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The construction sector is responsible for 20% of Greenhouse Gas (GHG) emissions, of whichdiesel-powered construction equipment are large contributors. Currently there are many ongoing Fuel Cell (FC) powered construction equipment projects as it is seen as an attractiveoption to power the futures zero-emission heavy-duty machines. Although an attractivealternative, hydrogen FC has drawbacks such as releasing liquid water and water vapor viathe exhaust as a byproduct which in their working environment can cause a suite of issues. Agap in the literature on the water exhausted is present and therefore this degree project seeksto investigate the amount, and ratio, of liquid water and water vapor released from threetypical construction equipment drive cycles which would allow further investigation onappropriate management. The method used for this degree project was to modify a pre-mademodel in Simulink built with Simscape blocks. The model was modified to represent a FCsystem used in a test-rig by implementing experimental and measured data for design andoperating parameters. Different pressures, temperatures, and cathode inlet RelativeHumidity (RH) were investigated to find their effect on the performance and water in theexhaust. A sensitivity analysis of different unknown parameters was also conducted tounderstand their influence on the results. For the reference case, the results showed that foran articulated hauler, the water in the exhaust was 26% liquid which translates to 8.6 kg for a1-hour drive cycle. The crawler excavator and wheel loader, both had 30-minute drive cyclesand had 1.1 kg liquid water with a liquid water ratio of 7% and 0.7 kg liquid water with aliquid water ratio of 5% in the exhaust respectively. For a full 8-hour workday with twoparallel FCs connected, the articulated hauler liquid water amount is 137.6 kg, the crawlerexcavator 35.2 kg, and the wheel loader 22.4 kg. Overall, it was found the liquid water ratiocould be changed to a large extent with different operating parameters, where thetemperature had the greatest influence. The system and stack efficiencies did not changeconsiderably with different operating parameters, meaning that the total water in the exhaustremained similar for the different respective drive cycles.

Important aspects of the adjustments to aerosol-cloud interactions can be examined using the relationship between cloud droplet number concentration (Nd) and liquid water path (LWP). Specifically, this relation can constrain the role of aerosols in leading to thicker or thinner clouds in response to adjustment mechanisms. This study investigates the satellite retrieved relationship between Nd and LWP for a selected case of mid-latitude continental clouds using high-resolution Large-eddy simulations (LES) over a large domain in weather prediction mode. Since the satellite retrieval uses the adiabatic assumption to derive the Nd, we have also considered adiabatic Nd (NAd) from the LES model for comparison. The joint histogram analysis shows that the NAd-LWP relationship in the LES model and the satellite is in approximate agreement. In both cases, the peak conditional probability (CP) is confined to lower NAd and LWP; the corresponding mean LWP (LWP) shows a weak relation with NAd. The CP shows a larger spread at higher NAd (>50 cm–3), and the LWP increases non-monotonically with increasing NAd in both cases. Nevertheless, both lack the negative NAd-LWP relationship at higher NAd, the entrainment effect on cloud droplets. In contrast, the model simulated Nd-LWP clearly illustrates a much more nonlinear (an increase in LWP with increasing Nd and a decrease in LWP at higher Nd) relationship, which clearly depicts the cloud lifetime and the entrainment effect. Additionally, our analysis demonstrates a regime dependency (marine and continental) in the NAd-LWP relation from the satellite retrievals. Comparing local vs large-scale statistics from satellite data shows that continental clouds exhibit only a weak nonlinear NAd-LWP relationship. Hence a regime-based Nd-LWP analysis is even more relevant when it comes to warm continental clouds and their comparison to satellite retrievals.

Water is of essential importance for life on earth, yet the physics concerning its various anomalous properties has not been fully illuminated. This thesis is dedicated to the understanding of liquid water from aspects of microscopic structures, dynamics, electronic structures, X-ray absorption spectra, and proton transfer mechanism. This thesis use the computational simulation techniques including density functional theory (DFT), ab initio molecular dynamics (AIMD), and theoretical models for X-ray absorption spectra (XAS) to investigate the dynamics and electronic structures of liquid water system. The topics investigated in this thesis include a comprehensive evaluation on the simulation of liquid water using the newly developed SCAN meta-GGA functional, a systematic modeling of the liquid-water XAS using advanced ab initio approaches, and an explanation for a long-puzzling question that why hydronium diffuses faster than hydroxide in liquid water. Overall, significant contributions have been made to the understanding of liquid water and ionic solutions in the microscopic level through the aid of ab initio computational modeling. / Physics

