This dissertation investigates the importance of diffusional and convective fluxes for salts in reverse osmosis (RO) and nanofiltration (NF) membranes. Moreover, the physical and thermodynamic factors controlling the salt permeability are analyzed. The study utilizes direct osmosis (DO) experiments and RO experiments, the later using both flat sheet and spiral wound membrane configurations. The salts considered are chlorides and acetates of alkali metals and alkaline earth metals. The equation governing the salt transport in DO experiments is derived and a phenomenon inverse to concentration polarization in RO is observed. The salt permeability in DO is equal to the salt permeability calculated for the valid cases of the used RO models. DO is suggested as an alternative method in characterizing the salt transport in membranes. The method can be more advantageous than RO due to the lower costs and simplicity of the apparatus. The models used to calculate the salt transport parameters in RO experiments are Spiegler-Kedem model, which considers both diffusion and convection of salt, and Kimura-Sourirajan model, which considers only diffusion of salt. It is found that diffusion is the dominant mechanism of transport in both RO and NF membranes. The percentage of the salt diffusional flux of the total flux is highest for seawater membranes and it is approximately equal for brackish water and nanofiltration membranes. The salt diffusive flux contribute more to the total flux for the 1:2 salts than for 1:1 salts. The two RO models are found equivalent in determining the salt permeability for only the seawater membranes. The Kimura-Sourirajan model overestimates the salt permeability coefficient for salts with rejection coefficient lower than 86%. The permeation rates for studied salts follow the lyotropic series regardless the membrane type (RO or NF), the membrane configuration (flat sheet or spiral wound), the process (DO or RO), or the models used for the calculations. This order of salt permeability is explained by the hydration of the cations, which is quantified by the enthalpy and entropy of hydration. The relative free energy theory can also be used to predict the salt permeability in a membrane based on preliminary data.

Includes vita. / Title from PDF of title page. / Document formatted into pages; contains 187 pages. / Thesis (Ph.D.)--University of South Florida, 2003. / Includes bibliographical references. / Text (Electronic thesis) in PDF format. / ABSTRACT: This dissertation investigates the importance of diffusional and convective fluxes for salts in reverse osmosis (RO) and nanofiltration (NF) membranes. Moreover, the physical and thermodynamic factors controlling the salt permeability are analyzed. The study utilizes direct osmosis (DO) experiments and RO experiments, the later using both flat sheet and spiral wound membrane configurations. The salts considered are chlorides and acetates of alkali metals and alkaline earth metals. The equation governing the salt transport in DO experiments is derived and a phenomenon inverse to concentration polarization in RO is observed. The salt permeability in DO is equal to the salt permeability calculated for the valid cases of the used RO models. DO is suggested as an alternative method in characterizing the salt transport in membranes. The method can be more advantageous than RO due to the lower costs and simplicity of the apparatus. / ABSTRACT: The models used to calculate the salt transport parameters in RO experiments are Spiegler-Kedem model, which considers both diffusion and convection of salt, and Kimura-Sourirajan model, which considers only diffusion of salt. It is found that diffusion is the dominant mechanism of transport in both RO and NF membranes. The percentage of the salt diffusional flux of the total flux is highest for seawater membranes and it is approximately equal for brackish water and nanofiltration membranes. The salt diffusive flux contribute more to the total flux for the 1:2 salts than for 1:1 salts. The two RO models are found equivalent in determining the salt permeability for only the seawater membranes. The Kimura-Sourirajan model overestimates the salt permeability coefficient for salts with rejection coefficient lower than 86%. / ABSTRACT: The permeation rates for studied salts follow the lyotropic series regardless the membrane type (RO or NF), the membrane configuration (flat sheet or spiral wound), the process (DO or RO), or the models used for the calculations. This order of salt permeability is explained by the hydration of the cations, which is quantified by the enthalpy and entropy of hydration. The relative free energy theory can also be used to predict the salt permeability in a membrane based on preliminary data. / System requirements: World Wide Web browser and PDF reader. / Mode of access: World Wide Web.

