The standard enthalpies of formation of phenylphosphonic, phenyl-phosphinic, and diphenylphosphnic acids have been determined by oxygen static bomb calorimetry to be: [equations] These values were compared and combined with the results of solution reaction calorimetry on related compounds and the standard enthalpy of formation of dibromophenylphosphine derived, [equation]. The existing literature on these compounds has been critically reviewed and the significance of bonding in halo-phenylphosphines briefly discussed. The standard enthalpy of formation of tri(p-tolyl) methanol has been determined from the enthalpy of combustion measured by oxygen static bomb calorimetry, [equations] derived for the gas-phase enthalpy of formation increment per p-methyl group.

The work in this thesis shows that it is possible to design a diffusion cell which will allow access to the flux and lag time of a permeant without the need for invasive sampling and that this novel cell is both sensitive and reproducible. It was also shown that the cell could be used in conjunction with both simple model membranes and more complex biological membranes, namely the epidermis. From the data achieved from the cell it was possible to derive a series of equations which allowed access to thermodynamic parameters such as ?H, ?G and ?S. An extension of this calculational approach revealed that manipulation of the van’t Hoff isochore, under the condition where enthalpy is constant over the temperature range, it should be possible to calculate the partition coefficient. Ultimately these parameters can be used in the description of structure activity relationships. The systems described in this thesis are of a complex biological nature consequently the returned data reflect this complexity. In order to utilise the data to their full potential some method for dealing with this complexity was sought. One approach widely discussed in the literature is that of chemometric analysis or soft modelling. Initial studies into the use of chemometric analysis proved positive for the data presented in this thesis, and suggested that formulation contributions from components with close absorbance maxima could be separated.

In binary systems, surfactant molecules can self-assemble into a large variety of structures depending on their chemical structure, concentration and temperature. The properties and stability of the phases, their coexistence regions and the formation of metastable structures is of great importance not only for fundamental understanding, but also for applications in many fields including industry and medicine. This thesis presents studies of the equilibrium and non-equilibrium behaviour of two widely used surfactant systems. The understanding of the equilibrium behaviour of an aqueous surfactant system is often incomplete or partly incorrect, which is caused by experimental difficulties, long equilibration times and the occurrence of long-lived metastable states. By applying a set of complementary techniques and recording changes on different length scales, the equilibrium phase diagram of the surfactant didodecyldimethylammonium bromide (DDAB) in water has been studied and amended. Differential scanning calorimetry has been used to obtain thermodynamic parameters. The structure of phases and biphasic regions have been characterised by small angle X-ray scattering and microscopy, while the conformational properties of the surfactant molecules have been investigated using Raman spectroscopy combined with computational methods. The effects of impurities have been studied using analytical techniques and a sufficient purity of the samples could be ensured. As a result of the studies, a new crystalline phase which exists at temperatures below 16°C was found. This phase replaces the frozen lamellar phase (Lβ) in the previously reported phase diagram. The Lβ phase has been found to be a long-lived metastable phase. The amended phase diagram has been tested by studying phase transitions along isoplethal and isothermal paths. All experimental results could be explained in terms of the new phase diagram. The study of phase transition along isoplethal paths focused on the transition between the new crystalline phase (XWn) coexisting with a dilute monomer solution (W) and the lamellar phase (Lα). This transition was (except for a single composition DDAB≈3% DDAB) a non-isothermal transition involving the phase sequence: XWn +W → XWn + Lα → Lα upon heating and Lα → overcooled Lα → XWn +W upon cooling. The structural changes within the phases and their relative ratios could be characterised using small angle X-ray scattering, microscopy and Raman spectroscopy. During the dissolution of lamellar phases along an isothermal path, multilamellar wormlike interface instabilities (so called myelins) were found to grow from the lamellar/water interface into the water. The growth of these myelins as well as changes in the lamellar phase have been investigated using optical microscopy and direct observation. This has provided detailed quantitative information on the dynamics of myelin growth and the effect of the initial structure of the lamellar phase on the myelin growth. The dependence of the growing rate on surfactant concentration could be explained in terms of a previously reported model in which the osmotic pressure was stated to be the driving force for the myelin kinetics. It has been found that for lamellar phases in coexistence with a sufficient amount of crystals, the myelin growth could be suppressed. Preliminary measurements of a tertiary system, where the pure lamellar phase of DDAB was mixed with a crystalline phase formed by dioctadecyldimethylammonium bromide (DODAB), a DDAB analogue, were carried out. The myelin growth has also been studied for a second system, the non-ionic surfactant triethylene glycol monododecyl ether (C12E3), known for its formation of myelins of great stability. The optical methods were extended to confocal microscopy, resulting in a 3D image of the myelin formation, providing detailed quantitative information on myelin growth as well as on myelin size.

