A database containing Henry's law constants, infinite dilution activity coefficients and solubility data of industrially important chemicals in aqueous systems has been compiled. These properties are important in predicting the fate and transport of chemicals in the environment. The structure of this database is compatible with the existing DIPPR® 801 database and DIADEM interface, and the compounds included are a subset of the compounds found in the DIPPR® 801 database. Thermodynamic relationships, chemical family trends, and predicted values were carefully considered when designating recommended values. Henry's law constants and infinite dilution activity coefficients were measured for toluene, 1-butanol, anisole, 1,2-difluorobenzene, 4-bromotoluene, 1,2,3-trichlorobenzene, and 2,4-dichlorotoluene in water using the inert gas stripping method at ambient pressure (approximately 12.5 psia) and at temperatures between 8°C and 50°C. Fugacity ratios, required to determine infinite dilution activity coefficients for the solid solutes, were calculated from literature values for the heat of fusion and the liquid and solid heat capacities. Chemicals were chosen based on missing or conflicting data from the literature. A first-order temperature-dependent group contribution method was developed to predict Henry's law constants of hydrocarbons, alcohols, ketones, and formats where none of the functional groups are attached directly to a benzene ring. Efforts to expand this method to include ester and ether groups were unsuccessful. Second-order groups were developed at a reference condition of 298.15 K and 100 kPa. A second-order temperature-dependent group contribution method was then developed for hydrocarbons, ketones, esters, ethers, and alcohols. These methods were compared to existing literature prediction methods.

In underground oil reservoirs, Hydrogen sulfide is usually found coexisting with the oil due to bacteria reduction over a long period of time. The amount of H2S in the oil varies from place to place around the globe. When the oil extraction process begins, the presence of Hydrogen sulfide becomes noticeable as drilling tools, piping and other equipment suffer from sulfide stress cracking, electrochemical corrosion and corrosion fatigue. For this reason, the oil industry invests millions of dollars per year trying to find better ways to reduce the amount of H2S in oil. An important part of the current investigations deals with brine (sea water)/oil mixtures. The reasons are two-fold: 1) one way of extracting the petroleum from the reservoir is by injecting brine into it and since it has a higher density than oil, the latter will be ejected up to the surface. Taking into account the complex fluid flow occurring within the reservoir it is easy to understand that some brine will also be present as part of the ejected fluid; 2) brine is already present in the reservoir, so independent of the extraction method used, there will be a brine/oil mixture in the ejected flow. When brine and oil have absorbed H2S under pressure in the reservoir and then suffer a decompression during the extraction process, a certain amount of H2S is released from the liquid phase. In order to have a better prediction of how much Hydrogen sulfide can be liberated a good understanding of H2S absorption by these liquids is necessary. The amount of gas a solvent absorbs is a function of pressure, original gas concentration and temperature as described by Henry's Law. The purpose of this thesis is to experimentally analyze how much of the corrosive gas is absorbed into different brine/oil mixtures, and brine and oil, separately. In order to find sufficient data for a thorough analysis, different reservoir simulation scenarios were created. The liquids were mixed from pure brine to pure oil, resulting in 33% and 66% water cuts. Data were obtained at 2 pressures of 20atm and 70atm at room temperature. H2S concentration was also a variable, changing the original gas concentration through different values: 50, 100, and 300ppm. These experiments were conducted in an autoclave system and will better explain the hydrostatic process that occurs inside the reservoir. It was found that throughout all the water cuts, the role that total pressure plays in the absorption phenomena is of less importance as the original H2S concentration is increased. In the same manner it was observed that the highest mass-absorption ratios are always found between 50 and 100ppm and the lowest at 300ppm, this is observed for all water cuts and total pressures. Another important finding was that the ability to absorb the corrosive gas decreases as the original H2S concentration increases and this proves to be true for all water cuts and system pressures. After conducting these different reservoir scenarios, tests were conducted to simulate 300m of the horizontal section of the pipe that connects the head of the well with the platform. This was done with a high pressure 300-meter long loop. It was found that the corrosive gas is absorbed at a higher rate when there is a flow, opposite to a hydrostatic case. Henry's Law constant was identified for each water cut and each pressure, however, the test procedure could not be validated since the gas being studied was not in its pure form. Understanding the absorption phenomena of Hydrogen sulfide in different water cuts will definitely be of great help to the oil industry to make better forecasts of H2S concentrations being ejected from each well.

