The intent of this research is to identify a simple diagnostic test to detect abnormal calciuresis and predict calcium oxalate (CaOx) urolith presence in Miniature Schnauzers. We investigated the impact of postprandial time on the specificity of urine calcium:creatine (UCa/Cr) in identifying affected dogs. The hypotheses were: 1) Significant differences exist in fasted and postprandial UCa/Cr between urolith-forming and control schnauzers. 2) UCa/Cr increases significantly from fasted baseline at one or more postprandial time point(s). Urine samples were collected from Miniature Schnauzers with (urolith-formers) and without (controls) CaOx uroliths in a fasted state and 1, 2, 4, and 8 hours after feeding a standardized diet. The change in UCa/Cr from baseline was calculated for each postprandial time. Urolithiasis status and the time point were assessed for impact on the UCa/Cr and change in UCa/Cr using a mixed model ANOVA. Based on 9 urolith-forming and 15 control dogs enrolled, urolith-forming Miniature Schnauzers have significantly higher mean UCa/Cr at 1 hour and 8 hours postprandial timepoints indicating altered calciuresis. The change in UCa/Cr was not significant at any post-prandial time point between or within groups. This pilot study shows male urolith-forming Miniature Schnauzers have excessive calciuresis throughout the day, providing insight into the mechanism behind their formation of CaOx uroliths. If using the Ca/Cr ratio, the postprandial sampling time is not critical. This simple urine measurement has potential as a marker of urolith presence and possibly risk of urolith formation. / Master of Science

Résumé confidentiel / Résumé confidentiel

Les oxydes mixtes d'uranium et de plutonium sont les matières premières privilégiées des combustibles nucléaires de nouvelles générations. Les mécanismes de leur élaboration par décomposition thermique d'oxalates mixtes, précurseurs de référence, font l'objet des présentes recherches, en vue d'une maîtrise plus aboutie des caractéristiques physico-chimiques du solide produit. La décomposition thermique de différents précurseurs oxalates en oxydes a donc été analysée expérimentalement sous atmosphères inerte et oxydante, les processus réactionnels ont été clarifiés, les paramètres thermodynamiques et cinétiques déterminés et des modèles physico-chimiques prédictifs ont été proposés. La méthodologie d'étude expérimentale de ce processus jusqu'à sa modélisation a tout d'abord été développée à l'aide de composés modèles à base de lanthanides, de complexité croissante. La conversion en oxyde des oxalates simples de Nd et Ce, comparée à celle de l'oxalate de Pu(III), a permis de cerner l'effet du redox du métal. Des oxalates doubles lanthanide-hydrazinium, par un comportement spécifique dû à leur structure cristallographique singulière, ont ensuite illustré de manière exacerbée l'importance des interactions gaz-gaz et solide-gaz en présence notamment de gaz réactifs azotés. La résolution globale des mécanismes de décomposition des oxalates mixtes d'actinides en oxydes a bénéficié ensuite d'une approche comparative des systèmes U-Ce, Th-Pu et U-Pu, compte tenu d'analogies structurales ciblées. Un mécanisme général en cinq étapes élémentaires principales a été proposé, associé à des données thermodynamiques et cinétiques. Ceci a notamment permis de simuler les diagrammes de spéciation de la phase solide suivant différentes programmations de température (linéaire ou de type double-four industriel), aussi bien pour le système simulant U-Ce utilisé dans les essais systématiques d'optimisation technologique du procédé que pour le système d'intérêt U-Pu. Enfin, une première ébauche de modèle « procédé » a été réalisée en considérant les phénomènes de transport associé à deux réactions-clés pour ces systèmes : l'étape de décomposition thermique de l'oxalate anhydre en oxyde et l'équilibre de Boudouard entre gaz carbonés. La réactivité du système et les phénomènes prépondérants concernant les flux de gaz de calcination dégagés et la formation de carbone élémentaire au sein d'un lit de poudre statique ont pu être simulés globalement / Mixed uranium-plutonium oxides are preferential raw materials for news generation nuclear fuels. The research project presented herein deals with their elaboration process by thermal decomposition of mixed oxalates, as reference precursors, in order to improve the physicochemical characteristics of the resulting product. The thermal decomposition of several oxalate precursors into oxides was thus experimentally studied under both inert and oxidizing atmospheres, the reaction mechanisms were determined, as well as the thermodynamics and kinetics, and predictive physicochemical