A survey of thermodynamic properties of the compounds of the elements CHNOPS Progress report, 1 Oct. - 31 Dec. 1966

Thermodynamic properties for compounds of the elements carbon, hydrogen, nitrogen, oxygen, phosphorus, and sulfu

The 1-((diorganooxyphosphonyl)-methyl)-2,4- and -2,6-diamido benzenes

1-((Diorgano oxyphosphonyl) methyl)-2,4- and -2,6-dinitro and diamino benzenes are prepared by nitrating an (organophosphonyl) methyl benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo grounds (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids (HO)2P(double bond O)single bond. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures

Fire-resistant phosphorus containing polyimides and copolyimides

Phosphorus-containing polyimides and copolyimides are synthesized in a two-step polycondensation reaction from 1- (diorganooxyphosphonl)methly 2,4- and 2,6-diaminobenzenes and tetracarboxylic anhydride. The diorgano position of the diorganooxyphosphonyl group includes alkyl, such as ethyl, substituted alkyl, such as 2-chloroethyl, and aryl such as phenyl. The tetracarboxylic anhydries include compounds such as pyrometallitic dianhydride and benzophenone tetracarboxylic dianhydride. The glass transition temperature (Tg) of the polyimides is reduced by incorporation of the (dialkoxyphosphonyl)methyl groups. The phosphorus-containing copolyimides show a considerably higher degree of fire-resistance as compared to that of the corresponding common polyimides

Combustive approach for measuring total volatile phosphorus content in landfill gas

A technique was developed to measure the total gaseous phosphorus content in biogas. The amount of air needed for a neutral to oxidising flame was mixed with the biogas. The gas mixture was burnt in a closed quartz burner and the combustion gasses were bubbled through a nitric acid solution. The phosphate content in the bubbling liquid was determined with sector field ICP-MS. The technique was validated in the lab with phosphine. Afterwards the set-up was installed on a landfill. The total gaseous phosphorus content in the landfill gas, measured with the combustive technique, ranged from 1.65 to 4.44 mug P/m(3). At the same time the phosphine concentration in the landfill gas was determined gas chromatographically (GC). The phosphine (PH3) content measured with GC ranged from 7.6 to 16.7 mug PH3-P/m(3). Since the phosphine-P content (GC) was consistently higher than the total gaseous phosphorus content (burner/ICP-MS), the hypothesised presence of highly toxic gaseous phosphorus compounds other than phosphine could not be demonstrated

Designing isoelectronic counterparts to layered group V semiconductors

In analogy to III-V compounds, which have significantly broadened the scope of group IV semiconductors, we propose IV-VI compounds as isoelectronic counterparts to layered group V semiconductors. Using {\em ab initio} density functional theory, we study yet unrealized structural phases of silicon mono-sulfide (SiS). We find the black-phosphorus-like $\alpha$-SiS to be almost equally stable as the blue-phosphorus-like $\beta$-SiS. Both $\alpha$-SiS and $\beta$-SiS monolayers display a significant, indirect band gap that depends sensitively on the in-layer strain. Unlike 2D semiconductors of group V elements with the corresponding nonplanar structure, different SiS allotropes show a strong polarization either within or normal to the layers. We find that SiS may form both lateral and vertical heterostructures with phosphorene at a very small energy penalty, offering an unprecedented tunability in structural and electronic properties of SiS-P compounds.Comment: 7 pages, 5 figure

