POF3 Research Articles

Thermodynamic Properties of Phosphoryl Fluoride from 12 to 240°K. The Zero-Point Entropy of the Solid

The heat capacity of phosphoryl fluoride has been measured from 12 to 240°K for a sample with a purity greater than 99.9 mole %. The solid–liquid–vapor triple-point temperature and pressure were, respectively, 233.45°K and 774.06 torr. The heat of fusion was 3086 cal/mole. The heat of vaporization was determined as 5150 cal/mole at a temperature of 236.00°K and a pressure of 880.25 torr. The vapor pressure data were fitted by the equation lnP(torr) = − 487.49218 + 14 223.578 / T + 79.446599 lnT for the solid and by lnP(torr) = 8.05651 − 1206.41 / T for a short temperature range in the liquid phase. An entropy discrepancy, Sspec − Scalc, of 1.33 cal/mole·°K at 236.00°K was found between the spectroscopic entropy of 64.777 cal/mole·°K and the calorimetric value of 63.45 cal/mole·°K. A tentative model to explain the discrepancy has been proposed in which it is assumed that the degree of degeneracy of the several lowest eigenstates of the molecular motion are reduced when the molecule in the solid is subjected to the field of neighboring molecules of a certain symmetry.

Spin-lattice relaxation and molecular motion in liquid phosphorus trichloride, phosphorus oxychloride and phosphorus oxyfluoride

The 31P spin-lattice relaxation time has been measured at 9 Mhz in liquid PCl3, POCl3 and POF3 from the supercooled liquid almost to the liquid-vapour critical temperature. The 19F spin-lattice relaxation time has also been measured in POF3. The phosphorus spin-lattice relaxation times for these liquids are believed to be mainly controlled by the spin-rotation interaction. This is the first time as far as we are aware that this has been observed for the 31P magnetic resonance. For phosphorus trichloride the contributions from direct dipolar and spin-rotation interactions to the experimental 31P spin-lattice relaxation times have been separated. Correlation times for molecular reorientation and molecular angular velocity are derived and the 31P spin-rotation constant is estimated to be about 14 khz. The 31P spin-lattice relaxation times can be satisfactorily interpreted in terms of molecular motion parameters evaluated using shear viscosity data. The spin-rotation constant for POCl3 is estimated from the measured 31P spin-lattice relaxation times and viscosity data to be about 18 khz. For liquid POF3 both the 19F and the 31P spin-lattice relaxation times are believed to be mainly controlled by the spin-rotation interaction. A detailed analysis is made of the molecular motion. The spin-rotation constants for the 19F and 31P nuclei are estimated to be about 14 khz and 24 khz respectively.

Chemistry of phosphorus fluorides. Part II. Secondary alkylamino derivatives of phosphoryl fluoride

Phosphoryl fluoride reacts with dimethylamine in an equimolar ratio to yield volatile dimethylaminophosphoryldifluoride. The residual solid is a mixture of dimethylammonium hexafluorophosphate and dimethylammonium difluorophosphate salts rather than the simple fluoride salt. Dimethylamine reacts slowly with dimethylaminophosphoryldifluoride to yield bis(dimethylamino)phosphorylfluoride and the same complex fluorophosphate anions in the solid products. Physical data are reported on the alkylamino phosphoryl fluorides. The reaction of the difluorophosphoryl compound with hydrogen halides has been studied.

Preparation of Phosphoryl Difluoride Isothiocyanate and Phosphoryl Fluoride Diisothiocyanate

Angewandte Chemie International Edition in EnglishVolume 6, Issue 1 p. 90-90 Communication Preparation of Phosphoryl Difluoride Isothiocyanate and Phosphoryl Fluoride Diisothiocyanate Dr. H. W. Roesky, Corresponding Author Dr. H. W. Roesky Anorganisch-Chemisches Institut der Universität Hospitalstr. 8–9, 34 Göttingeon (Germany)Anorganisch-Chemisches Institut der Universität Hospitalstr. 8–9, 34 Göttingeon (Germany)Search for more papers by this author Dr. H. W. Roesky, Corresponding Author Dr. H. W. Roesky Anorganisch-Chemisches Institut der Universität Hospitalstr. 8–9, 34 Göttingeon (Germany)Anorganisch-Chemisches Institut der Universität Hospitalstr. 8–9, 34 Göttingeon (Germany)Search for more papers by this author First published: January 1967 https://doi.org/10.1002/anie.196700901AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume6, Issue1January 1967Pages 90-90 RelatedInformation

