporization-rate measurements (Jungermann and Plieth, 1967;Behrens and Rosenblatt, 1972), the vapor in equilibrium with arsenic trioxide consists of As 4 O 6 molecules up to at least 800°C. Assuming an ideal behavior of As 4 O 6 in the vapor phase (Behrens and Rosenblatt, 1972), partial pressures of As 4 O 6 (gas) in equilibrium with solid or molten As 2 O 3 can be calculated from the vapor As concentrations measured in this study:…”

Section: Water-free Systemmentioning

confidence: 65%

Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

Pokrovski

Zakirov

Roux

et al. 2002

Geochimica et Cosmochimica Acta

162

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The stoichiometry and stability of arsenic gaseous complexes were determined in the system AsH 2 O Ϯ NaCl Ϯ HCl Ϯ H 2 S at temperatures up to 500°C and pressures up to 600 bar, from both measurements of As (III) and As (V) vapor-liquid and vapor-solid partitioning, and X-ray absorption fine structure (XAFS) spectroscopic study of As (III)-bearing aqueous fluids. Vapor-aqueous solution partitioning for As (III) was measured from 250 to 450°C at the saturated vapor pressure of the system (P sat) with a special titanium reactor that allows in situ sampling of the vapor phase. The values of partition coefficients for arsenious acid (H 3 AsO 3) between an aqueous solution (pure H 2 O) and its saturated vapor (K ϭ mAs vapor /mAs liquid) were found to be independent of As (III) solution concentrations (up to ϳ1 to 2 mol As/kg) and equal to 0.012 Ϯ 0.003, 0.063 Ϯ 0.023, and 0.145 Ϯ 0.020 at 250, 300, and 350°C, respectively. These results are interpreted by the formation, in the vapor phase, of As(OH) 3 (gas), similar to the aqueous As hydroxide complex dominant in the liquid phase. Arsenic chloride or sulfide gaseous complexes were found to be negligible in the presence of HCl or H 2 S (up to ϳ0.5 mol/kg of vapor). XAFS spectroscopic measurements carried out on As (III)-H 2 O(ϮNaCl) solutions up to 500°C demonstrate that the As(OH) 3 complex dominates As speciation both in dense H 2 O-NaCl fluids and low-density supercritical vapor. Vapor-liquid partition coefficients for As (III) measured in the H 2 O-NaCl system up to 450°C are consistent with the As speciation derived from these spectroscopic measurements and can be described by a simple relationship as a function of the vapor-to-liquid density ratio and temperature. Arsenic (III) partitioning between vapor and As-concentrated solutions (Ͼ2 mol As/kg) or As 2 O 3 solid is consistent with the formation, in the vapor phase, of both As 4 O 6 and As(OH) 3. Arsenic (V) (arsenic acid, H 3 AsO 4) vapor-liquid partitioning at 350°C for dilute aqueous solution was interpreted by the formation of AsO(OH) 3 in the vapor phase. The results obtained were combined with the corresponding properties for the aqueous As(III) hydroxide species to generate As(OH) 3 (gas) thermodynamic parameters. Equilibrium calculations carried out by using these data indicate that As(OH) 3 (gas) is by far the most dominant As complex in both volcanic gases and boiling hydrothermal systems. This species is likely to be responsible for the preferential partition of arsenic into the vapor phase as observed in fluid inclusions from high-temperature (400 to 700°C) Au-Cu (-Sn,-W) magmatic-hydrothermal ore deposits. The results of this study imply that hydrolysis and hydration could be also important for other metals and metalloids in the H 2 O-vapor phase. These processes should be taken into account to accurately model element fractionation and chemical equilibria during magma degassing and fluid boiling.

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Section: Water-free Systemmentioning

confidence: 65%

Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

Pokrovski

Zakirov

Roux

et al. 2002

Geochimica et Cosmochimica Acta

162

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“…Prominent stoichiometries for both metals are M 3 O 4 + , M 4 O 5 + , and M 5 O 7 + . These prominent metal oxide cations in the small size domain have been reported many years ago under laser desorption mass spectrometer conditions. − However, no clusters larger than about five metal atoms were observed and no explanations were given for these trends.…”

Section: Resultsmentioning

confidence: 85%

Antimony and Bismuth Oxide Clusters: Growth and Decomposition of New Magic Number Clusters

et al. 1997

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A series of new “magic number” metal oxide clusters are described for the group V metals antimony and bismuth. Specific nonstatistical stoichiometries of M x O y cation and anion clusters are formed preferentially in the gas phase when oxidized metal is vaporized or when metal is vaporized and combined with gas phase oxygen (e.g., Bi7O10 +, Bi9O14 +). Essentially the same stoichiometries are seen for antimony and bismuth analogues. The species produced in cluster growth are also produced preferentially by photodissociation of larger clusters. Localized covalent bonding schemes are suggested for these clusters, and polyhedral cage structures are proposed. The stoichiometries observed require a 3+ metal oxidation state in the small clusters, which shifts over to one or more 5+ metal atoms in larger clusters.

