Search results for "Thermodynamic"
showing 10 items of 2971 documents
Mechanistic and kinetic insight into spontaneous cocrystallisation of isoniazid and benzoic acid
2015
Solid-state cocrystallisation is of contemporary interest, because it offers an easy and efficient way to produce cocrystals, which are recognized as prospective pharmaceutical materials. Research explaining solid-state cocrystallisation mechanisms is important, but still too scarce to give a broad understanding of factors governing and limiting these reactions. Here we report an investigation of the mechanism and kinetics of isoniazid cocrystallisation with benzoic acid. This reaction is spontaneous; however its rate is greatly influenced by environmental conditions (humidity and temperature) and pre-treatment (milling) of the sample. The acceleration of cocrystallisation in the presence o…
Fourier transform infrared analysis of paint solvents
1991
Abstract The composition of solvent mixtures employed in the paint industry was determined by Fourier transform infrared spectrometry. A procedure based on the use of the ratio between the absorbance of characteristic bands of each component permits the ratio between two solvents in a binary mixture to be determined, independently of the thickness of the sample film. Typical mixtures of xylol with butan-1-ol and with butyl acetate (xylol=mixture of o-, m- and p-xylenes) were used as model systems to develop the proposed procedure and the accuracy was determined using synthetic formulations. Another possible application of the procedure is the characterization of azeotropic mixtures.
On the relaxation mechanisms of 6-azauracil
2011
The nonadiabatic photochemistry of 6-azauracil has been studied by means of the CASPT2//CASSCF protocol and double-ζ plus polarization ANO basis sets. Minimum energy states, transition states, minimum energy paths, and surface intersections have been computed in order to obtain an accurate description of several potential energy hypersurfaces. It is concluded that, after absorption of ultraviolet radiation (248 nm), two main relaxation mechanisms may occur, via which the lowest (3)(ππ*) state can be populated. The first one takes place via a conical intersection involving the bright (1)(ππ*) and the lowest (1)(nπ*) states, ((1)ππ*/(1)nπ*)(CI), from which a low-energy singlet-triplet crossin…
Structural relaxation in a molten salt probed by time-dependent dc conductivity measurements
1998
Abstract Time-dependent dc conductivity was measured after cooling steps of about 2 K in the glass transformation range of 2Ca(NO 3 ) 2 -3RbNO 3 . The shape and time scale of the structural relaxation function was thus monitored for times 60 s t 6 s. The time scale could be compared with results from scanning calorimetry measurements and good agreement was found. From the heat capacity data and from the solid state conductivity the expected liquid state conductivity relaxation time was calculated using several models. The good compatibility of these calculations with the experimental results provides evidence that near the calorimetric glass transition the mobile ions perform concerted moti…
Modelling of thermo-chemical properties over the sub-solidus MgO–FeO binary, as a function of iron spin configuration, composition and temperature
2014
Thermo-chemical properties and T–X phase relations diagram of the (Mg,Fe)O solid solution are modelled using mixing Helmholtz energy, ΔF(T,x)mixing, calculated by quantum mechanical and semi-empirical techniques. The sub-solidus MgO–FeO binary has been explored as a function of composition, with iron either in high-spin (HS) or low-spin (LS) configuration. Only the HS model provides physically sound results at room pressure, yielding a correct trend of cell edge versus composition, whereas LS’s issues are at variance with observations. Mixing Helmholtz energy has been parametrized by the following relationship: ΔF(T,x)mixing = x × y × [U0(T) + U1(T) × (x – y) + U2(T) × (x − y)2]−T × S(x,y)c…
Analysis and parametric sensitivity of the behavior of overshoots in the concentration of a charged adsorbate in the adsorbed phase of charged adsorb…
2003
In this work, an analysis of the parametric sensitivity of the overshoot in the concentration of the adsorbate in the adsorbed phase, which occurs under certain conditions during an ion-exchange adsorption process, is presented and used to suggest practical implications of the concentration overshoot phenomenon on operational policies and configurations of chromatographic columns and finite bath adsorption systems. The results presented in this work demonstrate and explain how the development of an overshoot in the concentration of the adsorbate in the adsorbed phase could be enhanced or suppressed by (i) varying the diffusion coefficient, D3, of the adsorbate relative to the diffusion coef…
Size Dependence of Tracer Diffusion in Supercooled Liquids
1996
We have determined by forced Rayleigh scattering the diffusion coefficients D of several photochromic tracers with van der Waals radii between 0.38 and 8 nm (the largest ones being photolabeled polystyrene micronetworks) in 10 glass-forming liquids at temperatures between the glass temperature Tg and ∼1.2Tg. The results were analyzed in terms of power law plots, D(T) ∝ T/η(T)ξ, where η is the solvent shear viscosity, and temperature shifts, D(T) ∝ T/η(T + ΔT). The shift ΔT was related with the width of the rotational correlation time distribution via the time−temperature superposition principle.
Transport coefficients of n-butane into and through the surface of silicalite-1 from non-equilibrium molecular dynamics study
2009
We have studied coupled heat and mass transfer of n-butane through a membrane of silicalite-1. A description of the surface was given using non-equilibrium thermodynamics, and transport coefficients were determined. Three independent coefficients were found for the whole surface: the resistance to heat transfer, the coupling coefficient and the resistance to mass transfer. These coefficients were defined in stationary state. All resistances are significant, and show that the surface acts as a barrier to transport. A new scheme was devised to find the enthalpy of adsorption, from two particular coupling coefficients, namely the measurable heats of transfer. The method yields the enthalpy of …
Activity mediated phase separation: Can we understand phase behavior of the nonequilibrium problem from an equilibrium approach?
2016
We present results for structure and dynamics of mixtures of active and passive particles, from molecular dynamics (MD) simulations and integral equation theory (IET) calculations, for a physically motivated model. The perfectly passive limit of the model corresponds to the phase-separating Asakura-Oosawa model for colloid-polymer mixtures in which, for the present study, the colloids are made self-propelling by introducing activity in accordance with the well known Vicsek model. Such activity facilitates phase separation further, as confirmed by our MD simulations and IET calculations. Depending upon the composition of active and passive particles, the diffusive motion of the active specie…