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A pre-flashover fire is very different from a post-flashover fire. The main difference is that in a pre-flashover fire the gas temperature and the radiation temperature differ. One thing that makes it a lot different is that the thermal exposure induced by a pre-flashover fire is largely affected by the smoke gas layer. These smoke gases can be very hot and therefore they emit heat radiation to their surroundings. The theory used, to calculate the thermal exposure of a pre-flashover fire, in this thesis relies on using thermal resistances to describe the heat transfer from the smoke gases. By doing so it is possible to calculate the temperatures of the smoke gases and the surfaces in touch with the smoke gases. Another approach is to use CFD software to numerically calculate the temperatures and in this thesis the two-zone model are compared to FDS, a CFD software. The two-zone model are also compared to a reduced-scale test. The comparisons gave good results, the two-zone model produced similar results compared to re reduced-scale test and FDS. This method of calculating thermal exposure can thereby be used to evaluate evacuation safety and save a lot of calculation time compared to calculating the thermal exposure with CFD software such as FDS.

Studies show that the use of cleaning products is related to adverse respiratory health effects ranging from irritation to asthma. Yet exposure to these chemicals is poorly understood. This dissertation summarizes the current state of knowledge of inhalation exposure to toxic chemicals in consumer cleaning products. An improved two-zone model that treats personal air space as distinct from bulk room air is presented. The model accounts for air exchange between the two zones, dynamic source characteristics (i.e., the time-varying liquid concentrations and emission rates of pollutants within a mixture), and the characteristics of chemical use (e.g., how frequently a cleaning chemical is applied to a new area). To assess exposure to cleaning products and validate the improved two-zone model twenty-three experiments, encompassing six cleaning scenarios, were completed in an environmentally-controlled chamber with a thermal mannequin. Then, the model was used to predict exposure for four hypothetical cleaning scenarios and compared against other models. The model's applicability is restricted by limited data available for parameterization. At low air exchange rates gas-phase experimental results show concentrations in the breathing-zone of the mannequin exceeded concentrations predicted by the well-mixed model by factors up to 2.1. Breathing-zone concentrations also exceed those measured at centralized room monitors by factors up to 6.1. Thus, studies that use the centralized room monitors or the well-mixed model as a surrogate for breathing-zone concentrations could potentially underpredict exposure at low air exchange rates. The two-zone model provides the best prediction of exposure to cleaning tasks, at low air exchange rates. The next best model is the well-mixed model with an exponentially decreasing emission rate, followed by the well-mixed model with a constant emission rate. At high air exchange rates the well-mixed assumption appears to be valid. The inner-zonal volume and inter-zonal air exchange were independent of fresh air ventilation rate. But both were dependant on the mannequin's body position, with standing having the highest inner-zonal volume and lowest intra-zonal air exchange rate of the three body positions investigates (standing, bent over 45°, and hands and knees). / text

The Two Element in Series (TEIS) and Two Zone models stand out as powerful tools that enable deeper understanding of compressor stage designs after they have been tested. The insights gained from these investigations have aided in improving new stage designs. Up to now, it has only been possible to use the TEIS and Two Zone models for analysis of test data due to the inability to predict the four required input parameters for untested machines. Empirical models for the TEIS and Two Zone model input parameters, ETAa5, ETAb5, Chi5, and DELTA5p, for two different types of vaned diffusers, channel and cascade, are proposed. These models were developed with frozen impeller modeling. This is the first time that modeling the TEIS and Two Zone input parameters has been attempted for vaned diffusers and impeller-diffuser coupling was not considered in this initial investigation. The centrifugal compressor experimental data used in the model building was obtained from Concepts NREC, an industry sponsor. Each dataset provided was evaluated for quality and reliability and only the data deemed reliable were used in the model building databases. The empirical models presented are built solely on this higher quality data. Seven models are proposed for use in predicting the TEIS and Two Zone model input parameters ETAa5, ETAb5, Chi5, and DELTA5p. Models for ETAa5, ETAb5, and DELTA5p are specific to the type of vane present in the diffuser, while the model for Chi5 is common to both diffuser types. These are the first models ever built for the TEIS and Two Zone model inputs applied to channel and cascade diffusers and become a benchmark for future studies. The work with these models is not complete, however. The databases are not of a size that data could be withheld from empirical model building for the express purpose of validation. Instead the model performance is evaluated by applying all of the models, simultaneously, to the database from which they were built. The determination of the effectiveness of the combined modeling is based on the average error across the entire speedline. The models proved to be effective and a contributing step to employing such models for use in future compressor design.

