Exact coexistence surfaces containing double critical points for a three-component solution on the Bethe,honeycomb, and square lattices

A model is considered in which the bonds of a lattice are covered by rodlike molecules. Neighboring molecular ends interact with orientation-dependent interactions. The model exhibits closed -loop phase diagrams and double critical points. Exact coexistence surfaces are calculated for the model on the Bethe, honeycomb, and square lattices. The nature of the doubling of the critical exponent near a double critical point is calculated. The behavior of the critical line in the neighborhood of a double critical point is calculated exactly.     

The pyrolysis and nonflaming oxidative degradation of poly(vinylfluoride)

The thermal degradation of poly(vinylfluoride) (PVF) was studied under slow heating conditions to 1000°C with and without the presence of air. The degradation products, classified as low-boiling volatiles, high-boiling volatiles, and nonvolatile residues, were analyzed quantitatively by gas chromatography—mass spectrometry and several spectroscopic methods. Initial stages of degradation begin at 420°C with the evolution of HF and benzene and rapidly reach a maximum in sample weight loss by 450°C. One-third of this weight loss was in the form of hydrofluoric acid (HF) and at least 70 low-boiling volatile compounds that consisted of substituted aromatics, unsaturated hydrocarbons, and multiple-ring compounds, many of which contained a fluorine atom. The high-boiling volatile fraction contained compounds with more aliphatic but less aromatic character than the low-boiling. The nonvolatile residue retained 4% of the original fluorine content and exhibited strong unsaturated character. In the presence of oxygen HF, CO, and H₂O were the major constituents of the low-boiling volatiles; the organic fraction was essentially unchanged in composition but reduced in overall concentration. The overall weight-loss process was bimodal in air and produced a thermally resistant residue that degraded by 650°C. A comparison of degradation products from poly(vinylchloride) with this work demonstrates that PVF forms more lower-molecular-weight, halogen-containing compounds, whereas the former produced more HCl and nonvolatile residue containing a lower halogen content.     

A novel sensitized chemiluminescence: Infrared emissions from thiazine dyes sensitized by singlet oxygen

An unusual infrared chemiluminescence emission (8130Å) of methylene blue, and other thiazine dyes, sensitized by singlet molecular oxygen is reported. This chemiluminescence does not correspond to the ordinary fluorescence of the dye and cannot be explained by previously proposed mechanisms for singlet oxygen sensitized emissions of dyes. From energetic considerations singlet molecular oxygen in its ¹Σ_g⁺ state is postulated as the sensitizing agent for the thiazine dye chemiluminescences. Schemes in which ¹Σ_g⁺ oxygen transfers electronic excitation energy (a) to the lowest triplet state of the dye, (b) to a combined multiplicity state of the lowest triplet state of the dye, and triplet molecular oxygen, or (c) to a charge-transfer state between the dye and oxygen, are compared. The chemiluminescence of methylene blue in aqueous solution may be used as a luminescent probe for ¹Σ_g⁺ oxygen.     

Hybrid catalysts: the synthesis, structure and ethene polymerisation activity of (salicylaldiminato)(pyrrolylaldiminato) titanium complexes

The mono(salicylaldiminato) complexes Ti{3-tBu-2-(O)C6H3CH=N(R)}Cl3(THF)(where R = C6H5, C6F5) react with the metallated pyrrolylaldiminato ligand, K[2-(C6H5NCH)C4H3N], to afford the first examples of hybrid salicylaldiminato-ligated octahedral titanium complexes; the pre-catalysts give from very high to extremely high ethene polymerisation productivities when activated with MAO.