Solute-solvent interactions in water-tert-butyl alcohol mixtures. VI. Enthalpies of solution for halo-para-substituted benzoates

Enthalpies of solution of sodium benzoate, potassium benzoate, and potassium halo-substituted benzoates are reported at 298.15°K in water and in nine water-tert-butyl alchol mixtures. Transfer enthalpies from water to the mixed solvent go through a maximum for about 0.055 mole fraction of alcohol. Additivity of ionic contributions in the enthalpies of transfer is verified. Substituent effects on the transfer enthalpies of benzoates are discussed in terms of size of the solutes and cohesion of the solvent mixtures. For Part V, see ref. 1.     

Thermodynamique des melanges binaires LiPO3-Pb(PO3)2: Diagramme de phases et étude thermodynamique du liquide

Study of solid-liquid phase diagram of LiPO₃-Pb(PO₃)₂ binary system, in certain calcination conditions, shows the existence of several metastable phasis. When heated at a temperature of 723 K the binary mixtures lead uncompletely to a defined compound Pb₂Li(PO₃). On heating these ternary solid mixtures, three eutectic reactions have been observed: LiPO₃+Pb(PO₃)₂→Liquid at a temperature of 793 K(1) LiPO₃+Pb₂Li(PO₃)₅→Liquid at a temperature of 843 K (2) Pb₂Li(PO₃)₅+Pb(PO₃)₂→Liquid at a temperature of 891 K (3) The metastable liquid phase appears in the system at temperature of 793 K. DTA experiments performed on the binary LiPO₃-Pb(PO₃)₂ mixtures, show a superposition of two diagrams. The first one is metastable and the second represents the stable equilibrium phase diagram. Measurements of liquid enthalpy of binary LiPO₃-Pb(PO₃)₂ system at temperature of 979.65 K were reported. The corresponding values were very small and so the binary system can be considered as athermal. Assuming an ideal behaviour, the liquidus curves in the metastable diagram were calculated and the eutectic reaction (LiPO₃-Pb(PO₃)₂→Liquid) was confirmed at 793 K. This revised version was published online in August 2006 with corrections to the Cover Date.     

Time-variable Method for Studying Reaction Rates in a Calorimeter

A novel method for the determination of rate constants of reactions, the time-variable method, is proposed in this paper. The method needs only three time points (t), peak heights () and pre-peak areas (), obtained from the measured thermoanalytical curve. It does not require the thermokinetic reaction to be completed. It utilizes data-processing on a computer to give the rate constants. Four reaction systems, including a first-order reaction, second-order reactions (with equal concentrations and with unequal concentrations) and a third-order reaction, were studied with this method. The method was validated and its theoretical basis was verified by the experimental results.This revised version was published online in November 2005 with corrections to the Cover Date.     

Polymer nanocomposites using zinc aluminum and magnesium aluminum oleate layered double hydroxides: Effects of the polymeric compatibilizer and of composition on the thermal and fire properties of PP/LDH nanocomposites

A series of five oleate-containing layered double hydroxides with varied ratios of zinc to magnesium, i.e., with the general formula Zn_2−yMg_yAl(OH)₆ [CH₃(CH₂)₇CHCH(CH₂)₇COO]·nH₂O, were synthesized and used to prepare nanocomposites of polypropylene (PP). The nanomaterials were characterized by elemental analysis, attenuated total reflection-infrared spectroscopy (ATR-IR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA), while the composites were characterized by XRD, TGA, transmission electron microscopy (TEM) and cone calorimetry. The zinc-containing LDH showed better dispersion in the polymer at the micrometer level than did the magnesium-containing LDH while both are equally well-dispersed at the nanometer level. The magnesium-containing composites led to more thermally stable systems in TGA experiments, while the zinc systems gave greater reductions in heat release rate during combustion. Dispersion was also affected by the amount of PP-g-MA which was present. More PP-g-MA gave better dispersion and a significantly reduced peak heat release rate, i.e., enhanced fire performance.     