The Two-Element In Series (TEIS) and Two-Zone models have been used successfully for over twenty years to model test data for radial flow compressors and pumps. The models can also be used to predict the performance of new machines provided that the model inputs can be accurately specified. Unfortunately, use of the TEIS and Two-Zone models as a predictive tool has been limited because an accurate and broadly applicable method of predicting the modeling parameters, etaA, etaB, chi and d2p does not exist. Empirical models have been developed to predict the TEIS and Two-Zone modeling parameters based on a large database of centrifugal pump and compressor test results. These test data were provided by ConceptsNREC and have been collected over the past 40 years. The database consists of a wide range of machines including some that were designed and tested by ConceptsNREC and others from the open literature. Only cases with a vaneless diffuser or volute have been included in the analysis to avoid any possible impeller-diffuser interactions. From the database, models for all of the TEIS and Two-Zone parameters have been derived using basic regression techniques. Three different models are proposed for each of the two TEIS modeling parameters, etaA and etaB. One model for pumps, another for compressors, and a combined model applicable for all machines is given. For the Two-zone parameters, chi and d2p, a single set of models was developed to represent the design point performance and another showing how chi and d2p vary off-design. The combined models for etaA and EtaB are 30% and 70% more accurate than the current state-of-the-art models, respectively. The new models account for the variance in chi and d2p at off-design flow conditions and further refine the accuracy of the overall prediction by correctly modeling the loss mechanisms in the impeller passage. Validation work has shown that the set of models that predict etaA, etaB, chi and d2p can be solved to consistently produce sensible results and yield a reasonable "blind" prediction of the performance of a wide range of radial compressors and pumps. These models constitute the first broadly applicable method for predicting the required TEIS and Two-Zone variables and are sufficiently accurate to provide initial performance estimates of new impeller designs

A ship to which vehicles and other loads can be rolled on and off is usually named ro-ro ship. A ro-ro ship consists of large corridor shaped space, normally extending to a considerable length or the entire length of the ship, which is usually loaded with various vehicles or stowage units. A ro-ro space can either be designed as an open space, closed space or a weather deck. There have been several fire incidents in ro-ro ship spaces and these fires occur with a relatively high frequency. A fire on a ro-ro ship is a very complex phenomenon. The fire development is hard to predict, and the fire tend to grow very quickly. One crucial parameter for the development of these fires is the ventilation, and the ventilation conditions may be totally different depending on the design of the ro-ro space.   This study was conducted in co-operation with RISE, the department of Fire Research, and the research project RO5. RO5 aims to clarify how the ventilation in ro-ro spaces affects the development of a fire and to possibly establish conceptual solutions for fire protection measures for ro-ro spaces with different ventilation conditions. The aim of this study is to explore tendencies of how both natural and mechanical ventilation affects the fire development within a ro-ro space. The intention is to provide basic knowledge regarding this subject, so that further simulations and tests could be optimized. The long-term goal of this study is to reduce the consequences, the severity and the number of fires within ro-ro spaces. The first step in the project is to explore the usefulness of two-zone models and compare the applicability of such method to experimental data. This is crucial in order to assess the applicability of two-zone models, especially as the aim is to make a parametric study of the influence of ventilation of fire development inside ro-ro space. A literature study of previous incident investigations of fires in ro-ro spaces was performed to gain knowledge concerning