Molten carbonate fuel cells (MCFCs) have become an attractive emerging technology for stationary co-generation of heat and power. From a technical perspective, dynamic operation has a significant effect on the fuel cell life cycle and, hence, economic viability of the device. The scope of this thesis is to present an improved understanding of the system behaviour at transient operation that can be used to design a more robust control system in order to overcome the cost and the operating lifetime issues. Hence, a comprehensive multi-component multidimensional transient mathematical model is developed based on the conservation laws of mass, momentum, species, energy and electric charges coupled through the reaction kinetics. In essence, this model is a set of partial differential equations that are discretized and solved using the finite-volume based commercial software, ANSYS FLUENT 12.0.1. The model is validated with two sets of experimental results, available in open literature, and good agreements are obtained. The validated model is further engaged in an extensive study. First, the MCFC behaviour at high current densities or oxidant utilization, when the mass transfer becomes dominant, is investigated using peroxide and superoxide reaction mechanisms. In brief, both mechanisms predicted the linear region of the polarization curve accurately. However, none of these mechanisms showed a downward bent in the polarization curve. A positive exponent for the carbon-dioxide mole fraction is probably essential in obtaining the downward bent (“knee”) at high current densities which is in contrast to what has been reported in the literature to date. Next, a sinusoidal impedance approach is used to examine the dynamic response of the unit cell to inlet perturbations at various impedance frequencies. This analysis is further used to determine the phase shifts and time scales of the major dynamic processes within the fuel cell. Furthermore, numerical simulation is utilized in order to investigate the underlying electrochemical and transport phenomena without performing costly experiments. Results showed that the electrochemical reactions and the charge transport process occur under a millisecond. The mass transport process showed a comparatively larger time scale. The energy transport process is the slowest process in the cell and takes about an hour to reach its steady state condition. Furthermore, the developed mathematical model is utilized as a predictive tool to provide a three-dimensional demonstration of the transient physical and chemical processes at system startiv up. The local distribution of field variables and quantities are presented. The results show that increasing the electrode thickness provides a higher reaction rate, but may lead to larger ohmic loss which is not desirable. The reversible heat generation and consumption mechanisms of the cathode and anode are dominant in the first 10 s while the heat conduction from the solid materials to the gas phase is not considerable. The activation and ohmic heating have the same impact within the anode and cathode because of their similar electric conductivity and voltage loss. Increasing the thermal conductivity of the cathode material will facilitate the process of heat transport throughout the cell. This can also be accomplished by lowering the effects of heat conduction by means of a cathode material with a smaller thickness. In addition, a thermodynamic model is utilized to examine energy efficiency, exergy efficiency and entropy generation of a MCFC. By changing the operating temperature from 883 K to 963 K, the energy efficiency of the unit cell varies from 42.8 % to 50.5 % while the exergy efficiency remains in the range of 26.8% to 36.3%. Both efficiencies initially rise at lower current densities up to the point that they attain their maximum values and ultimately decrease with the increase of current density. With the increase of pressure, both energy and exergy efficiencies of the cell increase. An increase in this anode/cathode flow ratio lessens the energy and exergy efficiencies of the unit cell. Higher operating pressure and temperature decrease the unit cell entropy generation. / UOIT

Polymer electrolyte membrane (PEM) fuel cells have increasingly become promising green energy sources for automobile and stationary cogeneration applications but its success in commercialization depends on performance optimization and manufacturing cost. The activation losses, expensive platinum catalyst, and water flooding phenomenon are the key factors currently hindering commercialization of PEM fuel cells. These factors are associated with the cathode catalyst layer (CCL), which is about ten micrometers thick. Given the small scale of this layer, it is extremely difficult to study transport phenomena inside the catalyst layer experimentally, either intrusively or non-intrusively. Therefore, mathematical and numerical models become the only means to provide insight on the physical phenomena occurring inside the CCL and to optimize the CCL designs before building a prototype for engineering application. In this thesis research, a comprehensive two-phase mathematical model for the CCL has been derived from the fundamental conservation equations using a volume-averaging method. The model also considers several water transport and physical processes that are involved in the CCL. The processes are: (a) electro-osmotic transport from the membrane to the CCL, (b) back-diffusion of water from the CCL to the membrane, (c) condensation and evaporation of water, and (d) removal of liquid water to the gas flow channel through the gas diffusion layer (GDL). A simple analytical model for the activation overpotential in the CCL has also been developed and an optimization study has been carried out using the analytical activation overpotential formulation. Further, the mathematical model has been simplified for the CCL and an analytical approach has been provided for the liquid water transport in the catalyst layer. The volume-averaged mathematical model of the CCL is finally implemented numerically along with an investigation how the physical structure of a catalyst layer affects fuel cell performance. Since the numerical model requires various effective transport properties, a set of mathematical expressions has been developed for estimating the effective transport properties in the CCL and GDL of a PEM fuel cell. The two-dimensional (2D) numerical model has been compared with the analytical model to validate the numerical results. Subsequently, using this validated model, 2D numerical studies have been carried out to investigate the effect of various physical and wetting properties of CCL and GDL on the performance of a PEM fuel cell. It has been observed that the wetting properties of a CCL control the flooding behavior, and hydrophilic characteristics of the CCL play a significant role on the cell performance. To investigate the effect of concentration variation in the flow channel, a three-dimensional numerical simulation is also presented.