Ce travail de thèse porte sur l’étude d’électrolytes pour utilisation dans des systèmes de stockage énergétiques tels que les batteries lithium-ions. Les matériaux spécifiques à cette étude sont des liquides ioniques à base de pyrrolidinium avec le fluorosulfonylimide (FSI) en tant que contre-ion, le tout dopé au lithium.La méthode de caractérisation principale est la spectroscopie par Résonance Magnétique Nucléaire (RMN) qui peut être utilisée pour résoudre la structure, la dynamique ou encore l’arrangement spatial entre les anions et les cations. Des mesures de diffusion et des expériences de relaxation réseau-spin, utilisant 1H pour les cations, 19F pour les anions et 7Li, sont effectuées pour étudier le transport ionique dans le liquide ainsi que la rotation moléculaire respective des différents ions.Toutefois, dans le but de mieux comprendre le mécanisme de transport des ions à un niveau moléculaire dans ces liquides ioniques, l’expérience Heteronuclear Overhauser Effect SpectroscopY (HOESY) a été employée. Cette technique est basée sur le transfert d’aimantation entre deux isotopes nucléaires dans l’espace. Puisque le transfert est généralement dû à des interactions de courtes portées, des informations concernant les différentes proximités des espèces dans le liquide sont obtenues.Une grande partie de cette étude est concentrée sur le développement de la technique HOESY elle-même, avec l’amélioration de la séquence d’impulsion RMN mais aussi de l’analyse du signal, dans l’optique d’une étude quantitative et du développement d’une procédure automatique et systématique d’ajustement des données théoriques aux données expérimentales. Des simulations par Dynamique Moléculaire (DM) et des mesures de relaxation RMN sont utilisées pour permettre l’analyse des expériences OESY, permettant alors d’accéder à la corrélation des distances entre les noyaux et des paramètres de relaxation tels que les temps de corrélation, pouvant permettre une meilleure compréhension du transport ionique. En plus du développement de cette technique, de nouveaux liquides ioniques incluant des chaînes alkyles plus longues, des cycles plus longs ou encore un groupe ethero-alkyle sur la chaine alkyle sont étudiés par HOESY dans le ut d’observer l’impact de la structure du cation sur les interactions ioniques. Une autre technique complémentaire, la polarisation dynamique nucléaire, est aussi adoptée afin d’étudier les liquides ioniques dans un état vitreux imitant leur structure à l’état liquide. / This work is focused on the study of electrolytes for energy storage devices such as lithium ion batteries. The specific materials are pyrrolidinium-based ionic liquid electrolytes with bis-fluorosulfonylimide (FSI) as the counter anion, and also containing lithium.The main experimental method of characterization is Nuclear Magnetic Resonance (NMR) spectroscopy, which can be used to probe structure, dynamics and spatial arrangements between anions and cations. NMR-based diffusion measurements or spin lattice relaxation experiments, using 1H for cations, 19F for anions and 7Li, are used to study the ionic transport in the liquid and the molecular tumbling of the different ions respectively.However, in order to attempt to better understand the ion transport mechanism at the molecular level in these ionic liquids, the HOESY (Heteronuclear Overhauser Effect SpectroscopY) experiment is used. This technique is based on a transfer of magnetization through space between two different nuclear isotopes. As this transfer is generally mediated by short-range interactions, it provides information on which species are close together in the liquid.A large part of this work is based on the development of the HOESY technique itself, both improving the implementation of the NMR pulse sequence to reduce the experimental time, but also improving ways to analyze the resulting data in a quantitative way and developing an automatic and systematic data fitting procedure. Molecular Dynamics (MD) simulations and NMR relaxation measurements are also used to assist the HOESY analysis, allowing correlations with distances between nuclei and motional parameters such as correlation times to be established, which will lead to a better understanding of the ion interactions. In addition to this technique development, others ionic liquids including longer alkyl, longer cycle or even an ether-o-alkyl group on the alkyl chain, are studied by HOESY in order to observe the impact of the cation structure on the ionic interactions. Another complementary technique, dynamic nuclear polarization, is also used in order to study the ionic liquid in the glassy state structure which mimics the liquid state.

