A note on the equivalence of shock manifold equations

The shock manifold equation is a first order nonlinear partial differential equation, which describes the kinematics of a shockfront in an ideal gas with constant specific heats. However, it was found that there was more than one of these shock manifold equations, and the shock surface could be embedded in a one parameter family of surfaces, obtained as a solution of any of these shock manifold equations. Associated with each shock manifold equation is a set of characteristic curves called lsquoshock raysrsquo. This paper investigates the nature of various associated shock ray equations.

Thermodynamic properties of the system toluene — 1, 1, 1-trichloroethane

Data on molar excess enthalpy on mixing at 298.15 K and 308.15 K, vapor-liquid equilibrium, latent heats of vaporization at 91.444 kPa and vapor pressures for the system toluene – 1, 1, 1-trichloroethane are presented. A simple adiabatic calorimeter designed for molar excess enthalpy measurements is described, tested and used. On présente, dans le cas du système toluène – 1, 1, 1-trichloréthane, des résultats relatifs aux grandeurs suivantes: a) enthalpie molaire d'excès à 298.15 K et 308.15 K; b) équilibre liquid-vapeur; c) chaleurs latentes de vaporisation à une pression absolue de 91.444 kP; d) pressions de vapeur. On décrit un calorimètre adiabatique simple, conçu pour mesurer l'enthalpie molaire d'excès, dont on a fait l'essai.

Thermodynamic properties of the systems benzene-chloroethanes

This paper presents the experimental data on vapor-liquid equilibrium and heats of mixing of mixtures of benzene with 1, e-dichloroethane, 1, l, 1 -trichloroethane, and lt1,2,2-tetrachloroethane.A literature survey revealed that the heats of mixing of benzene-l,2-dichloroethane have been studied and Table I shows the extent of study on this system.

Propagation of quasi-simple waves in a compressible rotating atmosphere

A class of self-propagating linear and nonlinear travelling wave solutions for compressible rotating fluid is studied using both numerical and analytical techiques. It is shown that, in general, a three dimensional linear wave is not periodic. However, for some range of wave numbers depending on rotation, horizontally propagating waves are periodic. When the rotation ohgr is equal to $$\sqrt {(\gamma - 1)/(4\gamma )}$$ , all horizontal waves are periodic. Here, gamma is the ratio of specific heats. The analytical study is based on phase space analysis. It reveals that the quasi-simple waves are periodic only in some plane, even when the propagation is horizontal, in contrast to the case of non-rotating flows for which there is a single parameter family of periodic solutions provided the waves propagate horizontally. A classification of the singular points of the governing differential equations for quasi-simple waves is also appended.

Structural effects on the vaporization of high molecular weight esters

To understand the effect of molecular weight and branching on the heats of vaporization (AH,) and their flow behavior, AH, and viscosity (7) were measured at different temperatures in the high molecular weight ester series: linear flexible di-n-alkyl sebacates and compact branched triglycerides with molecular weight ranging from 300 to 900. AHv" values (AHv corrected to 298 K) have been obtained with experimental AH, and also computed according to the group additivity method; a smaller-CH,- group value of 3.8 kJ mol-' compared to the normal value of 5.0 kJ mol-' is found to give good agreement with the experimental data (within 2-5% error). Both ester series have the same AH," irrespective of their molecular features, namely,shape, flexibility, and polarity, suggesting the coiling of the molecules during vaporization. The segmental motion of these ester series during their flow and its dependence on their molecular features unlike AH,' are demonstrated by the correlation of the enthalpy of activation for viscous flow (AH*) and the ratio AE,/AH* = n (AE, is the energy of vaporization) with molecular weight.

A parametric method 3 (PM3) study of trans‐stilbene

We report a comparative modified neglect of diatomic overlap (MNDO), Austin method one (AM1), and parametric method 3 (PM3) study of trans‐stilbene (tS) in its ground, excited (singlet and triplet), and ionic (positive and negative polarons and bipolarons) states. We have also calculated the barrier for ring rotation about the backbone single bond. Our results show that PM3 geometries are superior to MNDO and AM1, at least for tS. PM3 predicts, in contrast with MNDO, AM1 and even ab initio 3‐21G, a coplanar structure for tS, in accordance with recent experimental data. Singlet and triplet energies obtained from heats of formation are in surprisingly good agreement with experimental data.

Specific-heat measurements during cooling through the glass-transition region

In this paper we report the measurements of specific heats of five glass formers as they are cooled through the glass-transition region. The measurements are compared with other specific-heat measurements such as adiabatic-calorimetry and ac-calorimetry measurements. The data are then analyzed using a model of enthalpy relaxation and nonequilibrium cooling, which can track the nonequilibrium relaxation time tau(S). The relevant parameters that describe tau(S) are obtained, allowing us to compare the enthalpy-relaxation times obtained from this method with other methods. We display the clear connection of the unrelaxed enthalpy with the nonequilibrium relaxation time and also show the role played by the delayed heat release from the unrelaxed enthalpy in the glass-transition region. We have also made certain definite observations regarding the equilibrium configurational specific heat and the Vogel-Fulcher law, which describes tau(S).