abstract: How water behaves at interfaces is relevant to many scientific and technological applications; however, many subtle phenomena are unknown in aqueous solutions. In this work, interfacial structural transition in hydration shells of a polarizable solute at critical polarizabilities is discovered. The transition is manifested in maximum water response, the reorientation of the water dipoles at the interface, and an increase in the density of dangling OH bonds. This work also addresses the role of polarizability of the active site of proteins in biological catalytic reactions. For proteins, the hydration shell becomes very heterogeneous and involves a relatively large number of water molecules. The molecular dynamics simulations show that the polarizability, along with the atomic charge distribution, needs to be a part of the picture describing how enzymes work. Non Gaussian dynamics in time-resolved linear and nonlinear (correlation) 2D spectra are also analyzed. Additionally, a theoretical formalism is presented to show that when preferential orientations of water dipoles exist at the interface, electrophoretic charges can be produced without free charge carriers, i.e., neutral solutes can move in a constant electric field due to the divergence of polarization at the interface. Furthermore, the concept of interface susceptibility is introduced. It involves the fluctuations of the surface charge density caused by thermal motion and its correlation over the characteristic correlation length with the fluctuations of the solvent charge density. Solvation free energy and interface dielectric constant are formulated accordingly. Unlike previous approaches, the solvation free energy scales quite well in a broad range of ion sizes, namely in the range of 2-14 A° . Interface dielectric constant is defined such that the boundary conditions in the Laplace equation describing a micro- or mesoscopic interface are satisfied. The effective dielectric constant of interfacial water is found to be significantly lower than its bulk value. Molecular dynamics simulation results show that the interface dielectric constant for a TIP3P water model changes from nine to four when the effective solute radius is increased from 5 A° to 18 A° . The small value of the interface dielectric constant of water has potentially dramatic consequences for hydration. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

La spectroscopie de dissociation par absorption de photons infrarouges (IRPD) permet d’obtenir les signatures vibrationnelles d’espèces chargées en phase gazeuse, telles que de petits peptides ou des ions hydratés dans des agrégats d’eau. L’attribution des modes de vibration pour établir une relation entre le spectre expérimental et une structure moléculaire est une tâche délicate et nécessite le recours à la modélisation moléculaire.Ce manuscrit présente un ensemble d’outils théoriques pour le calcul et l’attribution de spectres vibrationnels, basée principalement sur la dynamique moléculaire classique et le champ de forces polarisable AMOEBA, ainsi que son application à des ions gazeux de tailles diverses. Les ions hydratés dans des agrégats d’eau M(H2O)n (n allant de 6 à 100) sont caractérisés par une dynamique importante, et leur spectre expérimental ne peut pas être décrit par une seule structure. La signature des peptides évolue avec la température et les effets d’anharmonicité dynamique. Ils peuvent également être le siège de mécanismes de transfert de proton, présentant une signature vibrationnelle très caractéristique.La surface d’énergie potentielle de ces systèmes est explorée par la dynamique moléculaire classique en trajectoires individuelles ou avec échange de répliques, afin d’engendrer des structures énergétiquement stables. Pour les plus petits systèmes, les méthodes quantiques DFT et post-HF sont utilisées pour confirmer les structures de plus basse énergie, calculer leurs spectres IR statiques et proposer des attributions des modes de vibration. Pour les plus systèmes de plus grandes tailles, c’est-à-dire les ions dans des gouttes d’eau de plusieurs dizaines de molécules, la simulation des spectres IR à température finie est basée sur la transformée de Fourier de la fonction d’autocorrélation du moment dipolaire (DACF), calculée pour une trajectoire de dynamique moléculaire classique. Cette méthode n’offrant pas d’accès direct aux modes normaux de vibration, nous avons implémenté une méthode d’attribution dynamique, basée sur la