Solid-State Chemistry with Nonmetal Nitrides

Among the nonmetal nitrides, the polymeric binary compounds BN and Si3N4are of particular interest for the development of materials for high-performance applications. The outstanding features of both substances are their thermal, mechanical, and chemical stability, coupled with their low density. Because of their extremely low reactivity, boron and silicon nitride are hardly ever used as starting materials for the preparation of ternary nitrides, but are used primarily in the manufacture of crucibles or other vessels or as insulation materials. The chemistry of ternary and higher nonmetal nitrides that contain electropositive elements and are thus analogous with the oxo compounds such as borates, silicates, phosphates, or sulfates was neglected for many years. Starting from the recent successful preparation of pure P3N5, a further binary nonmetal nitride which shows similarities with Si3N4 with regard to both its structure and properties, this review deals systematically with the solid-state chemistry of ternary and higher phosphorus(V) nitrides and the relationship between the various types of structure found in this class of substance and the resulting properties and possible applications. From the point of view of preparative solid-state chemistry the syntheses, structures, and properties of the binary nonmetal nitrides BN, Si3N4, and P3N5 will be compared and contrasted. The chemistry of the phosphorus(V) nitrides leads us to expect that other nonmetals such as boron, silicon, sulfur, and carbon will also participate in a rich nitride chemistry, as initial reports indeed indicate

Flammability behaviour of wood and a review of the methods for its reduction

Wood is one of the most sustainable, aesthetically pleasing and environmentally benign materials. Not only is wood often an integral part of structures, it is also the main source of furnishings found in homes, schools, and offices around the world. The often inevitable hazards of fire make wood a very desirable material for further investigation. As well as ignition resistance and a low heat release rate, timber products have long been required to resist burn-through and maintain structural integrity whilst continuing to provide protection when exposed to fire or heat. Various industry standard tests are thus required to ensure adequate protection from fire is provided. When heated, wood undergoes thermal degradation and combustion to produce gases, vapours, tars and char. In order to understand and alter the fire behaviour of wood, it is necessary to know in as much detail as possible about its processes of decomposition. Various thermal analysis and flammability assessment techniques are utilised for this purpose, including thermogravimetric analysis, cone calorimetry and the single burning item test. The results of such tests are often highly dependent on various parameters including changes to the gas composition, temperature, heating rate, and sample shape size. Potential approaches for fire retarding timber are reviewed, identifying two main approaches: char formation and isolating layers. Other potential approaches are recognised, including the use of inorganic minerals, such as sericrite, and metal foils in combination with intumescent products. Formulations containing silicon, nitrogen and phosphorus have been reported, and efforts to retain silicon in the wood have been successful using micro-layers of silicon dioxide. Nano-scale fire retardants, such as nanocomposite coatings, are considered to provide a new generation of fire retardants, and may have potential for wood. Expandable graphite is identified for use in polymers and has potential for wood provided coating applications are preferred

Sterically restricted tin phosphines, stabilized by weak intramolecular donor-acceptor interactions

Funding: Engineering and Physical Sciences Research Council (EPSRC)Four related sterically restricted pen-substituted acenaphthenes have been prepared containing mixed tin phosphorus moieties in the proximal 5,6-positions (Acenap[SnR3][(PPr2)-Pr-i]; Acenap = acenaphthene-5,6-diyl; R-3 = Ph-3 (1), Ph2Cl (2), Me2Cl (3), Bu2Cl (4)). The degree of intramolecular P-Sn bonding within the series was investigated by X-ray crystallography, solution and solid-state NMR spectroscopy, and density functional theory (DFT/B3LYP/SBKJC/PCM) calculations. All members of the series adopt a conformation such that the phosphorus lone pair is located directly opposite the tin center, promoting an intramolecular donor acceptor P -> Sn type interaction. The extent of covalent bonding between Sn and P is found to be much greater in triorganotin chlorides 2-4 in comparison with the triphenyl derivative 1. Coordination of a highly electronegative chlorine atom naturally increases the Lewis acidity of the tin center, enhancing the Ip(P)-sigma*(Sn-Y) donor acceptor 3c-4e type interaction, as indicated by conspicuously short Sn-P peri distances and significant (1)J(P-31,Sn-119) spin spin coupling constants (SSCCs) in the range 740-754 Hz. Evidence supporting the presence of this interaction was also found in solid-state NMR spectra of some of the compounds which exhibit an indirect spin spin coupling on the same order of magnitude as observed in solution. DFT calculations confirm the increased covalent bonding between P and Sn in 2-4, with notable WBIs of ca. 0.35 obtained, in comparison to 0.1 in 1.PostprintPeer reviewe