L’apparition de fibres de SiC de haute pureté au cours des années 1990 a permis de considérer leur utilisation dans les réacteurs nucléaires en tant que renfort des composites à matrice SiC, dits composites SiC/SiC. Envisagés en tant que matériau de cœur des réacteurs du futur (SFR, GFR) et en remplacement des gaines en zirconium des réacteurs REP, la compatibilité thermochimique du SiC et des composites SiC/SiC avec l’environnement de tels réacteurs a été examinée. Des traitements thermiques en systèmes ouvert et fermé entre le SiC et l’UO2 ont montré une réactivité marquée au-delà de 1200°C avec la formation principalement de CO et de siliciures d’uranium dans la phase condensée, voire l’apparition d’une phase liquide entre 1500 et 1650°C. L’exposition au sodium liquide à 550°C jusqu’à 2000h a été étudiée en fonction de la concentration en oxygène. Une amélioration des propriétés mécaniques des composites SiC/SiC fabriqués pour cette étude (déformations et contraintes à rupture plus importantes) a été mise en évidence après immersion quelle que soit la concentration en oxygène du sodium liquide. Enfin, les compositions et les cinétiques de croissance des zones de réaction du SiC avec le niobium et le tantale (métaux utilisés pour assurer l’étanchéité d’une gaine en composite SiC/SiC) ont été mesurées entre 1050 et 1500°C. / The development of high purity SiC fibers during the nineties has led to their consideration as nuclear reactors components through the use of SiC/SiC composites. SiC and SiC/SiC composites are considered as core materials of future nuclear reactors (SFR, GFR) and as a potential replacement for the zirconium cladding of PWR. Therefore, the thermochemical compatibility of these materials with typical environments of those nuclear reactors has been studied. The composition and the growth kinetics of the reaction zone of SiC towards niobium and tantalum (considered as materials to ensure the leak-tightness of a SiC/SiC cladding for GFR) have been studied between 1050 and 1500°C. High temperature heat treatments in open and closed systems between SiC and UO2 have shown a significant reactivity over 1200°C characterized by the formation of CO and uranium silicides. Moreover, a liquid phase has been detected between 1500 and 1650°C. The exposure of SiC/SiC to liquid sodium (550°C, up to 2000h) has been studied as a function of the oxygen concentration dissolved in liquid sodium. An improvement of the mechanical properties of the composites elaborated for this study (increase of the tensile strength and strain at failure) has been highlighted after immersion in the liquid sodium independently of its oxygen concentration. It is believed that this phenomenon is due to the presence of residual sodium in the material.

