Pitfalls on computing liquid-liquid phase equilibria using the k-value method

Poster presented in the 11th Mediterranean Congress of Chemical Engineering, Barcelona, October 21-24, 2008.

Geometrical study of the three-dimensional temperature–composition diagrams. An important aid to understand the behavior of the liquid–vapour equilibrium in ternary systems

In this work the usefulness of qualitatively studying and drawing three-dimensional temperature–composition diagrams for ternary systems is pointed out to understand and interpret the particular behavior of the liquid–vapour equilibrium of non-ideal ternary systems. Several examples have been used in order to highlight the interest and the possibilities of this tool, which should be an interesting support not only for lecturers, but also for researchers interested in experimental equilibrium data determination.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Solubility, Density, Refractive Index, and Viscosity for the Polyhydric Alcohol + CsBr + H2O Ternary Systems at Different Temperatures

The solubility, density, refractive index, and viscosity data for the ethylene glycol + CsBr + H2O, 1,2-propanediol + CsBr + H2O, and glycerin + CsBr + H2O ternary systems have been determined at (288.15, 298.15, and 308.15) K. In all cases, the solubility of CsBr in aqueous solutions was decreased significantly due to the presence of polyhydric alcohol. The liquid–solid equilibrium experimental data were correlated using the NRTL (nonrandom two-liquid) activity coefficient model, considering nondissociation of the dissolved salt in the liquid phase, and new interaction parameters were estimated. The mean deviations between calculated and experimental compositions were low, showing the good descriptive quality and applicability of the NRTL model. The refractive indices, densities, and viscosities for the unsaturated solutions of the three ternary systems have also been measured at three temperatures. Values for all of the properties were correlated with the salt concentrations and proportions of polyhydric alcohol in the solutions.

Mapping Binary Liquid-Vapor or Liquid-Liquid-Vapor Equilibria Regions, including the Different Azeotropic Behaviours, as a Function of the NRTL Binary Parameters

13th Mediterranean Congress of Chemical Engineering (Sociedad Española de Química Industrial e Ingeniería Química, Fira Barcelona, Expoquimia), Barcelona, September 30-October 3, 2014

Gibbs Energy of Mixing Function: Topological Analysis in Azeotropic Systems

ESAT 2014. 27th European Symposium on Applied Thermodynamics, Eindhoven University of Technology, July 6-9, 2014.

Investigation of Performance Enhancements for a Liquid-Desiccant Solar Air-Conditioner

Thermally driven liquid-desiccant air-conditioners (LDAC) are a proven but still developing technology. LDACs can use a solar thermal system to reduce the operational cost and environmental impact of the system by reducing the amount of fuel (e.g. natural gas, propane, etc.) used to drive the system. LDACs also have a key benefit of being able to store energy in the form of concentrated desiccant storage. TRNSYS simulations were used to evaluate several different methods of improving the thermal and electrical coefficients of performance (COPt and COPe) and the solar fraction (SF) of a LDAC. The study analyzed a typical June to August cooling season in Toronto, Ontario. Utilizing properly sized, high-efficiency pumps increased the COPe to 3.67, an improvement of 55%. A new design, featuring a heat recovery ventilator on the scavenging-airstream and an energy recovery ventilator on the process-airstream, increased the COPt to 0.58, an improvement of 32%. This also improved the SF slightly to 54%, an increase of 8%. A new TRNSYS TYPE was created to model a stratified desiccant storage tank. Different volumes of desiccant were tested with a range of solar array system sizes. The largest storage tank coupled with the largest solar thermal array showed improvements of 64% in SF, increasing the value to 82%. The COPe was also improved by 17% and the COPt by 9%. When combining the heat recovery systems and the desiccant storage systems, the simulation results showed a 78% increase in COPe and 30% increase in COPt. A 77% improvement in SF and a 17% increase in total cooling rate were also predicted by the simulation. The total thermal energy consumed was 10% lower and the electrical consumption was 34% lower. The amount of non-renewable energy needed from the natural gas boiler was 77% lower. Comparisons were also made between LDACs and vapour-compression (VC) systems. Dependent on set-up, LDACs provided higher latent cooling rates and reduced electrical power consumption. Negatively, a thermal input was required for the LDAC systems but not for the VC systems.

The development of a thermionic converter module suitable for liquid metal heating.

"Project 8173, Task no. 817305-9."

