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* Guidelines are provided on the reliability of various methods, as well as information for selecting the appropriate technique. * Unique coverage of the whole range of solubility measurements. * Very useful for investigators interested in embarking upon solubility measurements.
Supercritical fluids are neither gas nor liquid, but can be compressed gradually from low to high density and they are therefore interesting and important as tunable solvents and reaction media in the chemical process industry. By adjusting the density the properties of these fluids can be customised and manipulated for a given process - physical or chemical transformation. Separation and processing using supercritical solvents such as CO2 are currently on-line commercially in the food, essential oils and polymer industries. Many agencies and industries are considering the use of supercritical water for waste remediation. Supercritical fluid chromatography represents another, major analytical application. Significant advances have recently been made in materials processing, ranging from particle formation to the creation of porous materials. The chapters in this book provide tutorial accounts of topical areas centred around: (1) phase equilibria, thermodynamics and equations of state; (2) critical behaviour, crossover effects; (3) transport and interfacial properties; (4) molecular modelling, computer simulation; (5) reactions, spectroscopy; (6) phase separation kinetics; (7) extractions; (8) applications to polymers, pharmaceuticals, natural materials and chromatography; (9) process scale-up.
The book begins with an overview of the phase diagrams of fluid mixtures (fluid = liquid, gas, or supercritical state), which can show an astonishing variety when elevated pressures are taken into account; phenomena like retrograde condensation (single and double) and azeotropy (normal and double) are discussed. It then gives an introduction into the relevant thermodynamic equations for fluid mixtures, including some that are rarely found in modern textbooks, and shows how they can they be used to compute phase diagrams and related properties. This chapter gives a consistent and axiomatic approach to fluid thermodynamics; it avoids using activity coefficients. Further chapters are dedicated to solid-fluid phase equilibria and global phase diagrams (systematic search for phase diagram classes). The appendix contains numerical algorithms needed for the computations. The book thus enables the reader to create or improve computer programs for the calculation of fluid phase diagrams. introduces phase diagram classes, how to recognize them and identify their characteristic features presents rational nomenclature of binary fluid phase diagrams includes problems and solutions for self-testing, exercises or seminars
Traditionally, the teaching of phase equilibria emphasizes the relationships between the thermodynamic variables of each phase in equilibrium rather than its engineering applications. This book changes the focus from the use of thermodynamics relationships to compute phase equilibria to the design and control of the phase conditions that a process needs. Phase Equilibrium Engineering presents a systematic study and application of phase equilibrium tools to the development of chemical processes. The thermodynamic modeling of mixtures for process development, synthesis, simulation, design and optimization is analyzed. The relation between the mixture molecular properties, the selection of the thermodynamic model and the process technology that could be applied are discussed. A classification of mixtures, separation process, thermodynamic models and technologies is presented to guide the engineer in the world of separation processes. The phase condition required for a given reacting system is studied at subcritical and supercritical conditions. The four cardinal points of phase equilibrium engineering are: the chemical plant or process, the laboratory, the modeling of phase equilibria and the simulator. The harmonization of all these components to obtain a better design or operation is the ultimate goal of phase equilibrium engineering. - Methodologies are discussed using relevant industrial examples - The molecular nature and composition of the process mixture is given a key role in process decisions - Phase equilibrium diagrams are used as a drawing board for process implementation
This chapter illustrates the wide variety of binary fluid phase equilibrium diagrams that can be obtained using models based on equations of state (EOS). It also highlights the need for paying attention to the predicted binary key lines, such as the critical and the liquid–liquid–vapor equilibrium lines, when fitting binary interaction parameters of an EOS model. In addition, efficient algorithms for the EOS-based automated computation of complete Univariant Lines Phase Equilibrium Diagrams and of complete restricted binary phase equilibrium diagrams, such as isoplethic, isothermal, or isobaric diagrams, are described.
The book provides fundamental chemistry and properties of near-critical water (NCW) and supercritical water (SCW), criteria and challenges/solutions in reactor design for NCW and SCW processes, and up-to-date reviews and practice of a wide range of their applications in bio refineries including: production of hydrochars from biomass, SCW oxidation (SCWO) for waste treatment, SCW gasification (SCWG) of biomass and waste for hydrogen and methane production, hydrothermal liquefaction of biomass, production of chemicals and SCWO of biofuels for energy. It also presents techno-economic analysis of hydrogen production via SCWG of biomass. The book will be highly essential for both academic researchers and industrial practitioners for developing novel bio refinery technologies and processes employing NCW or SCW for treatment of various organic waste streams and production of bio-energy and bio-based chemicals from bio-renewable resources. Prof. Dr. Zhen Fang is leader and founder of biomass group, Xishuangbanna Tropical Botanical Garden, Chinese Academy of Sciences, China. Dr. Chunbao (Charles) Xu is currently an Associate Professor of Chemical Engineering and NSERC/FP Innovations Industrial Research Chair in Forest Bio refinery at Western University, Canada.
This book has been prepared under the auspices of Commission I.2 on Thermodynamics of the International Union of Pure and Applied Chemistry (IUPAC). The authors of the 18 chapters are all recognized experts in the field. The book gives an up-to-date presentation of equations of state for fluids and fluid mixtures. All principal approaches for developing equations of state are covered. The theoretical basis and practical use of each type of equation is discussed and the strength and weaknesses of each is addressed. Topics addressed include the virial equation of state, cubic equations and generalized van der Waals equations, perturbation theory, integral equations, corresponding stated and mixing rules. Special attention is also devoted to associating fluids, polydisperse fluids, polymer systems, self-assembled systems, ionic fluids and fluids near critical points.
Foaming with Supercritical Fluids, Volume Nine provides a comprehensive description of the use of supercritical fluids as blowing agents in polymer foaming. To this aim, the fundamental issues on which the proper design and control of this process are rooted are discussed in detail, with specific attention devoted to the theoretical and experimental aspects of sorption thermodynamics of a blowing agent within a polymer, the effect of the absorbed blowing agent on the thermal, interfacial and rheological properties of the expanding matter, and the phase separation of the gaseous phase, and of the related bubble nucleation and growth phenomena. Several foaming technologies based on the use of supercritical blowing agents are then described, addressing the main issues in the light of the underlying chemical-physical phenomena. - Offers strong fundamentals on polymer properties important on foaming - Outlines the use of supercritical fluids for foaming - Covers theoretical points-of-view, including foam formation of the polymer/gas solution to the setting of the final foam - Discusses the several processing technologies and applications