Energetic materials encompass a wide range of chemical compounds all associated with a significant risk of fire and explosion. They include explosives, fireworks, pyrotechnics, powders, propellants and other unsteady chemicals. These materials store a high level of chemical energy and are able to release it rapidly without external contribution of oxygen or any other oxidizer. The behaviour of these materials in case of explosive detonations is relatively wellknown from empirical and practical points of view. However, fundamental scientific questions remain unanswered related to the mechanisms of heat release. The current understanding of these mechanisms lacks appropriate thermochemical characterisation. The aim of the study is the analysis of thermal and chemical characteristics of energetic materials under conditions that exclude detonations. Detonation is excluded in order to better isolate the thermal and chemical mechanisms involved in the burning process. The experimental work has been conducted using the FM Global Fire Propagation Apparatus (FPA) [ASTM E2058‐03]. One of the benefits of using this experimental apparatus rather than the Cone Calorimeter is that it allows controlling the feed of heat and oxidizer to the reaction zone. The material chosen to conduct experiments on is a ternary smoke powder based on a mixture of starch and lactose as fuel components and potassium nitrate as oxidizer. This product is currently used by fire brigades to assess smoke venting systems efficiency of buildings. The kinetics associated with the combustion of the material was assessed slow enough to allow measuring instruments to capture the thermal and chemical evolution during combustion reaction. Thermal analysis has first been carried out by means of DSC, TGA, DTA, MS and FTIR data in order to understand the decomposition of the material and its energetic evolution when undergoing heating. However, if the latter methods help defining the decomposing path of the material, they do not provide an integral view of its combustion behaviour, in particular, the emissions of toxics which are kinetic path dependent. Subsequently, combustion tests have been carried out using the FPA. Its ability to capture the evolution of gases emissions formed during the reaction has been proved. The influence of two configuration parameters on the combustion behaviour and on the gaseous emissions of the material has been investigated. The proportion fuel/oxidizer has been varied as well as the composition of the reacting atmosphere. Results shows that the quantity of oxidizer in the material affects the kinetics of the reactions taking place in the condense phase. Increasing the concentration of potassium nitrate in the mixture enhanced the reaction rate of the smouldering combustion. Higher quantity of volatiles is released which favoured the initiation of a diffusion flame regime in the gaseous phase, above the sample. While the kinetics of the condense phase is governed by the oxidizer concentration, experiments show that the flaming regime is influenced by the concentration of oxygen (O2) in the reacting atmosphere. A transition from diffusion to premixed flame is found when the concentration of O2 surrounding the sample is reduced below 18%. An analytical model has been used to explain the existence of a transition for a critical O2 concentration. Finally, thermal and combustion analyses have allowed to characterise the behaviour of the material under critical conditions, in terms of decomposition taking place in the condense phase but also potential toxic emissions that can be released. Toxicity, kinetics, temperature evolution do not provide a complete view of the combustion phenomenon. Beside these elements that characterise the behaviour of a material for given conditions as well as also the degree of fire hazard encountered, the energetic issue holds as an essential feature that cannot be neglected. The heat release rate (HRR) is a critical parameter that defines a fire. It does not constitute an intrinsic material property but it describes the energetic response of the couple formed by the material and its environment. Oxygen Consumption calorimetry (OC) and Carbon Dioxide Generation calorimetry (CDG) are widespread methods to calculate the HRR resulting from a combustion reaction. Apparatuses such as the FPA or the cone calorimeter have already proved their potential to qualify the burning behaviour of common fuels in addition to polymers when their data are combined with an adapted calorimetric procedure. The same approach has been applied to energetic materials. However, prior to using these techniques, it is fundamental to have identified their restrictions. These techniques provide approximate estimations of the HRR. Results are affected by the propagation of uncertainties. Several sources of uncertainties can be found. One can cite: 1. Uncertainties associated with the sample material; 2. Uncertainties associated with the test conditions; 3. Uncertainties associated with the measurements; 4. Uncertainties associated with calculation assumptions. If uncertainties cannot always be estimated, the three first sources cited have received attention in the past from the scientific community, alike the last one. The restrictions associated with the assumptions developed for using the OC and CDG principles have to be clarified. The limits of validity of the hypotheses have to be clearly defined. In particular, the present dissertation questions the relevance of the energy constants that have been specified for OC and CDG as well as their related uncertainties. One of the purposes of the research deals with the ability to estimate accurate error bars for the calculation of the HRR. Once uncertainties related to the calorimetric methods are assessed, a method adapted from the basic OC and CDG principles is introduced that allows estimating the HRR of energetic materials. The approach is based on considering the chemical decomposition of the burning compound and defining a fictitious molecule for which energy coefficients can be calculated. Nevertheless, it requires the material to be known. Finally, the question of the advantage brought by these techniques over others, in terms of accuracy, is discussed within the framework of unconventional products, such as energetic materials or compounds whose composition is ignored. The results from this work will contribute to the development of fireanalysis methodologies and validate their use with energetic materials.