Nowadays, the development of novel materials involves diverse branches of science as a consequence of the new requirements imposed by modern society. This includes aspects ranging from the optimization of the manufacturing processes to the durability of the materials themselves. Ideally, some synergism should exist between the durability, the properties of interest in the material. Although metals in their pure state are often desired, the best properties or combination of properties often cannot be satisfactorily achieved with a single metal. In these situations, the desired properties can be attained by the formation of alloys of these metals with others. Ni-Co alloys are no exceptions and so have received considerable attention especially in microsystem technology due to the magnetic properties of cobalt and the corrosion and wear resistance of nickel. Moreover, this interest has been further stimulated by its use in the manufacture of sensors, magnetic devices, microrelays, inductors, actuators, memory devices and hard drives. The fabrication of these alloys (particularly coatings) via electroplating has been shown to be techno-economically feasible in comparison with other processes: capability of high volume production, low cost and the ability to coat thin layers on non-planar substrates. In addition, the materials fabricated by this technology exhibit excellent characteristics such as refined grain structure, smoothness, low residual stress and coercivity, etc., making them advantageous to materials produced by other physical methods of deposition. Nevertheless, one of the biggest problems faced during the formation of Ni-Co alloys is its anomalous behavior whereby cobalt preferentially deposits over nickel under most conditions, even when the Ni(II) concentration is significantly higher than that of Co(II). This problem has complicated the prediction and control of the metal composition in these alloys during their production and as a consequence the ability to obtain the desirable properties associated with high nickel content. Although this problem is not recent, the studies that have been carried out so far to analyze this system have not always been as comprehensive as they could be in terms of the experimental conditions investigated or the reaction mechanisms and mathematical models developed to describe its behavior. Consequently, the origin of this behavior is still not completely understood. Thus, this work presents a contribution in terms of the analysis of the reaction mechanisms for single metal deposition of nickel and cobalt and for the formation of Ni-Co alloys in sulphate media with the intention of gaining a better understanding of the phenomena controlling the anomalous behavior of this system. Analyses of the single metal deposition of nickel and cobalt are first carried out to better understand their reaction mechanisms. Such an approach should allow the contributions of the reduction of each metal ion and interactions between the two systems during alloy co-deposition to be more clearly understood. In order to analyse the aforementioned systems, both steady state and transient techniques are employed. Among these techniques, electrochemical impedance spectroscopy (EIS) is employed since it is a robust and powerful method to quantitatively characterize the various relaxation phenomena occurring during the electrodeposition of metals. The experimental data acquired from this technique are analyzed with comprehensive physicochemical models and the electrochemical processes are quantified by fitting the models to these data to determine the kinetic parameters. During the development of the physicochemical models, several assumptions (e.g. neglect of convection, homogeneous reactions and single electron-transfer steps) made in former models are relaxed in order to investigate their combined impact on the predicted response of the system. Estimates of the kinetic parameters determined by EIS for the deposition of the single metals reveals that the first step of Co(II) reduction is much faaster tha the corresponding step of Ni(II) reduction. Some limitations of the EIS technique (i.e. analysis at high overpotentials) are exposed and compared in the case of the nickel deposition using linear sweep voltammetry (LSV). Likewise, physicochemical models accounting for most of the important phenomena are derived and fitted to experimental data. Ni-Co alloy formation is analyzed using LSV and steady state polarization experiments for different pH, current density and electrolyte composition. Current efficiencies for metal depsoition and alloy composition are also evaluated. To date, no experimental study considering all these variables has been reported in the literature. Then a steady state model is presented to describe the electrode response during alloy formation and used to provide insight into the anomalous behavior of this system. This model is based on information obtained from previous studies reported in the literature and from the current research. After being fitted to the experimental data, the model reveals that the anomalous behavior observed for this alloy is likely caused by the much faster charge-transfer of Co(II) reduction than that of Ni(II) reduction and not by other previously proposed mechanisms such as competition between adsorbed species for surface sites, formation of aqueous hydroxides (MeOH+) or mixed intermediate species (NiCo(III)ads) on the surface of the electrode.

