Queen's University - Utility Bar

QSpace at Queen's University >
Graduate Theses, Dissertations and Projects >
Queen's Graduate Theses and Dissertations >

Please use this identifier to cite or link to this item: http://hdl.handle.net/1974/1577

Title: Supercritical aqueous solutions of sodium chloride: Classical insights into nucleation and reactivity
Authors: Nahtigal, Istok

Files in This Item:

File Description SizeFormat
Nahtigal_Istok_G_200811_MSc.pdf1.88 MBAdobe PDFView/Open
Keywords: Supercritical water
Molecular Dynamics
Particle electrostatics
Order parameter
Issue Date: 2008
Series/Report no.: Canadian theses
Abstract: In recent years, technologies using supercritical water have gained considerable attention, mainly due to versatility and uniqueness of water at elevated temperatures and pressures. The physical conditions required to generate supercritical water also make it prone to large intrinsic thermal and density fluctuations, exacerbated if there are impurities present in the system. These fluctuations induce nucleation, the initial stage of a first-order phase transition, and subsequent mixing of the new phase within the original phase. When this new phase reaches its critical size it grows irreversibly to macroscopic proportions, otherwise, tending to disintegrate. The presence of a polydispersed solid phase within the supercritical phase is responsible for unfavorable phenomena such as particle deposition and corrosion of structural components, both of which result in decreased efficiency and reliability of the supercritical water employing process. Molecular Dynamics (MD) simulation method has been the primary tool of investigation. Molecular motions are tracked on the femto and picosecond time-scales which are particularly important for the study of nucleation. Sodium chloride has been chosen in this research since it is computationally tractable and is unavoidably involved in most industrial water based applications. Cluster size distributions, the size of critical nuclei and cluster life-times are reported. The size distribution of emerging clusters shows a very strong dependence on the system’s density, with larger clusters preferentially formed at lower densities. Also, a materials science application is presented where the rapid quenching of hydrothermally formed sodium chloride clusters leads to a variety of nanostructures, characterizable by prominent vibrational modes. And lastly, during the conditions prior to crystallization, water is not only physically adsorbed to the cluster’s surface but also exists in a “confined” state within subsurface regions for several picoseconds during the nucleation process. A mechanism for the sodium chloride hydrolysis reaction is presented as well as showing that asymmetric electrostatic fields generated by the coalescing ions are on the order of 1010 V/m, sufficient to drive the hydrolysis of confined water molecules. The HCl molecule and hydroxide ions are formed, with the latter segregating preferentially to sub-surface regions in the amorphous NaCl particles. Both HCl and hydroxide are implicated in corrosion.
Description: Thesis (Master, Chemistry) -- Queen's University, 2008-11-03 13:54:56.021
URI: http://hdl.handle.net/1974/1577
Appears in Collections:Queen's Graduate Theses and Dissertations
Department of Chemistry Graduate Theses

Items in QSpace are protected by copyright, with all rights reserved, unless otherwise indicated.


  DSpace Software Copyright © 2002-2008  The DSpace Foundation - TOP