THE SULFURIC ACID SOLVENT SYSTEM: PART VIII. SOLUTIONS OF SOME PHOSPHORUS(V) AND VANADIUM(V) COMPOUNDS

It is shown that a number of phosphates ionize in sulfuric acid to give the P(OH)4+ion. Triphenyl phosphine and triethyl phosphate are fully protonated but phosphorus oxyfluoride and phosphorus oxychloride are shown to be nonelectrolytes.Ammonium metavanadate and vanadium pentoxide give the acid H[VO(HSO4)4] and there is evidence that the dimer H[V2O3(HSO4)6] and possibly higher polymers are present in increasing amounts with increasing concentration.

Normal Coordinate Treatments and Calculated Thermodynamic Properties of Phosphoryl Chloride, Thiophosphoryl Chloride, and Phosphoryl Fluoride

The infrared and Raman spectra for phosphoryl chloride, thiophosphoryl chloride, and phosphoryl fluoride were collected and examined for the most probable values for the wave numbers, intensities, and depolarization factors. The data are as follows: The Raman displacements Δσ in cm—1, the relative intensities I, and the depolarization factors ρ are for POCL3: Δσ(1)ρ = 192.85 (8) 0.83, 267.39 (6) 0.64, 337.44 (7) 0.81, 486.24 (10) 0.05, 581.2 (3) 6/7, and 1289.9 (5) 0.04; for PSCl3: 172 (5) 6/7, 247 (7) 6/7, 247 (calculated) 430 (10) 0.1, 538 (1) 6/7, and 753 (1) P; and for POF3: 337 (w) 6/7, 476 (m) 6/7, 483 (from infrared) P, 875 (s) 0.05, 982 (vw) 6/7, and 1395 (m) 0.1. As for the infrared spectral data, those of G. Cilento et al., were used for PSCl3, and those of Gutowsky and Liehr were used for POF3. No published infrared spectral data were found for POCl3. Also normal coordinate treatments were conducted for POCl3, PSCl3, POF3, and PSF3 on the basis of a model having C3v symmetry. The normal coordinate treatments gave the listed wave numbers as fundamentals and lend support for the 247 cm—1 band for PSCl3 and 483 cm—1 band (observed in the infrared and assigned as fundamental by Gutowsky and Liehr) for POF3 as the missing Raman bands. Moreover, the F matrix elements obtained for these molecules were determined in such a manner that those potential constants for the PCl3 group had nearly the same values in both POCl3 and PSCl3, those for the PF3 group had nearly the same values in both POF3 and PSF3, the one for the PO group had nearly the same value in both POCl3 and POF3, and the one for the PS group had nearly the same value in both PSF3 and PSCl3. The potential constants determined had the following values in md/A: For POCl3, fPO=9.890, fPCl=2.466, fPClPCl=0.399, for PSCl3, fPS=0.030, fPCl=2.466, fPClPCl=0.399; for POF3, fPO=9.890, fPF=5.633, fPFPF=0.483, and for PSF3, fPS=2.9694, fPF=5.333, fPFPF=0.183. Finally, the values of the thermodynamic properties for these substances were computed for the ideal gaseous state using the rigid rotor harmonic oscillator approximation at 1 atm from 200° to 1000°K.

Phosphorus-Halogen Compounds from Phosphorus Pentoxide and Halides. Properties of Phosphorus Trifluoride and Phosphorus Oxyfluoride*

Phosphorus-Halogen Compounds from Phosphorus Pentoxide and Halides. Properties of Phosphorus Trifluoride and Phosphorus Oxyfluoride^*