Area averaging is one of the techniques used to solve problems encountered in the transport of momentum, heat, and mass. The application of this technique simplifies the mathematical solution of the problem. However, it necessitates expressing the local value of the dependent variable and/or its derivative(s) on the system boundaries in terms of the averaged variable. In this study, these expressions are obtained by the two-point Hermite expansion and this approximate method is applied to some specific problems, such as, unsteady flow in a concentric annulus, unequal cooling of a long slab, unsteady conduction in a cylindrical rod with internal heat generation, diffusion of a solute into a slab from limited volume of a well-mixed solution, convective mass transport between two parallel plates with a wall reaction, convective mass transport in a cylindrical tube with a wall reaction, and unsteady conduction in a two -layer composite slab. Comparison of the analytical and approximate solutions is shown to be in good agreement for a wide range of dimensionless parameters characterizing each system.

Πολλοί μικροοργανισμοί έχουν την ικανότητα να σχηματίζουν βιοφίλμ στη διεπιφάνεια μεταξύ ενός υδατικού διαλύματος και ενός άλλου ρευστού, στερεού ή πορώδους υλικού. Η ανάπτυξη βιοφίλμ σε πορώδη υλικά έχει σημαντικό ρόλο σε πληθώρα διεργασιών, όπως η βιοαποδόμηση ρύπων στο έδαφος και η βιολογικά ενισχυμένη απόληψη πετρελαίου από ταμιευτήρες. Στην παρούσα εργασία μελετώνται τα φαινόμενα μεταφοράς και η δυναμική συμπεριφορά της ανάπτυξης μικροβιακών βιοφίλμ κατά τη βιοαποδόμηση οργανικών ενώσεων σε πορώδη υλικά. Οι κύριοι στόχοι και τα αποτελέσματα της διατριβής εντάσσονται σε τρεις άξονες. Ο πρώτος άξονας περιλαμβάνει τη διεξαγωγή πειραμάτων ανάπτυξης βιοφίλμ σε γυάλινα δοκίμια πορώδους μέσου για την αποσαφήνιση των μηχανισμών φραξίματος στην κλίμακα των πόρων και την συσχέτιση πορώδους-διαπερατότητας στην κλίμακα του πορώδους μέσου. Ο δεύτερος άξονας περιλαμβάνει την ανάπτυξη μιας μεθοδολογίας για τη μαθηματική περιγραφή: α) της διεργασίας μεταφοράς μάζας δια μοριακής διαχύσεως, και β) της διεργασίας μεταφοράς ορμής κατά τη ροή του εξωκυτταρικού υδατικού διαλύματος, σε κυτταρικά βιολογικά υλικά (βιοφίλμ, μικροβιακά συσσωματώματα, ιστοί). Η μεθοδολογία συνδυάζει τη μέθοδο χωρικής στάθμισης δια συνάρτησης βάρους για την ανάπτυξη των διεπουσών εξισώσεων, με μοντέλα μοναδιαίων κελιών για τον υπολογισμό των συντελεστών που υπεισέρχονται στις διέπουσες εξισώσεις. Ο τρίτος άξονας περιλαμβάνει την ανάπτυξη ενός νέου, ιεραρχικού, υβριδικού εξομοιωτή της δυναμικής συμπεριφοράς μικροβιακών βιοφίλμ σε πορώδη υλικά. Ο εξομοιωτής προβλέπει: α) τη δομική και βιολογική ετερογένεια στην κλίμακα του βιοφίλμ, β) τη μορφή και το ρυθμό ανάπτυξης του βιοφίλμ μέσα στους πόρους ρεαλιστικών πορωδών δομών, και γ) τη συζυγή μεταβολή του πεδίου ροής και της χωρικής κατανομής των συγκεντρώσεων διαλελυμένων χημικών ειδών. / Numerous bacteria are able to form biofilms at the interface between an aqueous solution and another fluid, solid or porous material. Biofilm growth in porous media is of key importance in a variety of processes, such as the biodegradation of pollutants in soil and biologically enhanced oil recovery from subsurface reservoirs. In the present work, the transport phenomena and the dynamics of biofilm growth during the biodegradation of organic pollutants in porous media are studied. The main goals and results of the dissertation are developed along the following axes. The first axis involves the conduction of experiments of biofilm growth in glass models of porous media for the elucidation of the clogging mechanism on the pore scale and the permeability-porosity correlation on the scale of the porous medium. The second axis involves the development of a