Dans les applications industrielles et lors des opérations de transport du gaz naturel, la présence d'eau sous forme liquide ou en phase vapeur peut entraîner la formation d'hydrates provoquant le colmatage des unités industrielles et des lignes de conduites et il est indispensable de définir précisément les seuils de déshydratation à réaliser, afin d'éviter la formation d'hydrates. Cela est réalisé à l'aide d'un modèle thermodynamique qui prédit la stabilité des hydrates, en fonction de la température, de la pression et de la composition du gaz.Les modèles thermodynamiques classiques, développés uniquement sur la base de données expérimentales de formation d'hydrates en présence d'eau liquide, surestiment fortement la température de dissociation des hydrates en l'absence d'une phase aqueuse.Dans le but de définir un modèle thermodynamique capable de représenter convenablement les équilibres de phases vapeur-hydrate et prédire ainsi la température de dissociation des hydrates que l'on soit en présence ou en l'absence d'eau liquide, nous avons mis au point une méthodologie originale pour la détermination de la température de dissociation des hydrates de corps purs et de mélanges en l'absence d'eau liquide. Cette méthodologie, basée sur le suivi de la teneur en eau de phase vapeur, en fonction de la température par coulométrie Karl Fischer, a permis la détermination de la température de dissociation de plusieurs hydrates simples et mixtes à des teneurs en eau et pressions différentes ainsi que les quantités d'hydrates formées dans ces conditions.Sur la base de ces nouvelles données, nous avons défini un modèle thermodynamique basé sur l'utilisation de l'approche de Dharmawardhana pour le calcul de la fugacité de l'eau dans l'hydrate vide,le potentiel de Kihara pour le calcul de la constante de Langmuir et l'équation d'état CPA (Cubic Plus Association) pour la modélisation des phases fluides. Nous avons montré que l'utilisation de l'équation d'état CPA, capable de prendre en compte l'auto association de l'eau apporte une amélioration très significative.Le développement d'un flash biphasique hydrate-fluide nous a permis de calculer les quantités d'hydrates mixtes formées et de les comparer à nos données expérimentales. / In industrial applications and during natural gas transport, the presence of water under liquid form or within a vapour phase can lead to gas hydrate formation causing the blockage of industrial units and transport lines. Hence, in order to avoid such situation, it is very important to well determine its formation conditions. It is occurred by using a rigorous thermodynamic model. Due to the lack of data in the literature concerning gas hydrates formation in the absence of an aqueous phase,usual thermodynamic models predict correctly gas hydrate dissociation temperature only in the presence of aqueous water. Our purpose is to propose a thermodynamic model with hydrate phase that can predict gas hydrate dissociation temperature in both cases: with and without water liquid phase.At first, using an existing apparatus, we have developed a new experimental protocol in order tomeasure gas hydrate dissociation temperature in the absence of liquid water. It consists in measuring the water content in the vapour phase as a function of the temperature by using a Karl Fischer coulometer. We have measured the dissociation temperature of many simple and mixture hydrates.We have also developed a thermodynamic model that is able to predict correctly gas hydrate dissociation temperature, in the absence and in the presence of liquid water. This model is based onthe use of Dharmawardhana's approach for the calculation of hydrate fugacity in the empty hypothetical hydrate, Kihara potential for the calculation of the Langmuir constant and CPA EoS forfluid phases modelling. We have shown that the use of CPA EoS improves the prediction of gas hydrate dissociation temperature. We have also developed a biphasic flash (hydrate-fluid) allowing the calculation of the formed mixture hydrate amounts. The calculated amounts are in agreement with the experimental ones.

<p>Water is one of the most common compounds on earth and is essential for all biological activities. Water has, however, been a mystery for many years due to the large number of unusual chemical and physical properties, e.g. decreased volume during melting and maximum density at 4 °C. The origin of the anomalies behavior is the nature of the hydrogen bond. This thesis will presented an x-ray absorption spectroscopy (XAS) study to reveal the hydrogen bond structure in liquid water.</p><p>The x-ray absorption process is faster than a femtosecond and thereby reflects the molecular orbital structure in a frozen geometry locally around the probed water molecules. The results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms. The molecular arrangement in the first coordination shell of liquid water is actually very similar as the two-hydrogen-bonded configurations at the surface of ice. This discovery suggests that most molecules in liquid water have two-hydrogen-bonded configurations with one donor and one acceptor hydrogen bond compared to the four-hydrogen-bonded tetrahedral structure in ice. This result is controversial since the general picture is that the structure of liquid water is very similar to the structure of ice. The results are, however, consistent with x-ray and neutron diffraction data but reveals serious discrepancies with structures based on current molecular dynamics simulations. The two-hydrogen-bond configuration in liquid water is rigid and heating from 25 °C to 90 °C introduce a minor change in the hydrogen-bonded configurations. Furthermore, XAS studies of water in aqueous solutions show that ion hydration does not affect the hydrogen bond configuration of the bulk. Only water molecules in the close vicinity to the ions show changes in the hydrogen bond formation. XAS data obtained with fluorescence yield are sensitive enough to resolved electronic structure of water molecules in the first hydration sphere and to distinguish between different protonated species. Hence, XAS is a useful tool to provide insight into the local electronic structure of a hydrogen-bonded liquid and it is applied for the first time on water revealing unique information of high importance.</p>

