Evidence for As4S6 molecule as a structural model for amorphous arsenic sulfide from mass spectrometric analysis

Hammam, M.; Santiago, J. J.

doi:10.1016/0038-1098(86)90705-2

Cited by 9 publications

(5 citation statements)

References 8 publications

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“…Although As 4 S 6 molecules are the least stable among the As 4 S n cages (Davorin and Sohrab, 1989), they have never been found in naturally occurring minerals. Their existence was reported in synthetic trisulfides prepared by melt quenching (Hamman and Santiago, 1986). Nakai et al (1986) obtained synthetic wakabayashilite with an (As+Sb)/S ratio close to 10:15 which could indicate, apart from the different Sb content, a dimorphic relation with orpiment (As 2 S 3 ) and would support the structural model obtained previously by Scott and Nowacki (1976).…”

Section: Introductionsupporting

confidence: 81%

Chemical variability in wakabayashilite: a real feature or an analytical artifact?

et al. 2014

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Wakabayashilite is a rare mineral with ideal formula [(As,Sb)6S9][As4S5]. Its structure consists of an [M6S9] bundle-like unit (M = As, Sb) running along the [001] axis and [As4S5] cage-like molecules. In this study, samples of wakabayashilite from different occurrences (Khaidarkan, Kyrgyzstan; Jas Roux, France; White Caps mine, USA; Nishinomaki mine, Japan) were selected to verify the possible presence of different molecular groups replacing the As4S5 molecule. Given the chemical (electron probe microanalysis-wavelength dispersive spectroscopy), spectroscopic (micro-Raman) and structural (single-crystal X-ray diffraction) results obtained, it appears evident that only the As4S5 molecular group is present in the wakabayashilite structure and that the apparent non-stoichiometry reported in literature is actually due to unreliable chemical analyses. The structural role of the minor elements (Cu, Zn and Tl) in wakabayashilite is also discussed.

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Section: Introductionsupporting

confidence: 81%

Chemical variability in wakabayashilite: a real feature or an analytical artifact?

et al. 2014

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“…Furthermore, although the As 4 S 6(g) dimer is often not detected, it is present as the predominant phase. Both Janai et al [45] and Hamman et al [46] agree that the As 4 S 6(g) phase is the predominant phase; however, it is not detected because it ionizes and dissociates into other species when analyzed spectrometrically.…”

Section: Arsenic Sulfidesmentioning

confidence: 96%

“…In 1986, Hamman and Santiago [46] emphasized the great interest in the study of As 4 S 6 properties, analyzing by mass spectrometry the volatilizations from two samples of As 4 S 6 , prepared in different ways in order to compare the volatilizations according to the way of crystal production. The first sample was prepared in a vacuum inside quartz tubes at 827 • C for 15 h, allowing the tube to cool down to room temperature to obtain a glassy sample, whereas the second was prepared by evaporation of a solution in Servofrax glass by spin coating.…”

Section: Arsenic Sulfidesmentioning

confidence: 99%

“…From the data analyzed for the simple arsenic sulfides' decomposition, we can conclude that arsenic sulfides volatilize in multiple phases in parallel; but the predominant gaseous phases are As 4 S 6 , As 4 S 4 , As 4 S 3 , and As 4 , shown in Figure 1. Additionally, according to Hammn et al [46] the magnitude of these volatilizations would depend directly on the thermal history of the samples studied, i.e., the previous conditions to which they were subjected before the study.…”

Section: Arsenic Sulfidesmentioning

confidence: 99%

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Behavior of As/AsxSy in Neutral and Oxidizing Atmospheres at High Temperatures—An Overview

Castro

Balladares

Jerez

et al. 2022

Metals

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The reaction mechanisms in As and As-S systems during their oxidation and/or thermal decomposition are complex to describe due to the physicochemical characteristics of arsenic and its sulfides; the information highlighted in the literature was analyzed and correlated to determinate the predominant phases and reaction mechanisms during the thermal decomposition and oxidation of arsenic, in its elemental form and in sulfurate phases. As a result of this analysis, it was determined that the predominant phases are mainly composed of allotropies of arsenic, sulfides, and dimers. In addition, reaction mechanisms are provided that describe the behavior of arsenic and its sulfides during its thermal decomposition and oxidation.

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“…although its molecular peak was not detectable by mass spectrometrypresumably due to its spontaneous fragmentation after electron This journal is © The Royal Society of Chemistry 2011 impact. 14 Further absorptions found at 384.4 and 355.5 cm -1 are attributed to the decomposition product As 4 S 4 .…”

Section: Matrix Ir Spectra Of the Gas Phase Over As 4 S 4 And As 2 Smentioning

confidence: 91%

AsS2Cl—an Arsenic(v) Compound? Formation, Stability and Structure of gaseous AsSCl and AsS2Cl—a combined experimental and theoretical study

2011

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By reaction of solid As 4 S 4 with gaseous Cl 2 at a temperature of 410 K gaseous AsSCl and AsS 2 Cl are formed. Unexpectedly in AsS 2 Cl the arsenic is not of formal oxidation state +V but +III: the molecular structure of AsS 2 Cl is arranged as a 1-chloro-dithia-arsirane and comprises an hitherto unknown AsS 2 three-membered ring. Thermodynamic data on AsSCl and AsS 2 Cl are obtained by mass spectrometry (MS). The experimental data are extended and confirmed by ab initio quantum chemical calculations (QC). The following values are given:

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Evidence for As4S6 molecule as a structural model for amorphous arsenic sulfide from mass spectrometric analysis

Cited by 9 publications

References 8 publications

Chemical variability in wakabayashilite: a real feature or an analytical artifact?

Chemical variability in wakabayashilite: a real feature or an analytical artifact?

Behavior of As/AsxSy in Neutral and Oxidizing Atmospheres at High Temperatures—An Overview

AsS2Cl—an Arsenic(v) Compound? Formation, Stability and Structure of gaseous AsSCl and AsS2Cl—a combined experimental and theoretical study

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