methodology for the mathematical description of: (a) the diffusive mass transfer process, and, (b) the momentum transfer during the flow of the extra-cellular aqueous solution in cellular biological media (biofilms, microbial flocs, tissues). The methodology combines the spatial averaging method via a weight function for the formulation of the governing equations, with unit cell models for the calculation of the coefficients that enter the governing equations. The third axis involves the development of a novel, hierarchical, hybrid simulator of the dynamic behavior of microbial biofilms in porous materials. The simulator predicts: (a) the structural and biological heterogeneity on the biofilm scale, (b) the pattern and rate of growth rate of biofilms in the pores of realistic porous structures, and (c) the conjugate alteration of the flow field and the spatial distribution of the concentration of solutes.

Polymer electrolyte membrane (PEM) fuel cells have increasingly become promising green energy sources for automobile and stationary cogeneration applications but its success in commercialization depends on performance optimization and manufacturing cost. The activation losses, expensive platinum catalyst, and water flooding phenomenon are the key factors currently hindering commercialization of PEM fuel cells. These factors are associated with the cathode catalyst layer (CCL), which is about ten micrometers thick. Given the small scale of this layer, it is extremely difficult to study transport phenomena inside the catalyst layer experimentally, either intrusively or non-intrusively. Therefore, mathematical and numerical models become the only means to provide insight on the physical phenomena occurring inside the CCL and to optimize the CCL designs before building a prototype for engineering application. In this thesis research, a comprehensive two-phase mathematical model for the CCL has been derived from the fundamental conservation equations using a volume-averaging method. The model also considers several water transport and physical processes that are involved in the CCL. The processes are: (a) electro-osmotic transport from the membrane to the CCL, (b) back-diffusion of water from the CCL to the membrane, (c) condensation and evaporation of water, and (d) removal of liquid water to the gas flow channel through the gas diffusion layer (GDL). A simple analytical model for the activation overpotential in the CCL has also been developed and an optimization study has been carried out using the analytical activation overpotential formulation. Further, the mathematical model has been simplified for the CCL and an analytical approach has been provided for the liquid water transport in the catalyst layer. The volume-averaged mathematical model of the CCL is finally implemented numerically along with an investigation how the physical structure of a catalyst layer affects fuel cell performance. Since the numerical model requires various effective transport properties, a set of mathematical expressions has been developed for estimating the effective transport properties in the CCL and GDL of a PEM fuel cell. The two-dimensional (2D) numerical model has been compared with the analytical model to validate the numerical results. Subsequently, using this validated model, 2D numerical studies have been carried out to investigate the effect of various physical and wetting properties of CCL and GDL on the performance of a PEM fuel cell. It has been observed that the wetting properties of a CCL control the flooding behavior, and hydrophilic characteristics of the CCL play a significant role on the cell performance. To investigate the effect of concentration variation in the flow channel, a three-dimensional numerical simulation is also presented.

