ISSN:
1572-9001
Keywords:
Bomb calorimetry
;
enthalpy of combustion
;
enthalpy of formation
;
enthalpy of fusion
;
enthalpy of vaporization
;
enthalpy of sublimation
;
estimation methods
;
group additivity
;
heat capacity
;
triphenylphosphine sulfide
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract The first measurements of the enthalpies of combustion, sublimation, and fusion of an organo-phosphorus sulfide, triphenylphosphine sulfide, are reported: δc H m o (C18H15PS, cr)=−(10752.58 ±2.90), δsub H m o (C18H15PS, 403 K)=(136.80±6.09), and δfus H 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 δsub H m o (298.15 K)=(142.8 ±6.8) and δfus H 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: δf H 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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF02275161
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