models were proposed. The methodology of the study up to the modelling was first developed using lanthanide model compounds with increasing complexity. The conversion into oxides of simple Nd and Ce oxalates, compared with Pu(III) oxalate, allowed to understand the role of the metal cation redox properties. Double lanthanide-hydrazinium oxalates, displaying a specific behaviour due to their peculiar crystallographic structure, underlined the importance of gas-gas and solid-gas interactions. Then, the global resolution of the decomposition mechanisms of mixed actinide oxalates into oxides was carried out through a comparative approach of U-Ce, Th-Pu and U-Pu systems, given ... analogies. A general mechanism including five main steps was proposed, with the corresponding thermodynamic and kinetic parameters. This especially enabled to simulate the speciation diagrams of the solid phases according to different temperature programs (linear or double industrial oven) for the U-Ce surrogate system (used in systematic technological process optimisation tests) as well as for the U-Pu system of interest. Finally, a first attempt at process modelling was undertaken, taking into account transport phenomena associated with two key-reactions for these systems: the thermal decomposition of anhydrous oxalate into oxide and the Boudouard equilibrium between carbonaceous species. The overall system reactivity and the predominant phenomena concerning evolved gas fluxes and elemental carbon formation, within a static powder bed, were simulated

This thesis describes the convenient routes and the preparation conditions (temperature, oxygen partial presssure) which lead to the formation of single phase materials within the quaternary system Cu-Ni-Fe-O. The investigated compositions are the solid solutions CuxNi1-xFe2O4, the ferrites occurring in the phase triangle Cu0.5Ni0.5Fe2O4 -Cu0.9Fe2.1O4 - Cu0.5Fe2.5O4 and some copper-nickel oxide solid solutions. Three synthesis routes have been used, namely (i) the preparation and the thermal decomposition of freeze-dried carboxylate precursors, (ii) the preparation and the oxidation of intermetallic phases and (iii) the preparation and the heat treatment in air of mixed oxide/metallic powders. The thermal decomposition of freeze-dried Cu-Ni-Fe formate has been found as a suitable method for preparing single spinel phases within the Cu-Ni-Fe-O system. In comparison with the conventional solid state reaction, the required temperature is much lower. Concerning the solid solution CuxNi1-xFe2O4 , a single phase spinel is formed at 1000¢XC for x < 0.7; for CuO is identified as second phase. In this latter range the formation of a pure phase required an increase of the iron content in the mixture. The other single spinel phases in the phase triangle Cu0.5Ni0.5Fe2O4 - Cu0.9Fe2.1O4 - Cu0.5Fe2.5O4 have been synthesized under special synthesis p(O2)/T-conditions. For copper ferrites Cu1-xFe2+xO4 with x ?­ 0.1, 0.2, 0.33, 0.4 and 0.5, the change in the conductivity with the temperature is irreversible. The deviation from the linearity of the conductivity ?ã as a function of the temperature occurs due to the thermal history of these samples. The saturation magnetic moment (nB) at 5K, of some synthesized CuxNi1-xFe2O4 compounds has been determined. It has been found that nB increases with the nickel content in the ferrite sample.

Calcium (Ca) is an essential macronutrient that is increasingly recognized as a biogeochemical factor that influences ecosystem structure and function. Progress in understanding the sustainability of ecosystem Ca supply has been hampered by a lack of information on the various forms and pools of Ca in forest ecosystems. In particular, few studies have investigated the role of Ca-oxalate (Ca-ox), a ubiquitous and sparingly soluble biomineral formed by plants and fungi, on Ca cycling. I investigated Ca-ox pools in two young Douglas-fir forests in the Oregon Coast Range, and found that Ca-ox comprised 4 to 18% of total ecosystem Ca in high- and low-Ca sites, respectively, with roughly even distribution in vegetation, detritus and mineral soil to 1 m depth. The proportion of ecosystem Ca existing as Ca-ox varied by ecosystem compartment but was highest in needle litterfall, foliage and branches. Calcium-ox could be a large amount of Ca in mineral soil; across nine sites comprising a local soil Ca gradient, we found as much as 20% of available Ca in 0 - 10 cm depth mineral soil occurs as Ca-ox. Ca-ox was the dominant form of Ca returned from plants to soil, but disappeared as rapidly as bulk Ca from decomposing litter, suggesting an important pathway for Ca recycling. In mineral soil, Ca-ox was a larger portion of total