Recently, considerable attention has been focused on the generation of nano- and micrometer scale multicomponent polymer particles with specifically tailored mechanical, electrical and optical properties. As only a few polymer-polymer pairs are miscible, the set of multicomponent polymer systems achievable by conventional methods, such as melt blending, is severely limited in property ranges. Therefore, researchers have been evaluating synthesis methods that can arbitrarily blend immiscible solvent pairs, thus expanding the range of properties that are practical. The generation of blended microparticles by evaporating a co-solvent from aerosol droplets containing two dissolved immiscible polymers in solution seems likely to exhibit a high degree of phase uniformity. A second important advantage of this technique is the formation of nano- and microscale particulates with very low impurities, which are not attainable through conventional solution techniques. When the timescale of solvent evaporation is lower than that of polymer diffusion and self-organization, phase separation is inhibited within the atto- to femto-liter volume of the droplet, and homogeneous blends of immiscible polymers can be produced. We have studied multicomponent polymer particles generated from highly monodisperse micrordroplets that were produced using a Vibrating Orifice Aerosol Generator (VOAG). The particles are characterized for both external and internal morphology along with homogeneity of the blends. Ultra-thin slices of polymer particles were characterized by a Scanning Electron Microscope (SEM), and the degree of uniformity was examined using an Electron Dispersive X-ray Analysis (EDAX). To further establish the homogeneity of the polymer blend microparticles, differential scanning calorimeter was used to measure the glass transition temperature of the microparticles obtained. A single glass transition temperature was obtained for these microparticles and hence the homogeneity of the blend was concluded. These results have its significance in the field of particulate encapsulation. Also, better control of the phase morphologies can be obtained by simply changing the solvent/solvents in the dilute solutions. Evaporation and drying of a binary droplet containing a solute and a solvent is a complicated phenomenon. Most of the present models do not consider convection in the droplet phase as solvent is usually water which is not very volatile. In considering highly volatile solvents the evaporation is very rapid. The surface of the droplet recedes inwards very fast and there is an inherent convective flow that is established inside the solution droplet. In this dissertation work, a model is developed that incorporates convection inside the droplet. The results obtained are compared to the size obtained from experimental results. The same model when used with an aqueous solution droplet predicted concentration profiles that are comparable to results obtained when convection was not taken into account. These results have significance for more rigorous modeling of binary and multicomponent droplet drying.

The synthesis of mesoporous silica thin films using surfactant templating typically leads to an inaccessible pore orientation, making these films not suitable for membrane applications. Recent advances in thin film synthesis provide for the alignment of hexagonal pores in a direction orthogonal to the surface when templated on chemically neutral surfaces. In this work, orthogonal thin film silica membranes are synthesized on alumina supports using block copolymer poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123) as the template. The orthogonal pore structure is achieved by sandwiching membranes between two chemically neutral surfaces, resulting in 90 nm thick films. Solvent flux of ethanol through the membrane demonstrates pore accessibility and suggests a silica pore size of approximately 10 nm. The permeability of ions and fluorescently tagged solutes (ranging from 4,000 to 70,000 Da) is used to demonstrate the membrane’s size selectivity characteristics. A size cut off occurs at 69,000 Da for the model protein BSA. By functionalizing the silica surface with a long chained alkyl group using n-decyltriethoxysilane (D-TEOS), the transport properties of the membranes can be altered. Contact angle measurements and FTIR results show the surface to be very hydrophobic after functionalization. Solvent flux of ethanol through the silica thin film membrane is similar before and after functionalization, but water flux decreases. Thin film silica membranes show much promise for applications in catalysis, bio-sensing, and affinity separations.

