Phosphorus thermodynamic properties

L. V. Gurvich, I. V. Veyts, and C. B. Alcock, Thermodynamic Properties of Individual Substances, Vol. 1 Elements Oxygen, Hydrogen (Deuterium, Tritium), Fluorine, Chlorine, Bromine, Iodine, Helium, Neon, Argon, Krypton, Xenon, Radon, Sulfur, Nitrogen, Phosphorus, and Their Compounds, Pt. 1 Methods and Computation, Hemisphere, New York, 1989. 

Farr (109)y of the Tennessee Valley Authority, has compiled a resume of the physical and thermodynamic properties of the allotropic forms of phosphorus. Based on entropy calculations from low temperature heat capacity measurements, Stephenson (318) believes that red crystalline triclinic phosphorus (T.V.A. designation V) is the most stable form at room temperature. This point of view is buttressed by the x-ray work of Roth, DeWitt, and Smith (376). Consequently we have selected red phosphorus V as the reference state up to its sublimation point at 704° K. 

SCH] Schlesinger, M. E., The thermodynamic properties of phosphorus and solid binary phosphides, Chem. Rev., 102, (2002), 4267-4301. Cited on page 204. 

Data on thermodynamic properties, mainly on the activity of phosphorus in liquid copper-iron alloys were... 

It is well known that liquids are characterized by a local order that is often close to one of the solid phases stable at the same density [1,2]. The existence of a well-defined local order is fundamental to understand liquid liquid transitions (LLTs), that is, the first-order transitions between two liquid phases different from each other in the local atomic arrangement and thermodynamic properties. Although an LLT can be possibly expected for multiatomic liquids, only quite recently it has been demonstrated that such transitions also exist for single component, isotropic liquids such as phosphorus [3,4], which polymerizes at high pressures and... 

Phosphorus see also Elements critical constants, 6-39 to 58 dielectric constant, 12-45 to 53 electron configuration, 1-18 to 19 heat capacity, 4-135 history, occurrence, uses, 4-1 to 42 ionization energy, 10-203 to 205 isotopes and their properties, 11-56 to 253 magnetic susceptibility, 4-142 to 147 physical properties, 4-133 to 134 thermodynamic properties, 5-1 to 3... 

The commonest form of phosphorus, and the one which is usually formed by condensation from the gaseous or liquid states, is the waxy, cubic, white form o -P4 (d 1.8232 gcm at 20°C). This, paradoxically, is also the most volatile and reactive solid form and thermodynamically the least stable. It is the slow phosphorescent oxidation of the vapour above these crystals that gives white phosphorus its most characteristic property. Indeed, the emission of yellow-green light from the oxidation of P4 is one of the earliest recorded examples of chemiluminescence, though the details of the reaction... 

The first kinetically stable dibenzosilafulvene (7), whose structure and properties should more correctly be described by the resonance hybrid 7a 7b with a great contribution of the ylide form 7a, reacts with phosphorus ylide to form betaine (8), which is rearranged, under thermodynamically controlled conditions, into the salt (9) (Scheme 4).24,25... 

Thus, we first discuss thermodynamics, paying attention to features that are important for polymer synthesis (e.g., dependence of equilibrium monomer concentration on polymerization variables) then we describe kinetics and thermodynamics of macrocyclization, trying to combine these two related problems, usually discussed separately. In particular we present the new theory of kinetic enhancement and kinetic reduction in macrocyclics. Thereafter, we describe the polymerization of several groups of monomers, namely cyclic ethers (oxiranes, oxetanes, oxolanes, acetals, and bicyclic compounds) lactones, cyclic sulfides, cyclic amines, lactams, cyclic iminoethers, siloxanes, and cyclic phosphorus-containing compounds, in this order. We attempted to treat the chapters uniformly we discuss practical methods of synthesis of the corresponding polymers (monomer syntheses and polymer properties are added), and conditions of reaching systems state and reasons of deviations. However, for various groups of monomers the quality of the available information differ so much, that this attempt of uniformity can not be fulfilled. 

Cyclic monomers with phosphorus atoms at different level of oxidation, namely, pentavalent (P ) and trivalent (P ), were polymerized according to anionic and/or cationic mechanism, giving as a result polymers with various structures and properties. The mechanism, kinetics, and thermodynamics of polymerization were described for selected groups of monomers. The structures of active centers were established and the rate constants, activation parameter, and thermodynamic parameter were determined. 

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