Electron transfer in supercritical carbon dioxide: ultraexothermic charge recombination at the end of the "inverted region"

Charge-recombination rates in contact radical-ion pairs, formed between aromatic hydrocarbons and nitriles in supercritical CO(2) and heptane, decrease with the exothermicity of the reactions until they reach -70 kcal mol(-1), but from there on an increase is observed. The first decrease in rate is typical of the "inverted region" of electron-transfer reactions. The change to an increase in the rate for ultra-exothermic electron transfer indicates a new free-energy relationship. We show that the resulting "double-inverted region" is not due to a change in mechanism. It is an intrinsic property of electron-transfer reactions, and it is due to the increase of the reorganisation energy with the reaction exothermicity.     

Calorimetric and thermogravimetric studies of UV-irradiated polypropylene/starch-based materials aged in soil

We studied the biodegradability in soil of mixtures of polypropylene and a starch-based biodegradable additive. The changes in their properties were studied using calorimetry and thermogravimetric analysis. To observe the effect of UV radiation, the mixtures were photo-oxidized before biodegradation. The results were compared with those obtained from previous studies on non-photo-oxidized samples. Using calorimetry, we observed changes in the crystallinity of the samples and in their crystallization kinetics, which we analyzed using the Avrami equation. Photo-oxidation was found to reduce the crystallinity of the mixtures while degradation in soil increases it. Using thermogravimetry, we observed changes in the thermal stability and in the associated kinetic parameters, which we determined using an isoconversional integral method. Biodegradation tended to increase the thermal stability of the starch units and did not affect the polypropylene. Photo-oxidation tended to decrease the thermal stability of the mixture, although it may make the starch slightly more stable. The thermooxidative degradation of the mixtures was also studied.     

Thermoanalytical characterization of polyphenylacetylene: III. Use of modulated differential scanning calorimetry (MDSC)

Four polyphenylacetylene samples, synthesized using different C₆H₅OH/Mo molar ratios, were investigated thermoanalytically by modulated temperature differential scanning calorimetry (MTDSC) in order to clarify a non-reversible exothermic event observed between 473 and 523 K on normal DSC. A stepwise, non-reversible change in heat capacity suggests the presence of internal reactions within the sample, that are followed by decomposition with loss of volatile products.     

A New Chemo‐Enzymatic Route to Side‐Chain Liquid‐Crystalline Polymers: The Synthesis and Polymerization of 6‐(4‐Methoxybiphenyl‐4′‐oxy)hexyl Vinyl Hexanedioate

A novel synthetic method combining chemo and enzymatic synthesis strategies was employed to prepare a vinyl acetate type monomer, 6‐(4‐methoxybiphenyl‐4′‐oxy)hexyl vinyl hexanedioate (VA‐LC). Homo‐ and copolymers of VA‐LC with maleic anhydride (MAn) were prepared by conventional free radical polymerization using 2,2′‐azobisisobutyronitrile (AIBN) and 1,1′‐azobis (cyclohexane carbonitrile) (AHCN) as an initiator at 95 and 60 °C, respectively. The thermal properties of the generated polymeric material were investigated by differential scanning calorimetry (DSC), and the optical texture was inspected by polarizing optical microscopy (POM). While the monomer VA‐LC does not exhibit liquid‐crystalline properties, poly(VA‐LC), and the alternating copolymer of VA‐LC with maleic anhydride both displayed such properties.

     

Standard molar enthalpies of formation of dimethylbenzophenones

The standard (p⁰ = 0.1 MPa) molar enthalpy of formation of 3,4‐dimethylbenzophenone was derived from the standard molar energy of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpy of sublimation of the compound. From these experimental parameters, the standard molar enthalpy of formation of 3,4‐dimethylbenzophenone, in the gaseous phase and at T = 298.15 K, was derived as ?(17.1 ± 2.9) kJ mol^?1. Density functional theory was used to investigate the gas‐phase molecular energetics of the 12 dimethylbenzophenones. Molecular geometries and vibrational frequencies were computed at the B3LYP/6‐31G(d) level of theory. The larger 6‐311+G(2d,2p) basis set was used to compute the energy of all dimethylbenzophenones and of the other compounds that were considered for the estimation of the standard molar enthalpies of formation at T = 298.15 K. The calculations show that the 2,2′‐ and 4,4′‐dimethylbenzophenones are the least and most stable isomers, respectively. Finally, the calculated enthalpy of formation of the benzophenone that was also studied experimentally, 3,4‐dimethylbenzophenone, is ?16.7 kJ mol^?1, which is in excellent agreement with the experimental result. Copyright © 2008 John Wiley & Sons, Ltd.