<p>Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode, which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed to view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools.</p><p>This thesis addresses the electronic structure of liquids and lithium battery materials using resonant inelastic X-ray scattering (RIXS) at high brightness synchrotron radiation sources. The electronic structure of battery electrodes has been probed, before and after lithiation, studying the doping of electrons into the host material. The chemical composition of the SEI on cycled graphite electrodes was determined. The local electronic structure of water, methanol and mixtures of the two have been examined using a special liquid cell. Results from the study of liquid water showed a strong influence on the 3a₁ molecular orbital and orbital mixing between molecules upon hydrogen bonding. The study of methanol showed the existence of ring and chain formations in the liquid phase and the dominating structures are formed of 6 and 8 molecules. Upon mixing of the two liquids, a segregation at the molecular level was found and the formation of new structures, which could explain the unexpected low increase of the entropy.</p>

1-km MODIS observations of ship tracks off the west coast of the U.S. are used to characterize changes in cloud visible optical depths, cloud droplet radii, cloud cover fraction, and column cloud liquid water amount as low-level marine clouds respond to particle pollution from underlying ships. This study re-examines the finding of earlier studies based on Advanced Very High Resolution Radiometer (AVHRR) observations showing that when restricted to pixels overcast by low-level, single-layered cloud systems, the polluted clouds in the ship tracks had on average ~20% less liquid water than the nearby uncontaminated clouds. This study uses Moderate Imaging Spectroradiometer (MODIS) observations from the Terra and Aqua satellites and takes advantage of the 1.6 and 2.1-µm channels in addition to the 3.7-µm channel available on AVHRR to derive droplet effective radii. The additional channels allow for different and presumably more comprehensive analyses of the cloud properties. In addition, this study uses a retrieval scheme that accounts for the effects of partial cloudiness within the 1-km pixels on the retrieved cloud properties. An improved automated track finding scheme that allows for the selection of unpolluted clouds to be closer to the clouds identified as being polluted is also employed in this study. When restricted to overcast pixels, as was done in earlier studies, results from the Terra and Aqua MODIS observations indicate that cloud droplet effective radii are significantly smaller and cloud optical depths significantly larger for polluted pixels than for unpolluted pixels. Cloud top height does not change when clouds become polluted but cloud liquid water path decreases slightly but significantly. The decrease in cloud liquid water obtained with the MODIS observations was at most ~10%, much less than the 20% obtained with the AVHRR observations. This decrease, however, depended on the wavelength used to derive the droplet effective radii. Also, the clouds that were most sensitive to pollution were those with small optical depths and large droplet effective radii. / Graduation date: 2007

Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode, which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed to view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools. This thesis addresses the electronic structure of liquids and lithium battery materials using resonant inelastic X-ray scattering (RIXS) at high brightness synchrotron radiation sources. The electronic structure of battery electrodes has been probed, before and after lithiation, studying the doping of electrons into the host material. The chemical composition of the SEI on cycled graphite electrodes was determined. The local electronic structure of water, methanol and mixtures of the two have been examined using a special liquid cell. Results from the study of liquid water showed a strong influence on the 3a1 molecular orbital and orbital mixing between molecules upon hydrogen bonding. The study of methanol showed the existence of ring and chain formations in the liquid phase and the dominating structures are formed of 6 and 8 molecules. Upon mixing of the two liquids, a segregation at the molecular level was found and the formation of new structures, which could explain the unexpected low increase of the entropy.

Water is one of the most common compounds on earth and is essential for all biological activities. Water has, however, been a mystery for many years due to the large number of unusual chemical and physical properties, e.g. decreased volume during melting and maximum density at 4 °C. The origin of the anomalies behavior is the nature of the hydrogen bond. This thesis will presented an x-ray absorption spectroscopy (XAS) study to reveal the hydrogen bond structure in liquid water. The x-ray absorption process is faster than a femtosecond and thereby reflects the molecular orbital structure in a frozen geometry locally around the probed water molecules. The results indicate that the electronic structure of liquid water is significantly different from that of the solid and gaseous forms. The molecular arrangement in the first coordination shell of liquid water is actually very similar as the two-hydrogen-bonded configurations at the surface of ice. This discovery suggests that most molecules in liquid water have two-hydrogen-bonded configurations with one donor and one acceptor hydrogen bond compared to the four-hydrogen-bonded tetrahedral structure in ice. This result is controversial since the general picture is that the structure of liquid water is very similar to the structure of ice. The results are, however, consistent with x-ray and neutron diffraction data but reveals serious discrepancies with structures based on current molecular dynamics simulations. The two-hydrogen-bond configuration in liquid water is rigid and heating from 25 °C to 90 °C introduce a minor change in the hydrogen-bonded configurations. Furthermore, XAS studies of water in aqueous solutions show that ion hydration does not affect the hydrogen bond configuration of the bulk. Only water molecules in the close vicinity to the ions show changes in the hydrogen bond formation. XAS data obtained with fluorescence yield are sensitive enough to resolved electronic structure of water molecules in the first hydration sphere and to distinguish between different protonated species. Hence, XAS is a useful tool to provide insight into the local electronic structure of a hydrogen-bonded liquid and it is applied for the first time on water revealing unique information of high importance.