available Ca in the low-Ca site, which had lower Ca-ox concentrations overall, suggesting that Ca-ox has limited potential to buffer against Ca depletion in forests where Ca is in shortest supply. I investigated foliar chemistry as a method for diagnosis of nutrient deficiencies in high and low-Ca sites where Ca varied inversely with soil nitrogen (N), and which had received fertilization with urea (for nitrogen, N), lime, and calcium chloride three years prior. Foliar vector diagrams suggested N limitation at the low-N site and N sufficiency at the high-N site, but did not suggest Ca deficiency at either site after urea, lime and Ca-chloride fertilization. The high-Ca site displayed 20-60 times higher concentrations of foliar Ca-oxalate than the low-Ca site, although this was unaffected by fertilization. Soil nitrification responded to both N and lime fertilization at both sites, suggesting that fertilization with N may stimulate nitrification that could accelerate soil Ca loss. I also investigated how Ca-ox may influence cation tracers such as Ca and strontium (Sr) ratios (i.e., Ca/Sr) and Ca-isotopes (⁴⁴Ca/⁴⁰Ca), which are used to identify sources and pathways of Ca cycling in ecosystem studies. Laboratory synthesis of Ca-ox crystals exhibited preference for Ca over Sr, and for ⁴⁰Ca over ⁴⁴Ca. In the field, discrimination between Ca and Sr was detected in bulk plant tissues due to Ca-ox accumulation, suggesting that Ca-ox accumulation related to tree Ca supply status could influence interpretations of Ca/Sr as a tracer of Ca cycling. I also found that standard methods of soil exchangeable Ca extraction could dissolve Ca-ox crystals and potentially contribute an additional 52% to standard measurements of exchangeable-Ca pools in low-Ca sites, thus complicating long-standing interpretations of available soil Ca pools and dynamics in many studies. Results of this work show overall that Ca-ox is found in large quantities in plants, detritus, and mineral soil in forest ecosystems, and is a more dynamic component of ecosystem Ca cycling than previously recognized. / Graduation date: 2012

Aquaculture production is increasing annualy and wild fisheries for fishmeal production remain stagnant. As a consequence, extensive research has been deployed to reduce dietary fishmeal inclusion in feeds of farmed species. Usage of alternative protein sources derived from plants continues to increase with the most popular sources being oilseeds, legumes and cereal grains. The downside of these sources is that most of them could directly be used for human consumption arising legitimate criticism from voices referring to countries where protein shortages lead to malnutrition among the population. Jatropha curcas is a tropical oilseed with upcoming popularity for sustainable fuel sourcing. The plant is thought to thrive in semi-arid and arid areas, not just producing oil, but at the same time reclaiming previously eroded land for the local population. For these reasons, annual cultivation of Jatropha curcas is thought to rise over the next decades. After oil is extracted from the seed, the remaining press cake, is currently used as a fertilizer or energy source. This is mostly due to toxic phorbol esters that until recent- ly limited any nutritional applications. In 2011, a method to detoxify Jatropha press cake was developed and paved the way for nutritional research on the resulting detoxified Jatropha curcas kernel meal (JKM) to be launched. JKM offers very high protein content with a balanced amino acid composition suggesting opportunities for usage as a feedstuff in aquaculture diets. JKM further has higher mineral content than comparable oilseeds. However, potential anti-nutritional factors (ANFs) present in the meal could lead to impairment of nutrient availability or other adverse effects. Previous research has already started to evaluate JKM as a protein source for a variety of aquaculture species. This thesis attempts to further identify the potential of JKM as a protein source and assess the effects of JKM on the development of two model cultured teleost species, common carp (Cyprinus carpio) and Nile tilapia (Oreochromis niloticus), as they represent two of the most farmed species, particularly in the tropics. The work comprises growth trials on both species using fishmeal as a subject of replacement in solely fishmeal protein-based diets and on more practical fishmeal/plant protein-based diets. It engages with the effects of phytate, a prominent component of JKM with potential anti-nutritional attributes and commercially available phytase feed supplements to diminish these attributes, as well as oxalate, another plant-specific component with high concentrations