possible fire scenarios, ship constructions, fire development, consequences etc. and to provide an insight into how the ventilation was used in the case of a fire. In 2002, the research project “Model Scale Fire Tests on a Vehicle Deck Aboard a Ship” was issued by SP Swedish National Testing and Research Institute (now RISE). The aim was to simulate possible fire scenarios on a vehicle deck and examine what parameters can affect the fire development. To study this, tests were performed in model scale 1:8. The model had the dimensions 11.425 m x 2.786 m x 0.625 m (length x width x height). It was concluded that the ventilation and air supply being crucial for the fire development in ro-ro space. Although fires in a closed ro-ro space can quickly become ventilation-controlled, the fire may initially grow to be very large. One part of this study was to simulate some of the tests in “Model Scale Fire Tests on a Vehicle Deck Aboard a Ship” in the same sized model (scale 1:8). This was done since no tests on a full-scale model could be found. The simulation programs used were CFAST and B-RISK. The results were used for comparison to see how the two-zone simulations cohere with the tests. This was considered necessary due to limitations of the simulation programs and to the simplifications of two-zone fire model. By the comparison it was possible to choose the most suitable simulation program of the two, to use for further simulations in the study. The most suitable program was CFAST. Another part of the study was to conduct a parameter study. Since the model used in the tests in 2002 corresponded to an eight times larger model, the model was upscaled using Froude scaling to the dimensions 91.4 m x 22.3 m x 5 m (length x width x height). This model (scale 1:1) was then used in the parameter study. In the model, steel was used as material of the walls, ceiling and floor in order to imitate a real ro-ro space. By the results of the parameter study using two-zone fire simulations in CFAST, it is concluded that increased natural ventilation results in larger fire development, as well as increased mechanical ventilation results in larger fire development. Due to the results, open ro-ro spaces are recommended to be avoided. The regulations and definitions addressing closed ro-ro spaces are suggested to be reviewed since a closed ro-ro space can have relatively large natural ventilation. If natural ventilation is nevertheless required, the simulations indicate that openings constructed as wide as possible and with as low sill- and soffit height as possible are preferable. Because of the large size of a ro-ro space, there is enough oxygen to sustain a large fire during a given period. The fire will produce inert gases in the burning process such as CO2. As the gases reaches down to the fire source, the fire will start to fade. The oxygen within the ro-ro space will get pushed away by the process. The phenomenon is called inerting/vitiation and may occur when there is a fire within a ro-ro space. Previous investigations show that, the mechanical ventilation has been used to extract smoke in order to improve visibility and locate the fire. This measure may however be risky since mechanical ventilation may increase the fire development. Also, the mechanical ventilation may not be designed to be used for this purpose. In order to locate the fire efficiently for final extinguishment new improved and safer tactical methods is suggested to be evaluated. / Ett ro-ro fartyg är ett fartyg där fordon och annan last kan rullas på och av. Ombord på ett ro-ro fartyg finns det rorolastutrymmen. Ett rorolastutrymme är ett stort, korridorformat utrymme som vanligtvis är fyllt med fordon eller andra typer av last. Ett rorolastutrymme kan designas som ett öppet rorolastutrymme, ett slutet rorolastutrymme eller ett väderdäck. Det har skett flera brandincidenter på ro-ro fartyg och i rorolastutrymmen, samt har bränderna inträffat med en relativt hög frekvens. En brand på ett ro-ro fartyg är ett väldigt komplext fenomen. Brandutvecklingen är svår att förutse, och branden tenderar att växa väldigt fort. En viktig parameter för brandens utveckling är ventilationen. I ett rorolastutrymme kan ventilationsförhållandena vara väldigt olika beroende på hur utrymmet är utformat. Denna studie genomfördes