Heat capacity and thermochemical study of trifluoroacetamide (C2H2F3NO)

The low-temperature heat capacities of trifluoroacetamide were precisely determined with a small sample precision automated adiabatic calorimeter over the temperature range from 78 to 404 K. A solid-to-solid phase transition, a fusion and a phase transition from a liquid crystalline phase to fully liquid phase have been observed at the temperatures of 336.911+/-0.102, 347.622+/-0.094 and 388.896+/-0.160 K, respectively. The molar enthalpies of these phase transitions as well as the chemical purity of the substance were determined to be 5.576+/-0.004, 11.496+/-0.007, 1.340+/-0.005 kJ mol(-1) and 99.30 mol%, respectively, on the basis of the heat capacity measurements. The molar entropies of the three phase transitions were calculated to be 16.550+/-0.012, 33.071+/-0.029 and 3.447+/-0.027 J mol(-1) K-1, respectively. Further researches of the thermochemical properties for this compound have been carried out by means of TG and DSC techniques. (C) 2000 Elsevier Science B.V. All rights reserved.

A combined DFT and SCRF study of solvent effects on 4-methyl-3-penten-2-one

The IR spectrum of 4-methyl-3-penten-2-one is interpreted with the aid of normal coordinate calculations within the Onsager self-consistent reaction field (SCRF) model, using a density functional theory (DFT) method at the Becke3LYP/6-31G* level. The solvent effects on the geometry, energy, dipole moment, and vibrational frequencies of 4-methyl-3-penten-2-one in the solution and in the liquid phase are calculated using the Onsager SCRF model. The calculated vibrational frequencies in the liquid-phase are in good agreement with the experimental values. The solvent reaction field has generally weak influence. For the two main bands of C=C and C=O mixed vibrational modes, small frequency shifts (5-6 cm(-1)), but relatively large changes in IR intensities (up to 101 km mol(-1) in the liquid phase) are found. (C) 1999 Elsevier Science BV. All rights reserved.

Measurements of the heat capacity of an azeotropic mixture of water and n-butanol from 78 to 320 K

Molar heat capacities of n-butanol and the azeotropic mixture in the binary system [water (x=0.716) plus n-butanol (x=0.284)] were measured with an adiabatic calorimeter in a temperature range from 78 to 320 K. The functions of the heat capacity with respect to thermodynamic temperature were established for the azeotropic mixture. A glass transition was observed at (111.9 +/- 1.1) K. The phase transitions took place at (179.26 +/- 0.77) and (269.69 +/- 0.14) K corresponding to the solid-liquid phase transitions of. n-butanol and water, respectively. The phase-transition enthalpy and entropy of water were calculated. A thermodynamic function of excess molar heat capacity with respect to temperature was established, which took account of physical mixing, destructions of self-association and cross-association for n-butanol and water, respectively. The thermodynamic functions and the excess thermodynamic ones of the binary systems relative to 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity and the calculated excess heat capacity with respect to temperature.

Thermodynamic properties of ethanol and gasoline blended fuel

The heat capacities (C-p) of five types of gasohol (50 wt % ethanol and 50 wt % unleaded gasoline 93(#) (E50), 60 wt % ethanol and 40 wt % unleaded gasoline 93(#) (E60), 70 wt % ethanol and 30 wt % unleaded gasoline 93(#) (E70), 80 wt % ethanol and 20 wt % unleaded gasoline 93(#) (E80), and 90 wt % ethanol and 10 wt % unleaded gasoline 93(#) (E90), where the "93" denotes the octane number) were measured by adiabatic calorimetry in the temperature range of 78-320 K. A glass transition was observed at 95.61, 96.14, 96.56, 96.84, and 97.08 K for samples from the E50, E60, E70, E80, and E90 systems, respectively. A liquid-solid phase transition and a solid-liquid phase transition were observed in the respective temperature ranges of 118-153 and 155-163 K for E50, 117-150 and 151-164 K for E60, 115-154 and 154-166 K for E70, 113-152 and 152-167 K for E80, and 112-151 and 1581-167 K for E90. The polynomial equations of Cp and the excess heat capacities (C-p(E)), with respect to the thermodynamic temperature, were established through least-squares fitting. Based on the thermodynamic relationship and the equations obtained, the thermodynamic functions and the excess thermodynamic functions of the five gasohol samples were derived.

