3141-10-4Relevant academic research and scientific papers
Synthesis of a Homologous Series of Trialkyl Arsines (C3-C12) and Applications of Arsenic Triiodide as a Synthetic Precursor
Ligiéro, Carolina B.P.,Francisco, Marcos A.S.,Gama, Michelle S.,Carbonezi, Carlos A.,Leocadio, Isabela C.L.,de Souza, Wladmir F.,Esteves, Pierre M.
, p. 912 - 916 (2021/03/17)
This work presents some modifications in the post-synthetic processing for a classical arsenic reagent: AsI3. In comparison with the widely used analog, the trichloride, arsenic triiodide presents several advantages such as low toxicity, air stability, and low volatility. It was used as a synthetic precursor in the preparation of a variety of arsenic(III) derivatives like arsines, arsenites, and thioarsenites. Besides that, AsI3 was submitted to a diversity-oriented Grignard reaction in the preparation of a homologous series of trialkyl arsines ranging from AsC3H9 to AsC12H27. The series was analyzed by comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry to provide a trialkyl arsines library that can be used for the direct analysis of natural samples.
Determination of the mean enthalpy of dissociation of arsenic-oxygen bonds in some arsenic (III) alkoxides
De Souza, Antonio G.,Brasilino, Maria G.A.,Airoldi, Claudio
, p. 1359 - 1367 (2007/10/03)
The standard molar enthalpy of formation of arsenic alkoxides in the liquid phase, As(OR)3 {R = ethyl (Et), n-propyl (Prn), i-propyl (Pri), n-butyl (Bun), and i-butyl (Bui)}, was determined through reaction-solution calorimetry in chloroform based on the reaction: As(NEt2)3(1) + 3ROH(1) = As(OR)3(1); ΔsolHmo at T = 298.15 K. This series of alkoxides gave the following molar enthalpy of formation ΔfHmo values: -(758.1 ± 9.0) kJ · mol-1, -(774.3 ± 9.0) kJ · mol-1, -(809.8 ± 9.0) kJ · mol-1, -(828.8 ± 8.9) kJ · mol-1, and -(863.4 ± 8.9) KJ · mol-1, respectively. The standard molar enthalpies of vaporization ΔvapHm (47.9 ± 1.1) kJ · mol-1, (51.2 ± 1.8) kJ · mol-1, (80.1 + 0.9) kJ · mol-1, (64.0 ± 1.8) kJ · mol-1 and (75.7 ± 1.2) kJ · mol-1, were obtained for the same sequence of alkoxides, by means of differential scanning calorimetry. By combining the preceding values with the standard molar enthalpy of formation of the alkoxide ΔfHm in the liquid phase, the standard molar enthalpy of formation of these compounds in the gas phase was obtained as -(710.2 ± 9.0) kJ · mol-1, -(723.1 ± 9.1) kJ · mol-1, -(729.3 ± 9.0) kJ · mol-1, -(764.8 ± 9.1) kJ · mol-1, and -(787.7 ± 9.0) kJ · mol-1, respectively. From these values, the mean enthalpy of dissociation of the arsenic-oxygen bond 〈Dm〉(As-O) was calculated for the sequence of the above alkoxides to give: (320 ± 5) kJ · mol-1, (301 ± 5) kJ · mol-1, (292 ± S) kJ · mol-1, (293 ± 5) kJ · mol-1, and (294 ± 5) kJ · mol-1. The linear correlation between the standard molar enthalpies of formation of the liquid alkoxides ΔfHm{As(OR)3,1} and the respective alcohol ΔfHm(ROH,1), suggests that these thermochemical data can be assessed for a series of normal and iso chain alcohols.