tillsammans med RISE och forskningsprojektet RO5. RO5 syftar till att klargöra hur ventilationen i rorolastutrymmen påverkar brandutvecklingen, samt om möjligt, etablera konceptuella brandskyddsåtgärder för rorolastutrymmen med olika ventilationsförhållanden. Målet med denna studien är att studera tendenser av hur både naturlig och mekanisk ventilation påverkar brandutvecklingen i ett rorolastutrymme. Avsikten med denna studien är att få grundläggande kunskap inom ämnet, för att ytterligare simuleringar och kommande tester ska kunna optimeras i forskningsprojektet RO5. Det långsiktiga målet med studien är att minska konsekvenserna, brandstorleken, samt antalet bränder i rorolastutrymme. Metoden som användes i studien var tvåzonssimuleringar. För att få kunskap om möjliga brandscenarion, fartygskonstruktion, brandutveckling, konsekvenser etc. studerades tidigare olycksutredningar av bränder i rorolastutrymmen. Litteraturstudien gav också en inblick i hur ventilationen används vid händelse av brand i rorolastutrymmen. År 2002 utfördes “Model Scale Fire Tests on a Vehicle Deck Aboard a Ship” av SP, Sveriges Tekniska Forskningsinstitut (nuvarande RISE). Målet var att testa möjliga brandscenarion i ett rorolastutrymme och undersöka vilka parametrar som kan påverka brandens utveckling. Detta studerades genom att utföra tester i en nerskalad modell (skala 1:8). Modellen hade dimensionerna 11,425 m x 2,786 m x 0,625 m (längd x bredd x höjd). En slutsats var att ventilationen och syretillförseln var avgörande för brandens utveckling i ett rorolastutrymme. Även om branden i ett slutet rorolastutrymme snabbt kan bli ventilationskontrollerad, kan branden initialt bli väldigt stor. En del av studien var att simulera några av testerna som genomfördes i “Model Scale Fire Tests on a Vehicle Deck Aboard a Ship” i en modell av samma storlek (skala 1:8). Detta gjordes eftersom inga fullskaliga tester kunde hittas. De simuleringsprogram som användes var CFAST och B-RISK. Resultaten användes för att se hur simuleringarna stämde överens med verkliga tester. Detta bedömdes nödvändigt på grund av simuleringsprogrammens begränsningar och förenklingarna i tvåzonsmodellen. Genom jämförelsen kunde det mest lämpliga programmet av de två väljas ut för att använda i studiens fortsatta simuleringar. CFAST var det mest lämpliga programmet. En annan del av studien var att genomföra en parameterstudie. Eftersom modellen som användes i testerna 2002 motsvarar en åtta gånger så stor modell, skalades modellen upp med Froudes skalningslagar till dimensionerna 91,4 m x 22,3 m x 5 m (längd x bredd x höjd). Denna modellen (skala 1:1) användes därefter i en parameterstudie. För att modellen skulle efterlikna ett rorolastutrymme användes stål som väggar, tak och golv i modellen. Med resultaten från parameterstudien som utfördes i tvåzonssimuleringsprogrammet CFAST, kan slutsatsen dras att ökad naturlig ventilation resulterar i en större brandutveckling, samt att ökad mekanisk ventilation resulterar i en större brandutveckling. Baserat på resultaten rekommenderas det att öppna rorolastutrymmen bör undvikas. Definitionen för ett slutet rorolastutrymme föreslås att ses över eftersom ett slutet rorolastutrymme kan ha relativt mycket naturlig ventilation. Om naturlig ventilation dock krävs, indikerar simuleringarna på att öppningar konstruerade så breda som möjligt och med så låg sill- och bröstningshöjd som möjligt är att föredra. På grund av att rorolastutrymmen ofta är väldigt stora finns det tillräckligt med syre för att underhålla en stor brand under en viss tid. Branden kommer i förbränningsprocessen att producera inerta gaser som CO2 och när gaserna når ned till brandkällan kommer branden att börja avta. Syret i rorolastutrymmet kommer att tryckas bort av processen. Fenomenet kallas inertering/vitiation och kan förekomma vid en brand i ett rorolastutrymme. Tidigare utredningar visar på att mekanisk ventilation har använts för att ventilera ut rökgaser för att öka sikten och därmed kunna lokalisera branden. Denna åtgärd kan dock vara riskfull då mekanisk ventilation kan öka brandförloppet. Den mekaniska ventilationen är förmodligen inte heller designad för detta ändamål. För att kunna lokalisera en brand effektivt så att släckning kan genomföras, föreslås att nya, förbättrade och säkrare taktiker utvärderas.