Les systèmes de stockage thermochimique s’avèrent être de bonnes alternatives aux technologies actuelles pour le stockage saisonnier ou intersaisonnier de la chaleur, car l’énergie est stockée sous forme d’un potentiel chimique et donc, il n’y a pas de pertes thermiques pendant la durée de stockage. Un grand nombre d’études a été mené sur le développement de réacteurs thermochimiques intégrés au système de stockage, et peu d’étude ont été menées sur les technologies de réacteur séparé du réservoir de stockage. Ces dernières présentent cependant l’avantage, entre autres, de dissocier la puissance thermique du réacteur et la capacité de stockage de l’installation, ce qui permettrait d’augmenter la densité de stockage.Cette étude se penche sur le développement d’un réacteur thermochimique à lit mobile fonctionnant avec des sels hydratés sous air humide, adapté à des applications aux réseaux de chaleur. Un prototype de réacteur, développé et construit durant cette étude, a permis d’analyser le fonctionnement du réacteur. Cette étude a, entre autres, mis en évidence l’impact des passages préférentiels de l’air sur les performances du réacteur (température et puissance), ainsi que l’importance du titre de vapeur de l’air à l’entrée du réacteur sur ces performances. Il apparaît également que la circulation du solide abaisse sensiblement le point d’équilibre atteint par la réaction.De plus, deux modèles mathématiques ont été développés : un modèle analytique 1D et un modèle 2D prenant en compte les phénomènes de transfert de matière et de chaleur au sein de la zone réactive. Le modèle 2D, validé avec les résultats expérimentaux, a été exploité à l’aide du logiciel de simulation par éléments finis COMSOL Multiphysics afin de mener une étude théorique sur le fonctionnement et les performances du réacteur. Cette étude numérique a porté sur l’influence des conditions opératoires (débit et taux d’humidité de l’air, vitesse du solide) sur les performances et le rendement du système et a permis la comparaison des réacteurs à lit mobile par rapport aux réacteurs à lit fixes, communément développés pour des applications de stockage thermochimique. Cette étude a montré l’importance de la régulation de la vitesse du solide pour l’optimisation des performances du réacteur à lit mobile.L’ensemble de cette étude a permis de mettre en évidence les avantages et les limitations d’un réacteur à lit mobile pour des applications de stockage thermochimique / Thermochemical storage systems prove to be good alternatives to current technologies for seasonal or inter-seasonal storage of heat, because energy is stored as a chemical potential and therefore, there is no heat loss during the storage period. Nowadays, a large number of studies have been conducted on the development of thermochemical reactor integrated in the storage system, andlittle study has been conducted on reactor technologies separated from the storage system. The latter, however, have the advantage, among others, of separating the thermal power produced or consumed and the storage capacity of the installation, which would increase the storage density.This study investigates the development of a moving-bed thermochemical reactor operating with hydrated salts and humid air cross-flow, suitable for district heating applications. A reactor prototype, developed and built during this study, allowed to analyze the functioning of the reactor. This study has, among others, highlighted the impact of the preferential air flow path on the reactorperformances (temperature and power), as well as the importance of the air humidity at the reactor inlet on these performances.In addition, two mathematical models have been developed : a 1D analytical model and a 2D model taking into account the heat and mass transfer phenomena within the reactive area. The 2D model, validated with the experimental results, was exploited using the finite element simulation software COMSOL Multiphysics to conduct a theoretical study on the functioning and the performances of the reactor. This numerical study focused on the influence of operating conditions (air flow rate and moisture content, solid flow rate) on the performances and the efficiency of the system and allowed the comparison of moving bed reactor over fixed bed reactors, commonly developed for thermochemical storage applications. This study has shown the importance of solid velocity control for optimizing the performances of the moving bed reactor.This study has highlighted the advantages and limitations of moving bed reactors for thermochemical storage applications