Pressure-induced amorphization and an amorphous-amorphous transition in densified porous silicon

Deb, S. K., Wilding, M. C., Somayazulu, M., McMillan, P. F. (2001). Pressure-induced amorphization and an amorphous-amorphous transition in densified porous silicon. Nature, 414, 528-530. RAE2008

Polyamorphism in aluminate liquids

McMillan, P. F., Wilson, M., Wilding, M. C. (2003). Polyamorphism in aluminate liquids. Journal of Physics: Condensed Matter, 15 (36), 6105-6121 RAE2008

Broadband cavity-enhanced absorption spectroscopy with incoherent light

Although broadband incoherent light does not efficiently couple into a high-finesse optical cavity, its transmission is readily detectable and enables applications in cavity-enhanced absorption spectroscopy in the gas phase, liquid phase and on surfaces. This chapter gives an overview of measurement principles and experimental approaches implementing incoherent light sources in cavity-enhanced spectroscopic applications. The general principles of broadband CEAS are outlined and general “pros and cons” discussed, detailing aspects like cavity mirror reflectivity calibration or the establishment of detection limits. Different approaches concerning light sources, cavity design and detection schemes are discussed and a comprehensive overview of the current literature based on a methodological classification scheme is also presented.

On the modelling of the thermal interactions between a spray curtain and an impinging cold gas cloud

A mixed Lagrangian-Eulerian model of a Water Curtain barrier is presented. The heat, mass and momentum processes are modelled in a Lagrangian framework for the dispersed phase and in an Eulerian framework for the carrier phase. The derivation of the coupling source terms is illustrated with reference to a given carrier phase cell. The turbulent character of the flow is treated with a single equation model, modified to directly account for the influence of the particles on the flow. The model is implemented in the form of a 2 D incompressible Navier Stokes solver, coupled to an adaptive Rung Kutta method for the Lagrangian sub-system. Simulations of a free standing full cone water spray show satisfactory agreement with experiment. Predictions of a Water Curtain barrier impacted by a cold gas cloud point to markedly different flow fields for the upward and downward configurations, which could influence the effectiveness of chemical absorption in the liquid phase.

Mechanism of motion of an optical fiber aligned by a solder droplet

Solder is often used as an adhesive to attach optical fibers to a circuit board. In this proceeding we will discuss efforts to model the motion of an optical fiber during the wetting and solidification of the adhesive solder droplet. The extent of motion is determined by several competing forces, during three “stages” of solder joint formation. First, capillary forces of the liquid phase control the fiber position. Second, during solidification, the presence of the liquid-solid-vapor triple line as well as a reduced liquid solder volume leads to a change in the net capillary force on the optical fiber. Finally, the solidification front itself impinges on the fiber. Publicly-available finite element models are used to calculate the time-dependent position of the solidification front and shape of the free surface.

High electric current density-induced interfacial reactions in micro ball grid array (μBGA) solder joints

The effect of a high electric current density on the interfacial reactions of micro ball grid array solder joints was studied at room temperature and at 150 °C. Four types of phenomena were reported. Along with electromigration-induced interfacial intermetallic compound (IMC) formation, dissolution at the Cu under bump metallization (UBM)/bond pad was also noticed. With a detailed investigation, it was found that the narrow and thin metallization at the component side produced “Joule heating” due to its higher resistance, which in turn was responsible for the rapid dissolution of the Cu UBM/bond pad near to the Cu trace. During an “electromigration test” of a solder joint, the heat generation due to Joule heating and the heat dissipation from the package should be considered carefully. When the heat dissipation fails to compete with the Joule heating, the solder joint melts and molten solder accelerates the interfacial reactions in the solder joint. The presence of a liquid phase was demonstrated from microstructural evidence of solder joints after different current stressing (ranging from 0.3 to 2 A) as well as an in situ observation. Electromigration-induced liquid state diffusion of Cu was found to be responsible for the higher growth rate of the IMC on the anode side.