Aspects of Markov Chains and Particle Systems

Thesis (Ph.D.)--University of Washington, 2016-06

Immobilization of aluminum chloride on MCM-41 as a new catalyst system for liquid-phase isopropylation of naphthalene

A great deal of effort has been made at searching for alternative catalysts to replace conventional Lewis acid catalyst aluminum trichloride (AlCl3). In this paper, immobilization of AlCl3 on mesoporous MCM-41 silica with and without modification was carried out. The catalytic properties of the immobilized catalyst systems for liquid-phase isopropylation of naphthalene were studied and compared with those of H/MCM-41 and H/mordenite. The structures of the surface-immobilized aluminum chloride catalysts were studied and identified by using solid-state magic angle spinning nuclear magnetic resonance (MAS NMR), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption, and X-ray diffraction (XRD) techniques. The catalytic activity of the immobilized catalysts was found to be similar to that of acidic mordenite zeolite. A significant enhancement in the selectivity of 2,6-diisopropylnaphthalene (2,6-DIPN) was observed over the immobilized aluminum chloride catalysts. Immobilization of aluminum chloride on mesoporous silica coupled with surface silylation is a promising way of developing alternative catalyst system for liquid-phase Friedel-Crafts alkylation reactions. (C) 2002 Elsevier Science B.V. All rights reserved.

Superplasticity and superplastic forming ability of a Zr-Ti-Ni-Cu-Be bulk metallic glass in the supercooled liquid recgion

The superplastic deformation behavior and superplastic forming ability of the Zr41.25Ti13.75Ni10Cu12.5Be22.5 (at.%) bulk metallic glass (BMG) in the supercooled liquid region were investigated. The isothermal tensile results indicate (hat the BMG exhibits a Newtonian behavior at low strain rates but a non-Newtonian behavior at hiqh-strain rates in the initial deformation stage. The maximum elongation reaches as high as 1624% at 656 K. and nanocrystallization was found to occur during the deformation process. Based cm the analysis on tensile deformation. a gear-like micropart is successfully die-forged via a superplastic forgings process. demonstrating that the BMG has excellent workability in the supercooled liquid region. (C) 2004 Elsevier B.V. All rights reserved.

A comparison between capillary and imaging techniques for sizing bubbles in flotation systems

This communication reports a laboratory and plant comparison between the University of Cape Town (UCT) device (capillary) and the McGill University bubble sizing method (imaging). The laboratory work was conducted on single bubbles to establish the accuracy of the techniques by comparing with a reference method (capture in a burette). Single bubble measurements with the McGill University technique showed a tendency to slightly underestimate (4% for a 1.3 mm bubble) and the UCT technique to slightly overestimate (1% for the 1.3 man bubble). Both trends are anticipated from fundamental considerations. In the UCT technique bubble breakup was observed when measuring a 2.7 mm bubble using a 0.5 mm ID capillary tube. A discrepancy of 11% was determined when comparing the techniques in an industrial-scale mechanical flotation cell. The possible sources of bias are discussed. (C) 2003 Elsevier Ltd. All rights reserved.

A quasi-chemical viscosity model for fully liquid slags in the Al2O3-CaO-'FeO'-SiO2 system

A structurally based viscosity model for fully liquid silicate slags has been proposed and applied to the Al2O3-CaO-'FeO'-SiO2 system at metallic iron saturation. The model links the slag viscosity to the internal structure of melts through the concentrations of various anion/cation structural units (SUs). The concentrations of structural units are equivalent to the second nearest neighbor bond concentrations calculated by the quasi-chemical thermodynamic model. This viscosity model describes experimental data over the entire temperature and composition range within the Al2O3-CaO-'FeO'-SiO2 system at metallic iron saturation and can be extended to other industrial slag systems.

On the chaotic rotation of a liquid-filled gyrostat via the Melnikov-Holmes-Marsden integral

The non-linear motions of a gyrostat with an axisymmetrical, fluid-filled cavity are investigated. The cavity is considered to be completely filled with an ideal incompressible liquid performing uniform rotational motion. Helmholtz theorem, Euler's angular momentum theorem and Poisson equations are used to develop the disturbed Hamiltonian equations of the motions of the liquid-filled gyrostat subjected to small perturbing moments. The equations are established in terms of a set of canonical variables comprised of Euler angles and the conjugate angular momenta in order to facilitate the application of the Melnikov-Holmes-Marsden (MHM) method to investigate homoclinic/heteroclinic transversal intersections. In such a way, a criterion for the onset of chaotic oscillations is formulated for liquid-filled gyrostats with ellipsoidal and torus-shaped cavities and the results are confirmed via numerical simulations. (c) 2006 Elsevier Ltd. All rights reserved.

On the chaotic instability of a nonsliding liquid-filled top with a small spheroidal base via Melnikov-Holmes-Marsden integrals

Chaotic orientations of a top containing a fluid filled cavity are investigated analytically and numerically under small perturbations. The top spins and rolls in nonsliding contact with a rough horizontal plane and the fluid in the ellipsoidal shaped cavity is considered to be ideal and describable by finite degrees of freedom. A Hamiltonian structure is established to facilitate the application of Melnikov-Holmes-Marsden (MHM) integrals. In particular, chaotic motion of the liquid-filled top is identified to be arisen from the transversal intersections between the stable and unstable manifolds of an approximated, disturbed flow of the liquid-filled top via the MHM integrals. The developed analytical criteria are crosschecked with numerical simulations via the 4th Runge-Kutta algorithms with adaptive time steps.