127323-69-7Relevant academic research and scientific papers
Acidity, basicity, and ion-molecule reactions of arsine in the gas phase by ion cyclotron resonance spectroscopy
Wyatt,Holtz,McMahon,Beauchamp
, p. 1511 - 1517 (1974)
The ion-molecule reactions of arsine, both in pure form and in binary mixtures with several other molecules, have been investigated by ion cyclotron resonance spectroscopy. Reaction pathways, product distributions, and rate constants have been determined for ion-molecule reactions of both positive and, to a lesser extent, negative ions. Rate constants are determined by examining variation of ion abundance with both pressure and time, the latter experiments utilizing trapped ion techniques. Arsine fragment ions condense with neutral AsH3 to generate product ions containing two and, on further reaction, three atoms af arsenic. In the process of condensation, one or two molecules of H2 are expelled. The formation of AsH4+ occurs from AsH3+ which does not undergo condensation reactions to any significant extent. Where possible, thermochemical data have been determined, including the gas-phase acidity, PA(AsH2-) = 360 ± 10 kcal/mol, and basicity, PA(AsH3) = 175 ± 5 kcal/mol, of AsH3. Observation of gas-phase nucleophilic displacement reactions involving AsH3 as a nucleophile have allowed limits to be placed on the basicity of AsH3 toward a soft acid, CH3+. The implications of these results are discussed and the ion-molecule reactions of AsH3 are compared with those of other hydrides.
Infrared Product Spectra of Arsine-Ozone Complexes, Reaction Products, and Photolysis in Solid Argon
Andrews, Lester,Withnall, Robert,Moores, Brian W.
, p. 1279 - 1285 (1989)
Codeposition of AsH3 and O3 at high dilution in argon gave a large yield of AsH3-O3 complex and a small yield of reaction products identified as cis- and trans-H2AsOH.The complex photolyzed with red light, which showed that a specific interaction within the complex markedly increased the red photodissociation probability for the O3 submolecule.The red photolysis products were H3AsO, H2AsOH, and an intermediate species tentatively identified as HAsO.Further blue and near-UV irradiations destroyed HAsO and produced HOAsO2.This AsH3 and O3 study parallels earlier PH3 work and shows that AsH3, is slightly more reactive than PH3 with O3.
Submillimeter-wave spectrum of the AsH2 radical in the 2B1 ground electronic state
Fujiwara, Hideo,Kobayashi, Kaori,Ozeki, Hiroyuki,Saito, Shuji
, p. 5351 - 5355 (1998)
The pure rotational spectrum of the AsH2 radical in its 2B1 ground electronic state was observed for the first time by microwave spectroscopy. The AsH2 radical was generated in a free-space cell by dc-glow discharge of a mixture of H2 and O2 gases over arsenic powder. Fifty-five fine and hyperfine components of six rotational transitions were measured in the frequency region of 304-374 GHz, and were analyzed by least-squares methods. Molecular constants, including the rotational constants, the centrifugal distortion constants, the spin-rotation coupling constant incorporating the centrifugal distortion term, and the hyperfine coupling constants associated with the arsenic and hydrogen nuclei, were precisely determined. The bonding in AsH2 was discussed on the basis of the hyperfine coupling constants, first determined in the present study.
Etching AlAs with HF for epitaxial lift-off applications
Voncken,Schermer,Van Niftrik,Bauhuis,Mulder,Larsen,Peters,De Bruin,Klaassen,Kelly
, p. G347-G352 (2004)
The epitaxial lift-off process allows the separation of a thin layer of III/V material from the substrate by selective etching of an intermediate AlAs layer with HF In a theory proposed for this process, it was assumed that for every mole of AIAs dissolved three moles of H2 gas are formed. In order to verify this assumption the reaction mechanism and stoichiometry were investigated in the present work. The solid, solution and gaseous reaction products of the etch process have been examined by a number of techniques, It was found that aluminum fluoride is formed, both in the solid form as well as in solution. Furthermore, instead of H2 arsine (AsH3) is formed in the etch process. Some oxygen-related arsenic compounds like AsO, AsOH, and AsO2 have also been detected with gas chromatography/mass spectroscopy. The presence of oxygen in the etching environment accelerates the etching process, while a total absence of oxygen resulted in the process coming to a premature halt. It is argued that, in the absence of oxygen, the etching surface is stabilized, possibly by the sparingly soluble A1F3 or by solid arsenic.