Thermoelectric MHD effects on equiaxed crystal morphology

The effects of a constant uniform magnetic field on a growing equiaxed crystal are investigated using a 3-dimensional enthalpy based numerical model. Two cases are considered: The first case looks at unconstrained growth, where the current density is generated through the thermo-electric effect and the current circulates between the tips and roots of the dendrite, the second represents an imposed potential difference across the domain. A jump in the electrical conductivity between the liquid and solid causes the current density to be non uniform. In both cases the resulting Lorentz force drives fluid flow in the liquid phase, this in turn causes advection of the thermal and solute field altering the free energy close to the interface and changing the morphology of the dendrite. In the first case the flow field is complex comprising of many circulations, the morphological changes are modelled using a 2D model with a quasi 3D approximation. The second case is comparable to classic problems involving a constant velocity boundary.

Polymer conditioning of alum sludge and discrepancies between estimates of the optimum dosage

The paper outlines the effects of polymer conditioning on alum sludge properties, such as floc size, density, fractal dimension (DF) and rheological properties. Experimental results demonstrate that polymer conditioning of alum sludge leads to: larger floc size with a plateau reached in higher doses; higher densities associated with higher doses; increased degree of compactness; and an initial decrease followed by an increase of supernatant viscosity with continued increase in polymer dose. The secondary focus of this paper dwells on a comparison of the estimates of optimum dose using different criteria that emanate from established dewatering tests such as CST, SRF, liquid phase viscosity and modified SRF as well as a simple settlement test in terms of CML30. Alum sludge was derived from a water works treating coloured, low-turbidity raw waters.

Solvation effects on equilibria: Triazoles and N-methyl piperidinol

We have performed calculations of the solvation effects on a number of equilibrium constants in water using a recently proposed hybrid quantum classical scheme in which the liquid environment is modelled using classical solvent molecules and the solute electronic structure is computed using modern quantum chemical methods. The liquid phase space is sampled from a fully classical simulation. We find that solvation effects on both triazole tautomeric equilibrium constants and piperidinol conformational equilibrium constants can be interpreted in terms of subtle differences in the local environment which can be seen in probability densities and radial distribution functions. Lower level calculations were performed for comparison and we conclude that the solvation thermodynamics can be predicted from a good classical model of solvent and solute molecules, but the implicit models that we tried are less successful.

PVT Property Measurements for Some Aliphatic Esters from (298 to 393) K and up to 35 MPa

The results of PVT measurements of the liquid phase within the temperature range of (298 to 393) K and up to 35 MPa are presented for some aliphatic esters. Measurements were made by means of a vibrating-tube densimeter, model DMA 512P from Anton Parr. The calibration of the densimeter was performed with water and n-heptane as reference fluids. The experimental PVT data have been correlated by a Tait equation. This equation gives excellent results when used to predict the density of the esters using the method proposed by Thomson et al. (AIChE J. 1982, 28, 671-676). Isothermal compressibilities, isobaric expansivities, thermal pressure coefficients, and changes in the isobaric heat capacity have been calculated from the volumetric data.

Steric effects in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol using an Ir/C catalyst

The liquid phase selective hydrogenation of cinnamaldehyde to cinnamyl alcohol has been carried out over a graphite-supported iridium catalyst. The effect of reaction parameters such as temperature, pressure, concentration of reactant, the effect of addition of product to the feed and pre-reduction of the catalyst were studied. In situ pre-reduction of the catalyst with hydrogen had a very significant enhancing effect on the conversion of cinnamaldehyde and selectivity of the catalyst to cinnamyl alcohol. Kinetic analysis of the pre-reduced catalyst showed that the reaction is zero order with respect to cinnamaldehyde and first order with respect to hydrogen. The reaction follows an Arrhenius behaviour with an activation energy of 37 kJ mol(-1). Detailed analysis of the reaction showed that hydrogenation of the C=C double bond to give hydrocinnamaldehyde predominantly occurred at low conversions of cinnamaldehyde (