Cette étude vise à mieux comprendre les réactions impliquées dans le craquage thermique des huiles en basins sédimentaires. Des pyrolyses d'octane, de toluène et de mélanges octane/toluène ont été effectuées entre 330°C et 450°C et des pressions allant de 1 bar à 700 bar. Le mécanisme radicalaire développé permet de rendre compte de l’influence de la température et de la pression sur la distribution des produits ainsi que sur la conversion jusqu'aux conditions de gisement (200°C, 150-1000 bar). Les pyrolyses du toluène pur et du mélange octane/toluène ont permis de modéliser le rôle inhibiteur des alkylaromatiques sur le craquage des hydrocarbures. Cette étude démontre l'importance des co réactions et donc de la composition des huiles sur la stabilité thermique des pétroles en gisements / This study aims at a better understanding of the reactions involved in the thermal cracking of oil within sedimentary basins. Pyrolysis of octane, toluene and mixtures of octane / toluene were performed between 330°C and 450°C and at pressures going from 1 bar to 700 bar. The constructed radical mechanism allows to report the influence of temperature and pressure on the distribution of products as well as the conversion from laboratory to reservoir conditions (200°C, 150-1000 bar). The pyrolysis of pure toluene and the octane / toluene mixture allowed to model the inhibition effect of alkylaromatics on the cracking of hydrocarbons. This study demonstrates the importance of co reactions and thus the composition of oil on the thermal stability of petroleums in reservoirs

Marine aerosols have attracted increasing attention over the past 15 years because of their potential significance for global climate modelling. The size distribution of these aerosols extends from super-micrometer sea salt mode particles down through 150 nm accumulation mode particles, 40 nm Aitken mode particles and nucleation mode particles which extend from 25 nm right down to clusters of a few molecules. The process by which the submicrometer modes form and grow and their composition have remained topics of debate throughout this time in large part because of the difficulties associated with determining their composition and relating it to proposed models of the formation process. The work compared the modality of marine aerosol influencing the South-east-Queensland region with that of other environmental aerosols in the region. The aerosol was found to be consistent with marine aerosols observed elsewhere with concentrations below 1000 cm-3 and frequently exhibiting the distinct bimodal structure associated with cloud processing, consisting of an Aitken mode at approximately 40 nm, an accumulation mode in the range 100-200 nm and a coarse mode attributed to sea salt between 600 and 1200 nm. This work included the development of two new techniques for aerosol research. The first technique measures aerosol density using a combination of aerosol size distribution and gravimetric mass concentration measurements. This technique was used to measure the density of a number of submicrometer aerosols including laboratory generated NaCl aerosol and ambient aerosol. The densities for the laboratory generated aerosols were found to be similar to those for the bulk materials used to produce them. The technique, extended to super-micrometer particle size range may find application in ambient aerosol research where it could be used to discriminate between periods when the aerosol is dominated by NaCl and periods when the density is more representative of crustal material or sulfates. The technique may also prove useful in laboratory or industrial settings for investigating particle density or in case where the composition is known, morphology and porosity. The second technique developed, integrates the existing physicochemical techniques of volatilisation and hygroscopic growth analysis to investigate particle composition in terms of both the volatilisation temperatures of the chemical constituents and their contribution to particle hygroscopic behaviour. The resulting volatilisation and humidification tandem differential mobility analyser or VH-TDMA, has proven to be a valuable research tool which is being used in ongoing research. Findings of investigations relating the composition of the submicrometer marine aerosol modes to candidate models for their formation are presented. Sea salt was not found in the numerically dominant particle type in coastal nucleation mode or marine Aitken and accumulation modes examined on the Southeast Queensland coast during periods where back trajectories indicated marine origin. The work suggests that all three submicrometer modes contain the same four volatile chemical species and an insoluble non-volatile residue. The volatility and hygroscopic behaviours of the particles are consistent with a composition consisting of a core composed of sulfuric acid, ammonium sulfate and an iodine oxide coated with a volatile organic compound. The volume fraction of the sulfuric acid like species in the particles shows a strong dependence on particle size.

This thesis focuses on the synthesis and characterisation of organoclays. X-ray diffraction has been used to study the changes in the basal spacings of montmorillonite clay and surfactant-intercalated organoclays. Variation in the d-spacing was found to be a step function of the surfactant concentration. Three different molecular environments for surfactant octadecyltrimethylammonium bromide (ODTMA) within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. High-resolution thermogravimetric analysis (HRTG) shows that the thermal decomposition of montmorillonite modified with ODTMA takes place in four steps attributing to dehydration of adsorbed water, dehydration of water hydrating metal cations, loss of surfactant and the loss of OH units respectively. In addition, it has shown that the decomposition procedure of DODMA and TOMA modified clays are very different from that of ODTMA modified ones. The surfactant decomposition takes place in several steps in the DODMA and TOMA modified clays while for ODTMA modified clays, it shows only one step for the decomposition of surfactant. Also TG was proved to be a useful tool to estimate the amount of surfactant within the organoclays. A model is proposed in which, up to 0.4 CEC, a surfactant monolayer is formed between the montmorillonite clay layers; up to 0.8 CEC, a lateral-bilayer arrangement is formed; and above 1.5 CEC, a pseudotrimolecular layer is formed, with excess surfactant adsorbed on the clay surface. While for dimethyldioctadecylammonium bromide (DODMA) and trioctadecylmethylammonium bromide (TOMA) modified clays, since the larger sizes of the surfactants, some layers of montmorillonite are kept unaltered because of steric effects. The configurations of surfactant within these organoclays usually take paraffin type layers. Thermal analysis also provides an indication of the thermal stability of the organoclay as shown by different starting decomposition temperatures. FTIR was used as a guide to determine the phase state of the organoclay interlayers as determined from the CH asymmetric stretching vibration of the surfactants to provide more information on surfactant configurations. It was used to study the changes in the spectra of the surfactant ODTMA upon intercalation into a sodium montmorillonite. Surfaces of montmorillonites were modified using ultrasonic and hydrothermal methods through the intercalation and adsorption of the cationic surfactant ODTMA. Changes in the surfaces and structure were characterized using electron microscopy. The ultrasonic preparation method results in a higher surfactant concentration within the montmorillonite interlayer when compared with that from the hydrothermal method. Both XRD patterns and TEM images demonstrate that SWy-2-Namontmorillonite contains superlayers. TEM images of organoclays prepared at high surfactant concentrations show alternate basal spacings between neighboring layers. SEM images show that modification with surfactant will reduce the clay particle aggregation. Organoclays prepared at low surfactant concentration display curved flakes, whereas they become flat with increasing intercalated surfactant. Fundamentally this thesis has increased the knowledge base of the structural and morphological properties of organo-montmorillonite clays. The configurations of surfactant in the organoclays have been further investigated and three different molecular environments for surfactant ODTMA within the surface-modified montmorillonite are proposed upon the basis of their different decomposition temperatures. Changes in the spectra of the surfactant upon intercalation into clay have been investigated in details. Novel surfactant-modified montmorillonite results in the formation of new nanophases with the potential for the removal of organic contaminants from aqueous media and for the removal of hydrocarbon spills on roads.