Abstract
The first measurements of the enthalpies of combustion, sublimation, and fusion of an organo-phosphorus sulfide, triphenylphosphine sulfide, are reported: δcH m o (C18H15PS, cr)=−(10752.58 ±2.90), δsubH m o (C18H15PS, 403 K)=(136.80±6.09), and δfusH m o (C18H15PS, Tm=435.92 K) =(30.53±0.21) kJ·mol−1. Correction of the phase change enthalpies toT=298.15K and po =0.1 MPa results in the standard phase change enthalpy values of δsubH m o (298.15 K)=(142.8 ±6.8) and δfusH m o (298.15 K)=(19.28±0.21) kj·mol−1. Accordingly, the enthalpies of formation of solid, liquid, and gaseous triphenylphosphine sulfide are derived: δfH m o (C18H15PS, cr) =(63.20±2.56), δfH m o (C18H15PS, l)=(82.48±2.57), and δfH m o (C18H15PS, g)=(206.0±7.3) kJ·mol−1. From these ancillary data, the P=S double-bond enthalpy is 394 kJ-mol−1 and in good agreement with earlier reaction calorimetry results. These phosphorus sulfide values are compared with those for the arsenic sulfides. Plausibility arguments are given for our results.
Published Version
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