in JKM and with limited attention in aquaculture nutrition research. Carp and tilapia showed varying results with different inclusion levels of JKM. For carp 50% fishmeal replacement was possible without losses in growth in diets where fishmeal was the only bulk protein source (Chapter 3.1), Tilapia showed slightly worse growth at a 30% replacement level (Chapter 3.2). A steep decline in growth could be observed when replacing 100% fishmeal with JKM in carp (Chapter 3.1), while tilapia showed no difference at that level compared to 30% replacement (Chapter 3.2). In practical diets, 100% of fishmeal could be replaced by JKM without any adverse effects on growth of carp (Chapter 3.3), while tilapia showed a slight, but significant linear negative correlation with higher inclusion levels of JKM (Chapter 3.4). Phytase addition in tilapia feeds was identified as having no obvious impact on growth in JKM based diets where enough available phosphorus was provided through mineral supplementation (Chapter 4.1). In JKM based diets where available phosphate was not added, phytase addition showed a tendency to increase growth and significantly increased mineral retention and decreased phosphorus effluent contamination (Chapter 4.2). Phytase application through pre-incubating JKM along with citric acid exerted a positive effect of growth on carp when fishmeal protein was replaced by 50% (Chapter 3.1). Phytase was further shown to completely hydrolyze phytate in vitro; however, incomplete hydrolysis was observed in vivo in tilapia (Chapter 4.3). Dietary soluble oxalate added to fishmeal based diets for carp showed better growth parameters, nutrient and mineral retention at inclusion levels 1.5% and higher (Chapter 5.1). For tilapia, a trial could demonstrate adverse effects of oxalate on potassium, calcium, manganese and zinc digestibilities, in this case without negative effects on growth (Chapter 5.2). For both, carp and tilapia, an impact of oxalate on lipid metabolism was evident, lowering body lipid content and blood cholesterol in inclusion levels from 1.5% or higher. JKM can become a valuable alternative to present dietary protein sources in aquaculture feeds. The nutritional attributes of JKM need further research, especially longer-term testing in a commercial scenario and application in commercially produced feeds. Results of this thesis pose a useful addition to previous research and can be referred to for realizing these next steps.

Foi sintetizada e caracterizada a spiro-ciclopentil-1,2-dioxetanona, um derivado de 1,2-dioxetanona inédito, de forma a se contribuir com informações acerca da quimiluminescência de peróxidos orgânicos. Estudos mecanísticos da decomposição quimiluminescente de 1,2-dioxetanonas são escassos, principalmente quando comparados à enorme quantidade de resultados existentes sobre a formação de estados excitados na decomposição de 1,2-dioxetanos. A spiro-ciclopentil-1,2-dioxetanona foi preparada pela ciclização do 1-carbóxi-1- hidroperóxiciclopentano com N,N-diciclohexilcarbodiimida, com rendimento de 1,2%, e caracterizada por RMN de 1H e 13C a baixa temperatura e pelo comportamento cromatográfico da solução peroxídica. Evidências para a ocorrência do mecanismo de Luminescência Iniciada Quimicamente por Troca de Elétron (CIEEL) na formação de estados excitados, na sua variante intermolecular, foram obtidas por estudos cinéticos da decomposição quimiluminescente dessa 1,2-dioxetanona por diferentes ativadores (ACTs). Entretanto, a decomposição desse peróxido ocorre com rendimentos de formação de estados excitados singlete baixos (ΦS≈ 10-4 E mol-1), indicando que essa 1,2-dioxetanona também possui baixa eficiência de formação de estados excitados, conforme constatado recentemente para outros derivados. Foram encontradas evidências para a ocorrência de uma transferência de elétron na etapa limitante de velocidade, onde o ACT é formado no estado excitado, com um coeficiente de transferência de elétron de α = 0,19. Ainda, foi observada uma correlação entre a energia livre liberada para a formação de estados excitados e os rendimentos quânticos, nos moldes do mecanismo CIEEL. De acordo com os resultados obtidos nesse trabalho e em trabalhos anteriores, postula-se que o tamanho do substituinte alquílico no anel da 1,2-dioxetanona causa um efeito drástico na eficiência da decomposição catalisada do peróxido na seqüência CIEEL, diminuindo o valor da constante de equilíbrio para a formação inicial do complexo de transferência de carga Em uma segunda parte do trabalho, foi averiguado o mecanismo da reação peróxi-oxalato em meios aquosos, uma vez que a maioria dos trabalhos sobre esta transformação nestes meios possui ênfase na aplicação