This research report examines the use of zone modelling compared with CFD modelling to determine when zone model approximation is valid and when a CFD model might be required. A series of computer simulations with enclosures and fires of various sizes was performed to compare the capabilities and limitations of the two computer methods. The relationship between the size of the enclosure space and the size of the fire has been demonstrated in a dimensionless form. The zone model BRANZFIRE and the CFD model FDS were used for simulating smoke development. The simulations included various full-scale experimental data on both small and large spaces found in the literature. Further simulations of large exemplar spaces with a range of fire sizes were performed to investigate different variables, which have not been examined in full-scale experiments. The simulation results have been compared based on the smoke layer height and the average layer temperature. Zukoski’s smoke filling equation was also used to compare the layer height predictions against BRANZFIRE and FDS. It was found that different data reduction techniques gave different approximations to the layer height. A perfect match between the experimental data and the model output was very difficult to achieve. FDS showed a large uncertainty of the smoke layer height and temperature in the early stages of fire across the enclosure space. In the later stages, this uncertainly became minimised where the smoke layer height and temperature were fairly uniformly developed across the space. For fire enclosures with instantaneous steady-state fires, the predictions between BRANZFIRE and FDS agreed well with each other if the fire size and the enclosure size were within a reasonable range. From the modelling of the full-scale experiments, FDS showed favourable layer-height comparisons against the full-scale experimental tests. However, the output results from BRANZFIRE are less comparable with those of FDS for the experiments with fire growth. An appropriate smoke transport time lag should be included for Zukoski’s smoke filling equation and BRANZFIRE; otherwise, they gave conservative estimates of the layer height to smaller fires with a growth phase. In general, the data reduction methods and zone models should not be used if the fire is too small relative to the enclosure size. A very low temperature rise within the enclosure space would give invalid predictions of the layer height and average layer temperature. This is because there is no clear indication of a separation between the upper and lower smoke layers or temperatures. Single point data of smoke concentrations and temperatures from CFD models should be considered through the entire space or at the specified location of interest. This also applies to an extremely large fire relative to the enclosure size where temperature distribution across the space might not be very homogenous. CFD models could also be used to investigate the details of the smoke properties in the early stages of growing fires, in which the smoke transport lag and the plume effects cannot be seen in BRANZFIRE. This research is intended to provide guidance for fire engineers by determining which of the computer methods can be used confidently and appropriately as a design tool.

The present work studies the use of a two-zone computer model to simulate the operation of an internal combustion engine with spark ignition fueled with alcohol fuels and gasohol. To fit the model to the experimental data, a parameter estimation technique was used and the heat transfer correlation that could better fit the tested fuels and engine was determined. The tested fuels were: hydrous ethanol, wet ethanol (from 10% to 40% of water, by volume), n-butanol, n-butanol/ethanol blend and gasohol. In addition to the experimental tests with the engine, tests with a packed distillation column under batch process were made in order to determine the energy efficiency involved between production and use as a fuel for hydrous ethanol and wet ethanol fuels. The results showed that the two-zone model was able to predict satisfactorily the behavior of all tested fuels, accurately obtaining the engine performance parameters. In terms of energy efficiency, wet ethanol fuels have advantage over hydrous ethanol fuel, especially in the case of 30% of water by volume, where energy efficiency reaches its maximum value, considering the distillation and engine combustion processes. The n-butanol fuel was capable of act as a surrogate for both hydrous ethanol and gasohol with efficiency, leading the engine to have good performance in the tested operational conditions and appearing, due to this, as an interesting alternative of renewable fuel to be inserted in the Brazilian energy matrix. / O presente trabalho investiga o uso de um modelo computacional de duas zonas para simular o funcionamento de um motor de combustão interna com ignição por centelha abastecido com álcoois combustíveis e gasolina. Para o ajuste do modelo fez-se uso de técnica de estimação de parâmetros e determinação da correlação de transferência de calor capaz de melhor se ajustar aos combustíveis e ao motor testados. Os combustíveis utilizados foram: etanol hidratado, etanol super-hidratado (de 10% a 40% de água, em volume), n-butanol, misturas de n-butanol e etanol e gasolina e etanol. Além dos testes experimentais com motor, testes de bancada com uma coluna de destilação recheada em regime descontínuo foram realizados a fim de determinar a eficiência energética do processo de produção e queima de etanol hidratado e super-hidratado. Os resultados obtidos mostraram que o modelo de duas zonas é capaz de prever de maneira satisfatória o comportamento de todos os combustíveis testados, com determinação precisa de parâmetros de desempenho do motor. Em termos de eficiência energética, o etanol super-hidratado tem vantagem em relação ao etanol hidratado combustível, em especial quando com 30% de água em volume, onde a eficiência energética é máxima, considerados os processos de destilação e queima no motor. O n-butanol combustível usado mostrou-se capaz de substituir eficientemente tanto o etanol hidratado como a gasolina brasileira, levando o motor a ter boa performance nas condições operacionais testadas e aparecendo, dessa forma, como interessante alternativa de combustível renovável a ser inserida na matriz energética brasileira.

