Search results for "THERMODYNAMICS"
showing 10 items of 2774 documents
Testing experimental designs in liquid chromatography (I): Development and validation of a method for the comprehensive inspection of experimental de…
2020
The basis of interpretive optimisation in liquid chromatography is the prediction of resolution, from appropriate solute retention models. The reliability of the process depends critically on the quality of the experimental design. This work develops, validates and applies a general methodology aimed to evaluate the quality of any training experimental design, which will be applied in Part II to design optimisation. The methodology is based on the systematic evaluation of the uncertainties associated to the prediction of retention times in comprehensive scans of both isocratic and gradient experimental conditions. It is able to evaluate comprehensively experimental designs of arbitrary comp…
Comparison of two serially coupled column systems and optimization software in isocratic liquid chromatography for resolving complex mixtures.
2012
Although there is a great deal of stationary phases having different selectivities (even practically orthogonal selectivities), these very rarely are taken as a factor to be optimized during method development. The chromatographer selects the stationary phase usually in a trial-and-error fashion (or based on the solute nature and expected interactions), and then optimizes continuous factors as the mobile phase composition, pH, temperature and flow-rate. However, the optimization of the stationary phase nature and column length (which are discrete factors) may be interesting. In this regard, the optimization of the coupling of individual columns may yield separations that are not possible wi…
Evaluating Thermal Corrections for Adsorption Processes at the Metal/Gas Interface
2019
International audience; Adsorption and desorption steps are key for active catalysts and rely on a subtle balance between enthalpic and entropic terms. While the enthalpic term is becoming ever more accurate through density functional development, the entropic term remains underrated and its precise determination a great challenge. In this work, we have performed extensive first principles thermodynamic integration (TI) simulations for the 1 adsorption of small (e.g., CO) to larger (e.g., phenol) molecules at metallic surfaces and compared their adsorption free energies to the values obtained by vertical, static statistical mechanics approximations to thermal corrections invoking three diff…
Structure and Dynamics of the Quasi-Liquid Layer at the Surface of Ice from Molecular Simulations
2018
We characterized the structural and dynamical properties of the quasi-liquid layer (QLL) at the surface of ice by molecular dynamics simulations with a thermodynamically consistent water model. Our simulations show that for three low-index ice surfaces only the outermost molecular layer presents short-range and mid-range disorder and is diffusive. The onset temperature for normal diffusion is much higher than the glass temperature of supercooled water, although the diffusivity of the QLL is higher than that of bulk water at the corresponding temperature. The underlying subsurface layers impose an ordered template, which produces a regular patterning of the ice/water interface at any tempera…
Modelling and simulation of gas-liquid hydrodynamics in mechnically stirred tanks
2007
Abstract Computational fuid dynamics (CFD) is an increasingly important tool for carrying out realistic simulations of process equipment. In the case of multiphase systems the development of CFD models is less advanced than for single-phase systems. In the present work CFD simulations of gas–liquid stirred tanks are reported. An Eulerian–Eulerian multi-fluid approach is used in conjunction with the simplest two-phase extension of the k–ɛ turbulence model. All bubbles are assumed to share the same size. The effect of inter-phase forces on simulation results is separately considered. As concerns drag, it is shown that the sole parameter needed to characterize the dispersed phase behaviour is …
Experimental Determination and Correlation of Liquid–Liquid Equilibria Data for a System of Water + Ethanol + 1-Butyl-3-methylimidazolium Hexafluorop…
2017
Over the past few years, interest has increased regarding the application of ionic liquids (ILs) as extraction solvents for separating azeotropic mixtures. Following this trend, this work presents the experimental data of liquid–liquid equilibria (LLE) of the system envolving water, ethanol, and 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) at different temperatures. The LLE data of the system was measured between 283.2 and 323.2 K to determine the temperature influence on the system. In the literature, reports of systems involving ILs that present type II behavior are scarce compared with those that present type I behavior; the system presented here also displays two immisc…
Liquid–liquid equlibria of the system dimethyl carbonate+methanol+water at different temperatures
2006
Abstract In this work, experimental liquid–liquid equilibria (LLE) data of the dimethyl carbonate + methanol + water system are presented. The LLE of this system has been measured from 283 to 333 K. On the other hand, LLE and LVE of the binary system dimethyl carbonate + water have been measured. The equilibrium data presented are correlated using NRTL and UNIQUAC equations. The reliability of these models is tested by comparison with experimental results. Finally, the VLE for the system DMC + water at 101.3 kPa was predicted using the UNIQUAC model, with the adjusted parameters obtained from the LLE data. This prediction was successful when is compared with the experimental VLE data.
Extended Validation of Dynamic Irreversible Thermoporation: A Novel Thermal Process for Microbial Inactivation
2015
A novel thermal treatment for microorganism inactivation, characterized by a very rapid temperature increase (up to 30°C/s) and a low final temperature (up to 65°C) maintained for a relatively short holding time, has been recently presented and tested by the authors, showing microbial load reduction greater than 5 log units against several common bacteria and yeasts. With the aim of extending the possible use of the new thermal treatment to a wider microorganisms class, in this work the dynamic irreversible thermoporation (DIT) treatment was further tested on a well-known thermoresistant strain, the Enterococcus hirae: The results of these new experimental tests confirmed the reliability of…
Heterogeneous kinetics: from solid–gas reaction to solid–liquid dissolution
2002
Abstract The extension of the formal kinetics of solid–gas reactions to solid–liquid dissolution is investigated theoretically. The work is based on modelling the dissolution of a solid in a closed system by a stoichiometrically simple chemical reaction A solid ⇄A liquid proceeding up to either an equilibrium state if the solid phase is initially in excess or exhaustion in the reverse situation. The initial amount of solid compared to the capacity of the liquid phase appears as a major factor of complexity. First, the rate equation is formulated in terms of the intensive variables without any assumption about the mechanism and the rate-limiting step. The resulting equations are compared to …
Early stages of beta2-microglobulin aggregation and the inhibiting action of alphaB-crystallin
2008
The interest of nucleation of protein crystals and aggregates (including oligomerization) spans from basic physics theory all the way to biophysics, nanophysics, clinical sciences, biotechnologies, food technologies and polymer-solvent interactions. Understanding nucleation within a theoretical framework capable of providing quantitative predictions and control of nucleation rates, or even the very occurrence of crystallization, is a long-sought goal of remarkable relevance to each of the above fields. A large amount of work has been aimed at such goal, but success has been so far rather limited. Work at our laboratory has more recently highlighted a direct link between nucleation rates and…