analítica. Foi observado que as reações dos oxalatos de bis(2,4,6-triclorofenila) (TCPO), moderadamente reativo, e bis(2,4-dinitrofenila) (DNPO), altamente reativo, com H2O2 e catálise por imidazol, ocorrem pelo mesmo mecanismo, em 1,2-dimetoxietano e em misturas aquosas desse solvente. Para TCPO, observou-se que há a formação de um intermediário de catálise nucleofílica, previamente ao ataque nucleofílico do H2O2. Para DNPO, há uma adição nucleofílica direta do H2O2 ao éster, com e sem catálise básica por imidazol. Em meios aquosos, a hidrólise do éster oxálico ocorre paralelamente à peridrólise, que leva à emissão de luz. Entretanto, as constantes de velocidade para a peridrólise do éster são significativamente maiores do que as para a sua hidrólise. Observou-se que a reação de TCPO com H2O2 em meios orgânico e aquoso, catalisada por 2,6-lutidina (2,6-dimetilpiridina), ocorre com essa base agindo como um catalisador não-nucleofílico. Por último, estudou-se a reação de TCPO com H2O2 em tampão carbonato de potássio, um meio essencialmente aquoso, onde a espécie reativa é a base conjugada do H2O2; entretanto, a constante de velocidade da peridrólise se mostrou similar à de hidrólise do éster oxálico. Nessa última parte do trabalho, foi demonstrado que a reação peróxi-oxalato também pode ser conduzida em meios aquosos. / Spiro-cyclopentyl-1,2-dioxetanone, a new 1,2-dioxetanone derivate, was synthesized and characterized, in order to contribute to the present mechanistic knowledge on organic peroxide chemiluminescence. Mechanistic studies on the chemiluminescent 1,2-dioxetanone decomposition are highly limited, especially when compared to the huge amount of data available for 1,2-dioxetanes. The spiro-cyclopentyl-1,2-dioxetanone was prepared by 1-carboxy-1-hydroperoxycyclopentane cyclization with N,N-dicyclohexylcarbodiimide, in a 1.2% yield and characterized by low temperature 1H and 13C NMR and the chromatographic behavior of the peroxide solution. Evidence for the occurrence of the Chemically Initiated Electron Exchange Luminescence (CIEEL) mechanism for excited states formation, in its intermolecular version, was obtained from kinetic studies of the chemiluminescent decomposition of this 1,2-dioxetanone with different activators (ACTs). However, the decomposition of this peroxide occurs with low yields of singlet excited state formation (ΦS≈ 10-4 E mol-1), showing that also this 1,2-dioxetanone possesses low excitation efficiency, as recently found for other derivatives. Evidence was found for the occurrence of an electron transfer in the rate limiting step, where the ACT is formed in its electronically excited state, with an electron transfer coefficient α= 0.19. Moreover, a correlation between the free energy released upon excited states formation and the quantum yields is observed, in agreement with the CIEEL mechanism. The results obtained in the present work together with previous data, allow to postulate that the size of the alkyl substituent on the 1,2-dioxetanone ring plays a crucial role for the efficiency of the catalyzed peroxide decomposition in the CIEEL sequence, by lowering the equilibrium constant for initial charge transfer complex formation. In a second part of this work, the mechanism of the peroxyoxalate reaction in aqueous media was studied, due to the fact that most of recent work on this system is mainly concerned only to analytical application aspects. The reaction of the moderately reactive bis(2,4,6-trichlorophenyl) (TCPO) and the highly reactive bis(2,4- dinitrophenyl) oxalate (DNPO) with H2O2 and imidazol catalysis, showed to occur by the same mechanism, in 1,2-dimethoxyethane as well as in its aqueous mixtures. For TCPO, the formation of an intermediate due to nucleophilic catalysis by imidazole was observed, preceding the H2O2 nucleophilic attack. For DNPO, direct nucleophilic addition of H2O2 to the ester occurs, with and without imidazole catalysis. In aqueous media, oxalic ester hydrolysis also occurs concomitantly to its perhydrolysis, which leads to light emission. However, the rate constants for perhydrolysis are significantly higher than the hydrolysis rate constants. For the reaction of TCPO with H2O2 in organic and aqueous medium, catalyzed by 2,6-lutidine (2,6-dimethylpyridine), it was shown that this base acts as a nonnucleophilic catalyst. Finally, the reaction of TCPO with H2O2 in potassium carbonate buffer, an essentially aqueous media, was studied, where the reactive species is the H2O2 conjugate base; however, the oxalic ester perhydrolysis rate constant proofed to be similar to its hydrolysis rate constant. In this last part it is also shown that the peroxyoxalate reaction can be carried out in aqueous media.