In terms of master’s thesis HAM-Tools library designed for MATLAB/Simulink was modified for the use in simulations of houses in the Czech Republic. Modified library and its parts were described in detail and tested by the simulation of the one-zone and two-zones models of the house. The simulations of models with same parameters were also realized in program TRNSYS. The corresponding results achieved in mentioned simulation tools were compared to each other. The one-zone model created by using HAM-Tools library is tested by the simulation of ventilating, heating, cooling, and sources of moisture. A demonstration of the practical use of the simulation is carried out in the thesis, namely by examining the influence of the insulation thickness on the thermal performance of the house (resp. its heat loss) on real atmospheric conditions. Among others, available resources of meteorological data are mentioned and compared to each other. The function for processing of the meteorological data to a file compatible with the HAM-Tools library was created. It was also created a material data file containing commonly used materials of building structures in the Czech Republic and their parameters.

Contexte : Les modèles physico-chimiques sont de plus en plus utilisés en hygiène du travail pour estimer l’exposition aux contaminants chimiques de l’air. Ils prédisent l’exposition à l’aide d’équations mathématiques qui relient les caractéristiques de l'émission des contaminants et leur dispersion dans l'air aux concentrations qui en résultent. La mise en œuvre de ces modèles est rapide, moins coûteuse que l’échantillonnage de l’air, et particulièrement indiquée pour les évaluations d'expositions passées et/ou futures. Les estimations de ces modèles, quoique généralement satisfaisantes, peuvent être, dans certains cas, biaisées du fait des incertitudes associées à l’estimation des paramètres d'entrée, notamment, le taux d'émission des contaminants, qui peut être particulièrement difficile à estimer. Objectifs : L’objectif principal de cette thèse était de proposer des améliorations aux modèles physico-chimiques utilisés en hygiène du travail afin de permettre des estimations plus fiables des concentrations de solvants dans l’air des milieux de travail. Trois objectifs spécifiques étaient définis pour l’étude : (1) effectuer une revue critique de la littérature existante sur le modèle à deux compartiments ; (2) améliorer l’estimation du taux d’émission des contaminants en situations de petits déversements de solvants organiques purs ou de mélanges idéaux de solvants ; (3) améliorer l’estimation du taux d’émission des contaminants en situations de petits déversements de mélanges non-idéaux de solvants organiques. Méthodes : Pour le premier objectif, une revue documentaire des publications scientifiques ayant utilisé le modèle à deux compartiments pour évaluer l'exposition aux vapeurs de solvants a été effectuée. Les données d’exposition (scénarios, solvants, conditions d’études), de modélisation (paramètres d’entrée, résultats) et d’évaluation des performances prédictives du modèle ont été compilées et analysées afin d’identifier les forces et les facteurs potentiels d’amélioration du modèle. Pour le deuxième objectif, trois équations d’estimation des constantes de taux d'évaporation de contaminants alphas (α) ont été développées, en se basant sur des modèles de régression statistiques mettant en relation des alphas expérimentaux mesurés pour cinq solvants purs lors de 183 tests d’évaporation simulant des petits déversements de solvants, et divers déterminants de alpha étudiés. La capacité prédictive des trois équations a été évaluée en comparant les alphas estimés avec des données expérimentales internes et externes à l’étude. Pour le troisième objectif, deux équations dérivées de la Loi de Raoult ont été proposées pour estimer les constantes de taux d'évaporation alphas lors de petits déversements de 12 mélanges aqueux binaires non-idéaux de solvants, en corrigeant ou non, pour la non-idéalité des mélanges. Les concentrations atmosphériques de contaminants, corrigées ou non, ont été prédites à l’aide d’un modèle de petit déversement proposé par le logiciel IHMOD. La qualité des estimations du modèle a été évaluée en comparant, graphiquement et numériquement, les concentrations prédites corrigées ou non, avec des mesures de concentrations réelles. Résultats : Pour le premier objectif, la revue de littérature a démontré l’efficacité du modèle à deux compartiments pour l’évaluation des expositions chimiques sur la base de ses performances de prédiction