Electrochemical preparation of H2S and H2Se
Bastide, Stephane,Huegel, Paul,Levy-Clement, Claude,Hodes, Gary
, p. D35-D41 (2005)
H2S and H2Se have been electrolytically prepared by electrolysis in aqueous H2SO4 solutions of composite cathodes made of S or Se and graphite. The efficiencies depended strongly on the electrolyte composition, in particular on the acid concentration and presence of K+. Faradaic efficiencies of 80% were obtained in dilute (0.05 M) acid, and this increased to 100% with added K2SO4. The efficiencies dropped drastically in concentrated acid (>a few moles). H 2Te and AsH3 generation were also briefly studied for comparison. The mechanisms of hydride formation are discussed. Both the reaction of nascent hydrogen with the free element and direct reduction of the element are considered. The latter is believed to be the dominant mechanism.
Ba11KX7O2 (X = P, AS): Two novel zintl phases with infinite chains of oxygen centered Ba6 octahedra, isolated X3- and dimeric X24- anions
Lulei, Michael
, p. 1796 - 1802 (1997)
Reactions of BaX (X = P, As) with Ba, K and BaO in tantalum tubes at 900-1000°C yielded black, very air-and moisture-sensitive crystals of Ba11KP7O2 and isotypic Ba11KAs7O2 which were characterized by EDX and X-ray diffraction (orthorhombic, Fddd, Z = 8; a = 1069.9(1), b = 1514.3(2), c = 3164.6(4) pm and a = 1087.8(2), b = 1542.3(2), c = 3232.4(4) pm, respectively). The structure contains infinite zigzag chains, 1∞[Ba4Ba2/2O], of oxygen-centered, corner-sharing Ba6 octahedra along [100]. They are connected by linear strings built of alternating isolated X atoms and X2 dimers to form layers parallel to (001). While the isolated X atoms are surrounded by eight Ba forming a distorted cube, the X2 dimers center a Ba12 polyhedron which is comprised of a pair of face-sharing Ba square antiprisms. This results in a cube-antiprism-antiprism-cube sequence of face-sharing Ba polyhedra. Additional X atoms function as spacers between the layers and connect them along [001]. Two atom positions are statistically occupied by Ba and K, and the formula may be written as Ba2+11K+X3-5(X 2)4-O2-2 according to the Zintl-Klemm concept.
Synthesis of volatile inorganic hydrides by electrochemical method
Turygin,Tomilov,Berezkin, M. Yu.,Fedorov
, p. 1459 - 1478 (2010)
Published data and results of our investigations on the problem of electrochemical synthesis of arsenic, phosphorus, and germanium hydrides are generalized. The results of the developments of the physicochemical bases of arsine synthesis by electrochemical reduction of arsenic acid, phosphine by reduction of white phosphorus in organic solvents, and monogermane by reduction of germanate in basic conditions are reported. The current yield of hydrides is 95, 90, and 40%, respectively. The promising guidelines of the practical use of electrochemical methods of the synthesis of the hydrides in the manufacture of semiconductor materials for microelectronics, optics, and laser engineering are discussed. The development of an arsine generator attracts considerable interest, which can serve as a basis for an aggregative continuous apparatus used in complex flow charts of manufacture of semiconductor materials.
Pnictogen-hydride activation by (silox)3Ta (silox = tBu3SiO); Attempts to circumvent the constraints of orbital symmetry in N2 activation
Hulley, Elliott B.,Bonanno, Jeffrey B.,Wolczanski, Peter T.,Cundari, Thomas R.,Lobkovsky, Emil B.