Dans le cadre du programme GenIV, les propriétés physico-chimiques d'intérêts des combustibles envisagés, telles que la durabilité chimique, doivent être évaluées. Ainsi, une étude préliminaire a été entreprise sur les composés modèles MIV1-xLnIIIxO2 (M=Ce,Th) preparés à partir de précurseurs oxalate. La structure fluorine caractéristique des oxydes CeO2 et ThO2 demeure stable jusqu'à x ≈ 0,4, la substitution d'ions MIV par LnIII étant accompagnée par la formation de lacunes en oxygène. Pour des valeurs de x plus importantes, une surstructure cubique est formée suite à l'ordonnancement des lacunes en oxygène. Par la suite, les tests de dissolution réalisés en milieu acide ont montré que la vitesse de dissolution normalisée dépend très fortement de la fraction en élément lanthanide incorporé. A l'opposé, la nature des éléments MIV et LnIII constitutifs du solide ne semble que peu modifier la vitesse de dissolution normalisée. Par ailleurs, les effets de paramètres plus " conventionnels " tels que la température ou la concentration en acide ont également été évalués, et ont permis de conclure à une dissolution contrôlée par des réactions de surface. Parallèlement à cette étude, l'évolution microstructurale de composés pulvérulents et frittés a montré d'importantes modifications de la surface réactive durant la dissolution. A partir des observations par MEBE, les joints de grains et les défauts cristallins sont apparus comme des zones préférentielles de dissolution. Par ailleurs, la formation de phases gélatineuses à la surface des solides, agissant comme une barrière de diffusion et ralentissant ainsi la dissolution du matériau a été démontrée.

Il semble actuellement raisonnable de penser que la notion de réaction simple,c onduisant à un équilibre univariant du type SGn → S' + nG et mettant en jeu deux phases solides pures (SGn et S') et le gaz G. n'est qu'une approximation, justifiable dans le cas de solides qui présentent de faibles écarts à la stoechiométrie. Si l'on se réfère aux hydrates (G = H₂O), il n'est pas rare en effet que la composition chimique de la phase sous-hydratée issue d'une réaction de déshydratation s'écarte largement de la stoechiométrie et varie avec la température et la pression de vapeur d'eau. C'est ainsi, par exemple, que l'oxalate de calcium dihydraté, le sulfate de calcium (forme γ) et l'oxalate de manganèse anhydres, dissolvent des quantités d'eau non négligeables jusqu'à apparition de formes hydratées saturées. Le but de ce travail consacré pour l'essentiel à l'étude des réactions de déshydratation de sels de formules brutes apparentes SGn, est donc d'introduire la non-stoechiométrie dans le diagramme d'état puis au niveau des processus élémentaires de décomposition; par ce biais, nous proposons une interprétation possible au caractère singulier de certaines courbes, traduisant à température constante, les variations de vitesse de décomposition en fonction de la pression du gaz G. Tout écart à la stoechiométrie, en élément G provenant du gaz, d'un solide SGn, se matérialise dans le diagramme d'équilibre pression-température par l'existence d'un domaine divariant ; borner ce domaine, revient à définir la notion de courbe limite de divariance, lieu des points du plan P_G - T de précipitation commençante de nouvelles phases solides.

La méthode quasi-chimique des éléments de structure permet une étude thermodynamique complète des équilibres divariants entre un solide et la vapeur d'eau. Cette méthode inclut comme cas particuliers les modèles déjà existants. Une continuité apparaît entre les différents modes de formulation des équilibres. La principale difficulté pour l'application pratique des relations obtenues est d'exprimer les coefficients d'activité, c'est-à-dire de disposer de modèles de solutions suffisamment complets. Même compte tenu de certaines approximations, la forme des isothermes est reliée à la plus ou moins grande mobilité des molécules d'eau dans le solide. L'expression des coefficients d'activité étant très souvent approchée, nous avons introduit, pour étudier les limites des domaines de divariance, des équilibres limites faisant intervenir ou non la vapeur d'eau. Ces modèles ont été appliqués à l'étude des systèmes divariants : Vapeur d'eau-sulfate de calcium anhydre et vapeur d'eau-oxalate de manganèse anhydre. Nous avons montré que dans ces deux cas les molécules d'eau dissoutes étaient non localisées et donc mobiles dans le solide, sauf toutefois pour les faibles teneurs en eau. Des différences cependant, existent entre ces deux équilibres : Pour le sulfate de calcium, la solution obéit dans un large domaine à la loi de Henry et sa limite inférieure du domaine divariant est la précipitation d'une nouvelle phase, alors que l'équilibre eau-oxalate de manganèse suit une loi de solution strictement régulière et que le domaine divariant est limité par la décomposition de l'oxalate.