Nowadays, the development of novel materials involves diverse branches of science as a consequence of the new requirements imposed by modern society. This includes aspects ranging from the optimization of the manufacturing processes to the durability of the materials themselves. Ideally, some synergism should exist between the durability, the properties of interest in the material. Although metals in their pure state are often desired, the best properties or combination of properties often cannot be satisfactorily achieved with a single metal. In these situations, the desired properties can be attained by the formation of alloys of these metals with others. Ni-Co alloys are no exceptions and so have received considerable attention especially in microsystem technology due to the magnetic properties of cobalt and the corrosion and wear resistance of nickel. Moreover, this interest has been further stimulated by its use in the manufacture of sensors, magnetic devices, microrelays, inductors, actuators, memory devices and hard drives. The fabrication of these alloys (particularly coatings) via electroplating has been shown to be techno-economically feasible in comparison with other processes: capability of high volume production, low cost and the ability to coat thin layers on non-planar substrates. In addition, the materials fabricated by this technology exhibit excellent characteristics such as refined grain structure, smoothness, low residual stress and coercivity, etc., making them advantageous to materials produced by other physical methods of deposition. Nevertheless, one of the biggest problems faced during the formation of Ni-Co alloys is its anomalous behavior whereby cobalt preferentially deposits over nickel under most conditions, even when the Ni(II) concentration is significantly higher than that of Co(II). This problem has complicated the prediction and control of the metal composition in these alloys during their production and as a consequence the ability to obtain the desirable properties associated with high nickel content. Although this problem is not recent, the studies that have been carried out so far to analyze this system have not always been as comprehensive as they could be in terms of the experimental conditions investigated or the reaction mechanisms and mathematical models developed to describe its behavior. Consequently, the origin of this behavior is still not completely understood. Thus, this work presents a contribution in terms of the analysis of the reaction mechanisms for single metal deposition of nickel and cobalt and for the formation of Ni-Co alloys in sulphate media with the intention of gaining a better understanding of the phenomena controlling the anomalous behavior of this system. Analyses of the single metal deposition of nickel and cobalt are first carried out to better understand their reaction mechanisms. Such an approach should allow the contributions of the reduction of each metal ion and interactions between the two systems during alloy co-deposition to be more clearly understood. In order to analyse the aforementioned systems, both steady state and transient techniques are employed. Among these techniques, electrochemical impedance spectroscopy (EIS) is employed since it is a robust and powerful method to quantitatively characterize the various relaxation phenomena occurring during the electrodeposition of metals. The experimental data acquired from this technique are analyzed with comprehensive physicochemical models and the electrochemical processes are quantified by fitting the models to these data to determine the kinetic parameters. During the development of the physicochemical models, several assumptions (e.g. neglect of convection, homogeneous reactions and single electron-transfer steps) made in former models are relaxed in order to investigate their combined impact on the predicted response of the system. Estimates of the kinetic parameters determined by EIS for the deposition of the single metals reveals that the first step of Co(II) reduction is much faaster tha the corresponding step of Ni(II) reduction. Some limitations of the EIS technique (i.e. analysis at high overpotentials) are exposed and compared in the case of the nickel deposition using linear sweep voltammetry (LSV). Likewise, physicochemical models accounting for most of the important phenomena are derived and fitted to experimental data. Ni-Co alloy formation is analyzed using LSV and steady state polarization experiments for different pH, current density and electrolyte composition. Current efficiencies for metal depsoition and alloy composition are also evaluated. To date, no experimental study considering all these variables has been reported in the literature. Then a steady state model is presented to describe the electrode response during alloy formation and used to provide insight into the anomalous behavior of this system. This model is based on information obtained from previous studies reported in the literature and from the current research. After being fitted to the experimental data, the model reveals that the anomalous behavior observed for this alloy is likely caused by the much faster charge-transfer of Co(II) reduction than that of Ni(II) reduction and not by other previously proposed mechanisms such as competition between adsorbed species for surface sites, formation of aqueous hydroxides (MeOH+) or mixed intermediate species (NiCo(III)ads) on the surface of the electrode.

This thesis deals with diffusion and flow of sub-critical hydrocarbons in activated carbon by using a differential permeation method. The hydrocarbons are selected according to the effect on environmental concerns and their unique characteristics such as polarity and affinity towards activated carbon. Although it has been known that transport processes in activated carbon consist of Knudsen diffusion, gaseous viscous flow, adsorbed phase diffusion (so called, surface diffusion) and condensate flow, there have been no rigorous models to describe the transport processes in activated carbon with a full range of pressures. In particular among the four processes, the mechanism of adsorbed phase diffusion in activated carbon is still far from complete understanding. Also due to the dispersion interactions between adsorbing molecules and the solid surface, one would expect that Knudsen diffusion is influenced by the dispersive forces. From intensive experimental observations with a great care over a full range of pressures, conventional methods (for example, direct estimation from inert gas experiments) to determine adsorbed phase diffusion are found to be inadequate for strongly adsorbing vapors in activated carbon. By incorporating the effect of adsorbate-adsorbent interactions into Knudsen diffusivity, the general behavior of adsorbed phase diffusion in terms of pressure (or surface loading) can be obtained, showing a significant role in transport at low pressures. For non-polar hydrocarbons such as benzene, carbon tetrachloride and n-hexane, a mathematical model, which accounts for the effects of adsorbate-adsorbent interactions and pore size distribution, is formulated and validated, resulting in a good agreement with experimental data. Moreover, the adsorption and dynamic behaviors of alcohol molecules (which are polar compounds) are investigated with an aim to compare their behaviors against those of non-polar compounds.