Although utilities attempt to avoid offensive smelling compounds in consumer's drinking water, their efforts are often hampered by a lack of data or knowledge of the physical, chemical, and sensory properties of odorants. Many factors affect the ability of a consumer to detect odors, including: concentration, presence of chlorine/other odorants, temperature, and the individual's sensitivity. This research developed a simplified static-headspace technique to determine Henry's Law constants at multiple temperatures and then use these data to calculate the enthalpy of solution so that new Henry's Law constants can be calculated at any temperature using the van't Hoff Equation. The method was applied to three taste-and-odor compounds of moderate water solubility (about 100 mg/L). 2-Methylisoborneol (2-MIB) is a methylated monoterpene alcohol that is produced by actinomycetes and blue-green algae and has a musty odor that is detectable at 4-10 ng/L water. Geosmin, also produced by actinomycetes and blue-green algae, has a detectable earthy odor at 5-10 ng/L. trans-2, cis-6-Nonadienal is enzymatically synthesized from poly-unsaturated fatty acids by diatoms like Synura and has cucumber and fishy odors detectable at 10-40 ng/L levels. The new static headspace method uses standard glassware used in odor-analyses. 500 mL wide-mouth Erlenmeyer flasks were modified with septum sampling ports to measure vapor phase concentrations by SPME/GC-MS. Unitless Henry's Law constants were determined at multiple temperatures using the vapor and aqueous phase concentrations. From the Henry's Law constants, the enthalpies of reactions were calculated. For these compounds, the values for Henry's Law constants ranged from 0.002 to 0.02 for four temperatures between 20 to 45 °C with geosmin and 2-MIB having similar and higher values than for nonadienal. The constants increased with increasing temperature. The enthalpies of vaporization from the aqueous phase were determined to be in the range of 50-80 kJoule/mole. The experiments were repeated with fulvic acid added to the aqueous media at different concentrations. The Henry's Law constants were decreased with the presence of fulvic acid; however no correlation between the concentration of fulvic acid and the decrease was observed. The decrease in constants for 2-MIB and geosmin were very small compared to nonadienal. Finally the measured Henry's Law constants were used to predict gas phase concentrations of odorants for known aqueous concentrations of geosmin, 2-MIB, and nonadienal. The results were correlated to the human sensory data obtained from flavor profile analysis. The data demonstrated that as the gas phase concentration increased, the perceived odor intensity also increased, but only up to a certain point. The vapor phase concentration increased linearly as the aqueous phase concentration increased, but the FPA intensity increased at a lower rate and leveled-off. The increase in the FPA rating at 25ï °C was greater than at 45 °C although the vapor phase concentration was greater at 45 °C. For samples containing 400 and 600 ng/L geosmin, 400 and 600 ng/L, 2-MIB, 100 and 200 ng/L nonadienal, the increase in gas phase concentration did not increase the FPA ratings of the panelists. It was concluded that, utilities will be challenged to assess and treat high concentrations of geosmin, 2-MIB, and nonadienal. Sensory analysis will not be predictive of aqueous or vapor concentration at high levels and may be misleading if used to determine a treatment strategy. Chemical analyses, especially solid phase microextraction technique is very effective in measuring these compounds even at low ng/L levels. The temperature-related Henry's Law constants can be used to assess remediation systems, human exposure and sensory perception by predicting gas phase concentration in a variety of situations, such as showering and washing dishes. / Master of Science

The Henry's law constant is important in the gas-liquid mass transfer process. This study investigates the apparent dimensionless Henry's law constant, also known as the gas-liquid partition coefficient (K'H), of both hydrophilic (methanol, isopropanol and acetone) and hydrophobic (toluene and p-xylene) organic compounds. The K'H in deionized (DI) water, wastewater with a maximum total dissolved organic carbon (DOC) content of 700 mg/L, and DI water mixed with a maximum activated sludge suspended solid (SS) concentration of 40,000 mg/L, are measured by the single equilibrium technique (SET) at 288 K, 293 K, 298 K and 303 K. Experimental results indicate that the K'H of the three tested volatile organic compounds (VOCs) varies according to three situations. First, the K'H of the hydrophilic compounds in mixed liquor with the maximum suspended solid concentration is higher than that in DI water. The maximum rates of increase of K'H from KH in the SS range between 288 K and 303 K are 27.2% for methanol, 23.5% for isopropanol and 16.1% for acetone. Second, the K'H values for toluene and p-xylene are lower than those in DI water. Between 288 K and 303 K, the maximum reduce rate of K'H from KH in the SS range are 87.3% for toluene and 93.0% for p-xylene. Third, the K'H values of all of the test compounds in the wastewater are lower than those in DI water. The maximum rates of decrease of K'H from KH in the DOC concentration range between 288 K and 303 K are 1.2% for methanol, 1.1% for isopropanol, 1.7% for acetone, 14.3% for toluene and 20.1% for p-xylene. A model is presented to related K'H to wastewater DOC and concentration of SS in the activated sludge, using an organic carbon-water partition coefficient (KOC) and activated sludge-water partition coefficient (KSS) as model parameters. The model is verified, and model parameters for test compounds are estimated. Temperature variations of K'H can be regressed using van't Hoff's equation. The gas-water phase change enthalpy £GH'gw rises approximately linearly with increasing SS for hydrophobic toluene and p-xylene. K'H variation can be controlled by SS concentration and temperature in activated sludge system. The temperature effect of KOC and KSS are also observed. KOC and KSS decrease with as the temperature rises from 288 K to 303 K. The VOCs phase change enthalpy and entropy can be calculated using thermodynamic analysis. The partition of VOCs into the organic carbon phase releases energy, and thus prefers low temperatures. Lower temperatures and higher SS concentrations lead to lower K'H for hydrophobic VOCs, while higher SS concentrations result in higher K'H for hydrophilic VOCs. Organic-rich wastewater or low-biomass mixed liquor can successfully remove hydrophilic VOCs from contaminated air streams by bioscrubber. However, bioreactors scrubbed with high biomass-containing mixed liquor perform better than regular activated sludge concentration in removing hydrophobic VOCs. The experimental results thus support the design and operation of bioscrubber and suspended operable bioreactors.