, p. 8524 - 8544 (2010/12/18)
Activation of N2 by (silox)3Ta (1, silox = tBu3SiO) to afford (silox)3Ta=N-N=Ta(silox) 3 (12-N2) does not occur despite ΔG°cald = -55.6 kcal/mol because of constraints of orbital symmetry, prompting efforts at an independent synthesis that included a study of REH2 activation (E = N, P, As). Oxidative addition of REH 2 to 1 afforded (silox)3HTaEHR (2-NHR, R = H, Me, nBu, C6H4-p-X (X = H, Me, NMe2); 2-PHR, R = H, Ph; 2-AsHR, R = H, Ph), which underwent 1,2-H2- elimination to form (silox)3Ta=NR (1=NR; R = H, Me, nBu, C6H4-p-X (X = H (X-ray), Me, NMe2, CF 3)), (silox)3Ta=PR (1=PR; R = H, Ph), and (silox) 3Ta=AsR (1=AsR; R = H, Ph). Kinetics revealed NH bond-breaking as critical, and As > N > P rates for (silox)3HTaEHPh (2-EHPh) were attributed to (1) ΔG°calc(N) calc(P) ～ ΔG°calc(As); (2) similar fractional reaction coordinates (RCs), but with RC shorter for N P～As. Calculations of the pnictidenes aided interpretation of UV-vis spectra. Addition of H2NNH2 or H2N-N(cNC2H3Me) to 1 afforded 1=NH, obviating these routes to 12-N2, and formation of (silox)3MeTaNHNH2 (4-NHNH2) and (silox) 3MeTaNH(-cNCHMeCH2) (4-NH(azir)) occurred upon exposure to (silox)3Ta=CH2 (1=CH2). Thermolyses of 4-NHNH2 and 4-NH(azir) yielded [(silox)2TaMe](μ- NαHNβ)(μ-NγHN δH)[Ta(silox)2] (5) and [(silox)3MeTa] (μ-η2-N,N: η1-C-NHNHCH2CH 2CH2)[Ta(κ-O,C-OSitBu2CMe 2CH2)(silox)2] (7, X-ray), respectively. (silox)3Ta=CPPh3 (1=CPPh3, X-ray) was a byproduct from Ph3PCH2 treatment of 1 to give 1=CH 2. Addition of Na(silox) to [(THF)2Cl3Ta] 2(μ-N2) led to [(silox)2ClTa](μ-N 2) (8-Cl), and via subsequent methylation, [(silox) 2MeTa]2(μ-N2) (8-Me); both dimers were thermally stable. Orbital symmetry requirements for N2 capture by 1 and pertinent calculations are given.
GASEOUS DIELECTRICS WITH LOW GLOBAL WARMING POTENTIALS
-
, (2010/12/31)
A dielectric gaseous compound which exhibits the following properties: a boiling point in the range between about ?20° C. to about ?273° C.; non-ozone depleting; a GWP less than about 22,200; chemical stability, as measured by a negative standard enthalpy of formation (dHf0); a toxicity level such that when the dielectric gas leaks, the effective diluted concentration does not exceed its PEL; and a dielectric strength greater than air.
Electrochemical reduction of As(III) in acid media
Smirnov,Turygin,Shalashova,Khudenko,Tomilov
, p. 25 - 29 (2008/10/09)
Measurements of the cathode potentials of different electrode materials in the galvanostatic electrolysis of As2O3 solutions in sulfuric acid indicate that the Pb cathode ensures the most stable negative potential, favorable for AsH3 formation. Preparative electrolyses confirm stability of the arsine yield in a series of experiments. The current efficiency for arsine on the Pb cathode is 60-70%. The byproduct of this process is As0, with a current efficiency of about 2%. We have designed and tested an electrolyzer with improved hydrodynamics, which makes it possible to avoid the formation of dead zones and to prevent the cathode chamber from being clogged.