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“…The Sb 2 –Se 3 bond with a bond length of 2.6649 Å is defined as type I, the Sb 2 –Se 2 bond with a bond length of 2.6418 Å is defined as type II, the Sb 1 –Se 2 bond with a bond length of 2.7776 Å is defined as type III, the Sb 1 –Se 1 bond with a bond length of 2.5573 Å is defined as type IV, and the Sb 1 –Se 1 bond with a bond length of 2.9821 Å is defined as type V. In this scenario, it is obvious that the type V Sb–Se bond will be broken preferentially and form Sb 2 Se 3 clusters. Then type III Sb–Se bonds will be broken and form SbSe 2 – and SbSe + clusters, which have been proven to be the main component of Sb 2 Se 3 . , In addition, the bonding energies of the Sb–Sb bond (42 kcal/mol) and Se–Se bond (49 kcal/mol) are lower than that of the Sb–Se bond (51 kcal/mol), and the Sb 2 Se 3 vapor will finally be dominated by Sb + , Se 2 , and SbSe clusters in ideal conditions. , To determine the degree of ease of the decomposition and composition processes of Sb 2 Se 3 , the Gibbs free energy of these two reactions from 0 to 600 °C are calculated, as shown in Figure (a). It is easy to find that the Sb 2 Se 3 can form spontaneously during the whole process, and a higher source temperature can promote the decomposition process of Sb 2 Se 3 .…”

Section: Results and Discussionmentioning

confidence: 99%

Remarkable Sb₂Se₃ Solar Cell with a Carbon Electrode by Tailoring Film Growth during the VTD Process

Wang

Cao

et al. 2021

ACS Appl. Energy Mater.

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The vapor transport deposition (VTD) method is regarded as one of the most effective approaches to obtain high-quality Sb2Se3 thin films. However, the orientation and morphology of Sb2Se3 limit the development of Sb2Se3 solar cells. Thus, a method to tailor the surface morphology of Sb2Se3 film growth by VTD is urgently needed. In this work, the growth of the Sb2Se3 thin film and the formation mechanism of Sb2Se3 nanorods appearing on the Sb2Se3 film are carefully studied. Sb2Se3 nanorods with [hk1] orientation and [hk0] orientation are distinguished. By controlling the growth of Sb2Se3 nanorods with [hk1] orientation, the interface defect density is reduced and the quality of the Sb2Se3 thin film is improved. Finally, Sb2Se3 solar cells with the configuration ITO/CdS/Sb2Se3/C/Ag achieve an efficiency of 6.09% with an open circuit voltage (V oc) deficit decreased by 34 mV, wherein over 85% of the efficiency of the Sb2Se3 device remains after replacing the Spiro-OMeTAD/Au structure with a carbon/Ag structure. This value is the champion efficiency for a VTD-processed Sb2Se3 solar cell with a carbon electrode. This work is expected to offer valuable information for the future development of Sb2Se3 or/and other highly anisotropic materials formed by physical vapor deposition.

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Mass-Spectrometric Study of the Laser-Induced Vaporization of Compounds of Arsenic and Antimony with the Elements of Group VIa

Cited by 36 publications

References 12 publications

Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

Antimony and Bismuth Oxide Clusters: Growth and Decomposition of New Magic Number Clusters

Remarkable Sb₂Se₃ Solar Cell with a Carbon Electrode by Tailoring Film Growth during the VTD Process

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Mass-Spectrometric Study of the Laser-Induced Vaporization of Compounds of Arsenic and Antimony with the Elements of Group VIa

Cited by 36 publications

References 12 publications

Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

Experimental study of arsenic speciation in vapor phase to 500°C: implications for As transport and fractionation in low-density crustal fluids and volcanic gases

Antimony and Bismuth Oxide Clusters: Growth and Decomposition of New Magic Number Clusters

Remarkable Sb2Se3 Solar Cell with a Carbon Electrode by Tailoring Film Growth during the VTD Process

Contact Info

Product

Resources

About

Remarkable Sb₂Se₃ Solar Cell with a Carbon Electrode by Tailoring Film Growth during the VTD Process