Temperature-programmed desorption and surface reaction of thiophene over co-mo/.gamma.-Al2O3 hydrodesulfurization catalysts

The temperature-programmed desorption (TPD) and temperature-programmed surface reaction (TPSR) of thiophene over a series of Co-Mo/gamma-Al2O3, hydrodesulfurization (HDS) catalysts with varying Co to Mo ratios have been studied with the objective of understanding the promotional role of Co in the HDS reaction. As part of the study, the desorptions (TPD) and hydrogenations (TPSR) of butane, butene, and butadiene over these catalysts have also been investigated. The TPD of the hydrocarbons over catalysts containing no Co showed a single desorption profile while incorporation of Co created an additional site, with higher heats of desorption, without significantly affecting desorption from the original site. The TPSR measurements showed that the two sites had separate and independent activity for the hydrogenation of the C-4 hydrocarbons. The TPD of thiophene over catalysts with varying Co to Mo ratios showed a single desorption profile with identical heats of desorption, implying that Co does not affect or influence the adsorption sites for thiophene. The TPSR of the HDS of thiophene, however, showed that, although the products of the HDS reaction-butane, butene, and H2S-are the same irrespective of the Co content, the temperature profiles and the activation barriers for the formation of these species show considerable change with the Co/Co+Mo ratio. The results are discussed in light of the existing models for the promotional role of Co in the HDS reaction.

Spontaneously Igniting Hybrid Fuel-Oxidizer Systems

After briefly outlining the recent developments in hybrid rockets, the work carried out by the author on self-igniting (hypergolic) solid fuel-liquid oxidiser systems has been reviewed. A major aspect relates to the solid derivatives of hydrazines, which have been conceived as fuels for hybrid rockets. Many of these N-N bonded compounds ignite readily, with very short ignition delays, on coming into contact with liquid oxidisers, like HNO3 and N2O4. The ignition characteristics have been examined as a function of the nature of the functional group in the fuel molecule, in an attempt to establish a basis for the hypergolic ignition in terms of chemical reactivity of the fuel-oxidiser combination. Important chemical reactions occurring in the pre-ignition stage have been identified by examining the quenched reaction products. Hybrid systems exhibiting synergistic hypergolicity in the presence of metal powders have been investigated. An estimation of the rocket performance parameters, experimental determination of the heats of combustion in HNO3, thermal decomposition characteristics, temperature profile by thin film thermometry and and product identification by the rapid scan FT-IR, are among the other relevant studies made on these systems. A significant recent development has been the synthesis of new N-N bonded viscous binders, capable of retaining the hypergolicity of the fuel powders embedded therein as well as providing the required mechanical strength to the grain. Several of these resins have been characterised. Metallised fuel composites of these resins having high loading of magnesium are found to have short ignition delays and high performance parameters.

Low-temperature specific heat of antiferromagnetic EuNi5P3 and mixed-valent EuNi2P2 in magnetic fields to 7 T

he specific heats of EUNi(5)P(3), an antiferromagnet, and EuNi2P2, a mixed-valence compound, have been measured between 0.4 and 30 K in magnetic fields of, respectively, 0, 0.5, 1, 1.5, 2.5, 5, and 7 T, and 0 and 7 T. In zero field the specific heat of EuNi5P3 shows a h-like anomaly with a maximum at 8.3 K. With increasing field in the range 0-2.5 T, the maximum shifts to lower temperatures, as expected for an antiferromagnet. In higher fields the antiferromagnetic ordering is destroyed and the magnetic part of the specific heat approaches a Schottky anomaly that is consistent with expectations for the crystal-field/Zeeman levels. In low fields and for temperatures between 1.5 acid 5 K the magnetic contribution to the specific heat is proportional to the temperature, indicating a high density of excited states with an energy dependence that is very unusual for an antiferromagnet. The entropy associated with the magnetic ordering is similar to R In8, confirming that only the Eu2+-with J=7/2, S=7/2, L=0-orders below 30 R. In zero field approximately 20% of the entropy occurs above the Neel temperature, consistent. with the usual amount of short-range order observed in antiferromagnets. The hyperfine magnetic field at the Eu nuclei in EUNi(5)P(3) is 33.3 T, in good agreement with a value calculated from electron-nuclear double resonance measurements. For EuNi2P2 the specific heat is nearly field independent and shows no evidence of magnetic ordering or hyperfine fields. The coefficient of the electron contribution to the specific heat is similar to 100 mJ/mol K-2.