Driven Molecular Dynamics (DMD) et couplée au DACF. La combinaison AMOEBA/DACF/DMD a été utilisée pour reproduire et attribuer le spectre du dipeptide Ace-Phe-Ala-NH2, et ceux d’ions hydratés dans des agrégats d’eau.Enfin, la signature vibrationnelle d’un transfert de proton ne peut être décrite, ni par des méthodes statiques quantiques, ni par la dynamique classique. Sa modélisation a nécessité le développement d’un modèle Empirical Valence Bond (EVB) à deux états, couplé au champ de forces polarisable AMOEBA. Le modèle EVB a été implémenté dans la suite logicielle Tinker. Il permet de reproduire le comportement dynamique du transfert de proton au sein de petits peptides et de diacides déprotonés, ainsi que la signature spectroscopique observée expérimentalement.Une partie importante des applications de ces développements concerne des ions simples hydratés dans des nano-gouttelettes, et en particulier l’ion sulfate de grande importance environnementale. Nous avons pu reproduire de façon satisfaisante, pour la première fois, les spectres d’agrégats contenant jusqu’à 100 molécules d’eau. Le principal contributeur à cette spectroscopie expérimentale est l’équipe d’E. Williams à l’université de Californie à Berkeley. Nous avons établi avec eux une collaboration pour compléter ce travail en modélisant les spectres IR d’ions sulfates hydratés [SO4(H2O)n=9-36]2-, dont ils ont obtenu les signatures expérimentales. / Spectroscopy dissociation by absorption of infrared photons (IRPD) provides vibrational signatures of charged species in the gas phase, such as small peptides or hydrated ions in water clusters. The vibrational normal modes assignment to establish a relationship between the experimental spectrum and molecular structure is a delicate task and requires the use of molecular modeling.This manuscript presents a set of theoretical tools for calculation and assignment of vibrational spectra, based mainly on classical molecular dynamics and polarizable AMOEBA force field, and its application to gaseous ions of various sizes. Hydrated ions in water clusters M(H2O)n (n in 6-100 range) are characterized by a dynamic behavior, and their experimental spectrum can not be described by a single structure. The signature of peptides changes with temperature and dynamic anharmonicity effects. They can also be the site of proton transfer mechanisms, with a very characteristic vibrational signature.The potential energy surface of these systems is explored by classical molecular dynamics in individual trajectories or replica exchange to generate energetically stable structures. For smaller systems, quantum methods, as DFT and post-HF, are used to confirm the lowest energy structures, calculate their static IR and propose normal modes assignments. For larger systems, i.e ions in water drops of several tens of molecules, the simulation of IR spectra at finite temperature is based on the Fourier transform of the autocorrelation function of the dipole moment (DACF), calculated during a classical molecular dynamics trajectory. As this method does not allow direct access to the vibrational normal modes, we implemented a method of dynamic assigments, based on the Driven Molecular Dynamics (DMD) and coupled to the DACF. The combination AMOEBA /DACF / DMD was used to reproduce and assign the spectrum of the dipeptide Ace-Phe-Ala-NH2, and those of hydrated ions in water clusters.Finally, the vibrational signature of a proton transfer can not be described by quantum static methods or by classical dynamics. Its modeling required the development of a two states Empirical Valence Bond Model (EVB), coupled with AMOEBA polarizable force field. The two states EVB model was implemented in the software TINKER. It can reproduce the dynamic behavior of proton transfer in small peptides and deprotonated acids, as well as the spectroscopic signatures observed experimentally.An important part of the applications of these developments relates simple hydrated ions in nano-droplets, and in particular the sulfate ion of great environmental importance. We were able to reproduce satisfactorily, for the first time, the spectra of clusters containing up to 100 water molecules. The main contributor to this experimental spectroscopy is the team of E. Williams from the University of California of Berkeley. We have established cooperation with them to complete this work by modeling the IR spectra of hydrated sulfates ions [SO4(H2O) n=9-36]2-, for which they obtained experimental signatures.