Sick building syndrome (SBS) is a particular concern in places with inadequate ventilation and frequently attributed to chemical contaminants such as volatile organic compounds (VOCs)released from indoor sources that are frequently encountered in everyday life such as adhesives, carpeting, upholstery, manufactured wood products, copy machines, pesticides, cleaning agents inside buildings, plumbing vents, and painting. Furthermore, it is a major issue for modern human beings who spend most of their time indoors or must stay indoors for self-isolation due to special circumstances such as the coronavirus disease-19 (COVID-19) pandemic that occurred in 2019 and 2020. Main indoor VOCs are trichloroethylene (TCE), benzene, toluene, and para-xylene (p-xylene). In general, these compounds are not present in indoor spaces at acute concentrations, but prolonged exposure to these compounds can have chronic health effects such as allergic sensitization, increased cancer risks, and respiratory diseases. In this study, the adsorption process with various advantages has been applied to remove VOC’s using commercially available hydrophobic adsorbents. The hydrophobic adsorbents can contribute to reducing the possibility of chemical adsorption (chemisorption) of moisture from the air, which can decrease the capacity of adsorbent by clogging the pores. The adsorption of these major VOCs was investigated in this work for three major types of industrial hydrophobic adsorbents: activated carbons, zeolites, and polymer. This study will show the investigation into finding the most promising hydrophobic adsorbent for removal of TCE, benzene, toluene, and p-xylene, which are the main VOCs found indoors. The promising hydrophobic adsorbent has been determined by comparing Henry’s law constants and heat of adsorption values for the different adsorbents, which were estimated by using a concentration pulse chromatographic technique by utilizing a gas chromatograph equipped with a flame ionization detector. For all adsorbents, Henry’s law constants at room temperature of p-xylene were always the highest followed by toluene, benzene, and TCE. For all adsorbates, Henry’s law constants at room temperature of AC BPL and HiSiv 3000 were higher than the other hydrophobic adsorbents. For a developing modern society dealing with a pandemic, this study can contribute to producing the optimized gas masks and indoor filters for the removal of indoor air pollutants, which can help people who suffer from SBS. It can also help society for taking preventative actions towards dealing with SBS.

L'utilisation du CO2 comme matière première pour la synthèse de produits à haute valeur ajoutée, comme les carbonates cycliques, est aujourd'hui l'une des alternatives proposées dans la réduction des émissions gazeuses à effet de serre. Ce travail de thèse vise à comprendre et concevoir un procédé de valorisation de CO2 à partir de la modélisation de la thermodynamique et des cinétiques de transfert de matière et de réactions, qui sont engendrées dans la synthèse de carbonates cycliques à partir des époxydes et un composé hétérocyclique comme catalyseur. Grâce à ce nouveau système, les carbonates cycliques très utilisés dans l'industrie de polymères, cosmétique ou pharmaceutique, sont obtenus avec de bons rendements, dans des conditions opératoires douces et en absence de solvants. Des propriétés thermodynamiques telles que la solubilité et la constante de Henry ont été estimées pour les systèmes binaires CO2/époxyde. L'étude du transfert de matière sans ou avec réactions a permis de déterminer respectivement le coefficient de transfert de matière en phase liquide et le régime de la réaction. Des suivis cinétiques ont été réalisés afin de proposer un modèle cinétique capable de représenter la réaction et d'estimer les paramètres cinétiques. Ces derniers ont été utilisés pour la conception préliminaire et la simulation du procédé de production du carbonate d' épichlorohydrine sur Aspen Hysys. / Today, the utilisation of CO2 as raw material for the synthesis of high-value added products like cyclic carbonates, is one of the alternatives used for reducing greenhouse gases. This thesis aims to understand and design a CO2 valorisation process by modelling the thermodynamic and the mass transfer/reaction kinetics generated during the cyclic carbonates synthesis from CO2, epoxides and a heterocyclic compound as catalyst. By using this new catalytic system, cyclic carbonates, which are used in the polymeric, pharmaceutic or cosmetic industry, can be produced with good yields at low temperatures and pressures and without any solvent. Thermodynamic properties as solubility and Henry's law constant have been estimated for CO2/epoxide binary systems. Mass transfer occurring without and with reaction has been studied in order to determine respectively the liquid volumetric mass transfer coefficient and the reaction regime. A kinetic study has been performed to propose a model able to represent the reaction and to estimate the kinetic parameters. This information has been used in the design and the simulation of the production process of epichlorohydrin carbonate on Aspen Hysys.