Mean field lattice model for adsorption isotherms in zeolite NaA

Using a lattice model for adsorption in microporous materials, pure component adsorption isotherms are obtained within a mean field approximation for methane at 300 K and xenon at 300 and 360 K in zeolite NaA. It is argued that the increased repulsive adsorbate-adsorbate interactions at high coverages must play an important role in determining the adsorption behavior. Therefore, this feature is incorporated through a "coverage-dependent interaction'' model, which introduces a free, adjustable parameter. Another important feature, the site volume reduction, has been treated in two ways: a van der Waal model and a 1D hard-rod theory [van Tassel et al., AIChE J. 40, 925 (1994)]; we have also generalized the latter to include all possible adsorbate overlap scenarios. In particular, the 1D hard-rod model, with our coverage-dependent interaction model, is shown to be in best quantitative agreement with the previous grand canonical Monte Carlo isotherms. The expressions for the isosteric heats of adsorption indicate that attractive and repulsive adsorbate-adsorbate interactions increase and decrease the heats of adsorption, respectively. It is concluded that within the mean field approximation, our simple model for repulsive interactions and the 1D hard-rod model for site volume reduction are able to capture most of the important features of adsorption in confined regions. (C) 1999 American Institute of Physics. [S0021-9606(99)70515-5].

Statistical thermodynamics of lattice models in zeolites: Implications of local versus global mean field interactions

The statistical thermodynamics of adsorption in caged zeolites is developed by treating the zeolite as an ensemble of M identical cages or subsystems. Within each cage adsorption is assumed to occur onto a lattice of n identical sites. Expressions for the average occupancy per cage are obtained by minimizing the Helmholtz free energy in the canonical ensemble subject to the constraints of constant M and constant number of adsorbates N. Adsorbate-adsorbate interactions in the Brag-Williams or mean field approximation are treated in two ways. The local mean field approximation (LMFA) is based on the local cage occupancy and the global mean field approximation (GMFA) is based on the average coverage of the ensemble. The GMFA is shown to be equivalent in formulation to treating the zeolite as a collection of interacting single site subsystems. In contrast, the treatment in the LMFA retains the description of the zeolite as an ensemble of identical cages, whose thermodynamic properties are conveniently derived in the grand canonical ensemble. For a z coordinated lattice within the zeolite cage, with epsilon(aa) as the adsorbate-adsorbate interaction parameter, the comparisons for different values of epsilon(aa)(*)=epsilon(aa)z/2kT, and number of sites per cage, n, illustrate that for -1 heats of adsorption predicted with the two approaches are similar. In general, the deviation between the LMFA and GMFA is greater for smaller n and less sensitive to n for epsilon(aa)(*)> 0. We compare the isotherms predicted with the LMFA with previous GMFA predictions [K. G. Ayappa, C. R. Kamala, and T. A. Abinandanan, J. Chem. Phys. 110, 8714 (1999)] (which incorporates both the site volume reduction and a coverage-dependent epsilon(aa)) for xenon and methane in zeolite NaA. In all cases the predicted isotherms are very similar, with the exception of a small steplike feature present in the LMFA for xenon at higher coverages. (C) 1999 American Institute of Physics. [S0021-9606(99)70333-8].

Solubilities of Pb+2, Bi+3, Sb+3 and Cu+1 sulphides in (NaCl KCl Na2S) melts

Solubilities of common metal sulfides have been determined in the (NaCl+KCl) eutectic melt with and without Na2S. A novel gas-phase equilibrium technique has been used for PbS, Bi2S3, and So2S3, and an improved liquid phase equilibrium technique for Cu2S, which eliminates the errors due to physical entrapment of the sulfide phase and segregation on quenching, enabling precise measurements to be made. Solubilities in the (NaCl+KCl) eutectic melt were determined as a function of temperature in the rante 700° to 950°C, and were found to be small. The partial molar heats of mixing of the sulfides in the eutectic melt have been calculated from the solubility measurements, to be 13.3, 31.4, 37.1, and 49.0 kcal for PbSs), Sb2S2(l), and Cu2S(s), respectively. Sodium sulfide addition was observed to enhance these solubilities, the effect being largest for Cu2S followed by Sb2S3, Bi2S3, and PbS. This effect is explained qualitatively. It was observed that PbS and Sb2S3 obey Henry's law up to saturation in (NaCl+KCl+Na2S) melts.

Thermodynamics of solid solutions of silver with indium and tin

A solid oxide galvanic cell and a gas-solid (View the MathML source) equilibration technique have been used to measure the activities of the solutes in the α-solid solutions of silver with indium and tin. The results are consistent with the information now available for the corresponding liquid alloys, the phase diagram and the heats of mixing of the solid alloy. When the results of this study are taken together with published data for the α-solid solutions in Ag + Cd system, it is found that the variation of the excess partial free energy of the solute with mole fraction can be correlated to the electron/atom ratio. The significant thennodynamic parameter that explains the Hume-Rothery findings in these alloys appears to be the rate of change of the excess partial free energy with composition near the phase boundary, and this in turn reflects the value of the solute-solute interaction energy.

Heat of Mixing and Activities in Liquid Al-Sn Alloys

The microscopic electron theory based on the pseudopotential formalism has been applied to the calculation of the heats of mixing and of activities in liquid Al·Sn alloys. The calculated values for both quantities were found to be in reasonable agreement with ,the experimental data.