qui étaient globalement dans un facteur de 0,3 à 3,7 fois les concentrations réelles avec 93 % des valeurs comprises entre 0,5 et 2. Le modèle surestimait les concentrations réelles dans 63 % des évaluations, ce qui témoigne de son utilité à faire prendre, généralement, des décisions conservatrices au profit des travailleurs. L’estimation adéquate des paramètres d’entrée, notamment, du taux d’émission des contaminants, et l’inclusion d’autres facteurs influents tels que la géométrie de la source d’émission, le type et la position du système de ventilation, la présence et l’orientation du travailleur dans une pièce, ont été identifiés parmi les points majeurs d’amélioration du modèle. Pour le deuxième objectif, les alphas expérimentaux mesurés pour les cinq solvants purs variaient entre 0,002 et 0,448 min-1 avec une moyenne de 0,076 min-1. Les principaux déterminants de alpha identifiés étaient la pression de vapeur du solvant, le volume de solvant déversé, la surface de déversement, le ratio de surface de déversement/volume de déversement, la vitesse d’air au-dessus du déversement et la forme du récipient de déversement. Les trois équations développées dans notre étude ont prédit les alphas expérimentaux externes avec un degré élevé d'exactitude et de précision. Les pourcentages moyens d'erreur étaient de –32,9, –32,0 et –25,5 %, respectivement, avec des écarts-types associés aux pourcentages moyens d'erreur de 17,7, 33,3 et 26,0 %, respectivement, et des R2 de 0,92, 0,65 et 0,87, respectivement. Pour le troisième objectif, concernant l’évaluation des mélanges de solvants, les alphas estimés corrigés pour la non-idéalité des mélanges (médiane = 0,0318 min-1) étaient supérieurs à ceux non corrigés (médiane = 0,00632 min-1). Les concentrations modélisées en utilisant les alphas corrigés concordaient raisonnablement avec les concentrations mesurées, avec un ratio médian des concentrations maximales prédites/mesurées de 0,92 (0,81 à 1,32) et une différence médiane entre les temps d’atteinte des concentrations maximales prédites et mesurées de –5 min. Sans correction pour la non-idéalité, le ratio médian des concentrations maximales prédites/mesurées était de 0,31 (0,08 à 0,75) et la différence médiane entre les temps d’atteinte des concentrations maximales prédites et mesurées était de +33 min, ce qui démontre l’importance de considérer la non-idéalité des mélanges lors du processus d’estimation des expositions aux mélanges non-idéaux de solvants. Conclusion : Cette thèse a permis de développer une base de données de scénarios d'exposition et de valeurs des paramètres d'entrée du modèle à deux compartiments, de même que, des équations pratiques et performantes pour estimer des taux d’émission de contaminants en situations de petits déversements de solvants purs ou de mélanges de solvants. En cela, nos résultats constituent un renforcement quantitatif et qualitatif des outils de modélisation existants et une avancée dans l'amélioration des modèles physico-chimiques utilisés en hygiène du travail pour estimer les expositions chimiques. / Context : Physico-chemical models are increasingly used in occupational hygiene to estimate airborne contaminant concentrations. They predict exposure concentrations through mathematical equations that relate the characteristics of the contaminants’ mass emission and their dispersion in the air to the resulting concentrations. These models are quick to use, low cost, and exclusively indicated for past and/or future exposure assessments. Their estimates have been shown to be, generally, in a good agreement with actual air contaminant concentrations. But, sometimes, these models’ outcomes can be substantially biased due to the uncertainty associated with the estimation of the input parameters, notably, the contaminant mass emission rate, which can be particularly challenging to estimate. Objectives : The main objective of this thesis was to propose some improvements to the physico-chemical models used in occupational hygiene in order to allow for more reliable estimates of solvents’ concentrations in the air of the workplaces. Three specific objectives were defined for the study : (1) to perform a critical review of the existing literature on the two-zone model; (2) to improve the estimation of the contaminants’ mass emission rate in exposure scenarios involving small spills of pure organic solvents or ideal solvent mixtures; (3) to improve the estimation of the contaminants’ mass emission rate in exposure scenarios involving small spills of non-ideal organic solvent mixtures. Methods : For the first