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- W2030892618 abstract "Abstract The thermal behaviour of A 4 B 3 cage molecules (A = P, As; B = S, Se) was investigated by differential scanning calorimetry, X-ray methods and high-performance liquid chromatography. On heating, the molecules P 4 S 3 , P 4 Se 3 , As 4 S 3 , and with rapid heating rates As 4 Se 3 , transform into the plastic-crystalline state, the structure of which is related to the β-Mn structure with space group R3m . The lattice constants of the so far not described plastic crystals of P 4 Se 3 and As 4 S 3 were determined to be: a = 1622.3(9) pm, α = 89.47(7)° at 370 K (P 4 Se 3 ); a =1660(1) pm, α = 87.86(15)° at 450 K (As 4 S 3 ). P 4 S 3 and P 4 Se 3 show a phase transition within the plastic-crystalline state, possibly in a simple cubic structure. The transformation temperature of P 4 S 3 is very close to the melting point and can be observed only on cooling. In the high-temperature X-ray photographs of P 4 Se 3 , As 4 S 3 and As 4 Se 3 , the decomposition into P 4 Se 4 , As 4 S 4 and As 4 Se 4 , respectively, and unidentified amorphous products were observed. This decomposition influences the melting behaviour of A 4 B 3 compounds. At equilibrium conditions most decompose peritectoidally on heating, with fast heating rates, congruent melting or a transformation into the plastic-crystalline modification [As 4 Se 3 ], occurs. In the melt, however, A 4 B 3 seems to be the stable species again. The extent and the starting temperature of this decomposition was investigated; the decomposition, or polymerization, of the A 4 B 3 molecules increased in the order: P 4 Se 3 4 S 3 4 Se 3 ." @default.
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- W2030892618 date "1984-11-01" @default.
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- W2030892618 title "Thermal behaviour of A4B3 cage molecules (A = P, As; B = S, Se)" @default.
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- W2030892618 doi "https://doi.org/10.1016/0040-6031(84)85123-0" @default.
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