objective, a literature review based on scientific publications that used the two-zone model to assess exposures to solvent vapours was performed. Data on the exposures (scenarios, solvents, study conditions), the modeling processes (input parameters, results) and on the predictive performance of the model were compiled and analyzed to identify the strengths and the potential areas for the improvement of the model. For the second objective, three equations for estimating the contaminants evaporation rate constants alphas (α) were developed, based on statistical regression models, relating experimental alphas measured for five pure organic solvents during 183 evaporation tests simulating small spills of solvents, and various determinants of alpha. The predictive ability of the three equations was assessed by comparing the estimated alphas with both internal and external experimental measured alphas. For the third objective, two equations derived from Raoult's Law were proposed to estimate the contaminants evaporation rate constants alphas during small spills of 12 non-ideal binary aqueous mixtures, correcting or not for the non-ideality of the mixtures. Corrected and non-corrected air contaminants concentrations were predicted using a small spill model proposed by the IHMOD modeling tool. The quality of the model estimates was assessed by comparing, graphically and numerically, the corrected and non-corrected predicted contaminants concentrations to measured contaminants concentrations. Results : For the first objective, the literature review demonstrated the effectiveness of the two-zone model for assessing chemical exposures based on its predictive performance which was globally within a factor of 0.3 to 3.7 times the actual concentrations, with 93 % of the values being between 0.5 and 2. The model overestimated the actual concentrations in 63 % of the evaluations, which underlines the usefulness of the model for, generally, leading to make conservative decisions that would be beneficial to the workers. The adequate estimation of input parameters, notably, the contaminant mass emission rate, and inclusion of other influential factors such as the geometry of the emission source, the type and position of the ventilation system, the presence and orientation of a worker in a room were the major avenues identified for the improvement of the model. For the second objective, the measured experimental alpha values varied from 0.002 to 0.448 min-1 with an average value of 0.076 min-1. The main determinants identified for alpha were the vapor pressure of the solvent, the spill volume, the spill surface area, the spill surface area-to-spill volume ratio, the air speed above the spill, and the shape of the spill container. The three equations developed in our study predicted the external experimental alphas with a high degree of accuracy and precision. The mean percentages of error were –32.9, –32.0 and –25.5 %, respectively, with associated standard deviations of the percentages of error of 17.7, 33.3 and 26.0 %, respectively, and associated R2 of 0.92, 0.65 and 0.87, respectively. For the third objective, regarding the evaluations of the solvent mixtures, the estimated alpha values which were corrected for the non-ideality of the mixtures (median = 0.0318 min-1) were higher than those which were not corrected (median = 0.00632 min-1). Modeled concentrations using the corrected alphas reasonably agreed with measured concentrations, with a median predicted peak concentrations-to-measured peak concentrations ratio of 0.92 (0.81 to 1.32) and a median difference between the predicted and the measured peak times of –5 min. Without correction for non-ideality, the median predicted peak concentrations-to-measured peak concentrations ratio was 0.31 (0.08 to 0.75) and the median difference between the predicted and the measured peak times was +33 min, which demonstrates the importance of accounting for the non-ideality effect during the process of estimating exposures related to non-ideal solvent mixtures. Conclusion : In this thesis, we developed a database of exposure scenarios and values for the input parameters of the two-zone model, as well as, new practical and efficiently robust equations for estimating contaminants’ mass emission rates in exposure scenarios involving small spills of pure and mixed volatile liquids. Our results constitute a quantitative and qualitative reinforcement of the existing modeling tools and a step further in the improvement of the physico-chemical models used in occupational hygiene to estimate chemical exposure levels.