La synthèse de particules d'oxydes mixtes en solution aqueuse est souvent difficile à contrôler en raison de la réactivité potentiellement différente des espèces qui coprécipitent. L’objectif de la thèse est de tenter de comprendre et piloter la synthèse dans le cas du système de particules d’oxydes mixtes de titane et d'étain, choisi en raison de l'existence d'une solution solide sur toute la gamme de composition et de la possibilité de recourir à une précipitation homogène plus simple à modéliser que le mélange réactif. Les synthèses sont réalisées par thermohydrolyse avec chauffage micro-ondes de solutions acides, fournissant des particules directement cristallisées avec des temps de réaction réduits. Les résultats des synthèses, à savoir le rendement et la composition du solide, sont modélisés par un calcul de sursaturation nécessitant la connaissance de la spéciation des solutions préparées. Cette dernière est calculée par la détermination à la température de thermohydrolyse des constantes d’équilibres en solution à partir de données bibliographiques et de mesures de solubilité à basse température d'une part et d'autre part de modélisation de la dépendance thermique des grandeurs thermodynamiques. Enfin, des nanocomposites Anatase-Rutile ont été obtenus par coprécipitation de titane avec de petites quantité d’étain et les propriétés photocatalytiques de ces nanoparticules ont été testées. / The synthesis of mixed oxide particles in aqueous solution is often difficult to control because of the potentially different reactivity of coprecipitating species. The aim of the thesis is to try to understand and control the synthesis in the case of mixed titanium oxide particles and tin system, chosen because of the existence of a solid solution over the entire range composition and the possibility of using a simpler homogeneous precipitation to model the reactant mixture. The syntheses are carried out by thermal hydrolysis of acidic solutions with microwave heating, providing particles directly crystallized with reduced reaction times. The results of the synthesis, namely the yield and composition of the solid, are modeled by a calculation of the supersaturation requiring knowledge of the speciation of the prepared solutions. This is calculated by determining the temperature of thermal hydrolysis in solution equilibrium constants from bibliographic data and low-temperature solubility measurements on the one hand and on the other hand, modeling of the temperature dependence of the thermodynamic. Finally, Anatase-Rutile nanocomposites were obtained by coprecipitation of titanium with small amounts of tin and the photocatalytic properties of these nanoparticles were tested

La télédétection thermique en temps réel de systèmes volcaniques actifs est une technique cruciale pour comprendre le comportement et l'activité éruptive de corps magmatiques chauds. Cette technologie repose sur la détermination de l'émissivité thermique du magma, un paramètre permettant d'identifier la température du magma. Nous avons utilisé une méthode directe pour obtenir des spectres dans la plage de nombres d’onde allant de 400 à 13000 cm-1; d’échantillons naturels volcaniques (volcan Erebus et Teide) et synthétiques (avec différents éléments). Ces matériaux ont été chauffés de la température ambiante à 2000K avec un laser CO2 et les données ont été collectées pendant toute la phase de chauffage avec un spectromètre IRTF.Nos résultats indiquent que l’émissivité d’une roche magmatique est affectée par les changements de composition et l’histoire thermique. Les mesures d'émittance montrent le rôle important du fer et de la vitesse de refroidissement du magma sur la réponse spectrale des compositions de type phonolitique. Ces observations sont importantes, car une méconnaissance des valeurs d’émissivité engendre des erreurs sur la détermination de la température et, donc à une interprétation erronée de la rhéologie et de l'efficacité thermique du corps magmatique. / Real time thermal remote sensing of active volcanic systems is a crucial technique for understanding the behavior and eruptive activity of hot magmatic bodies. Such technology relies on determining the thermal emissivity of the magma, a parameter to identify the temperature of magma. We used a direct method to obtain a spectrum in the wavenumber range from 400 to 13000 cm-1; the natural (volcano Erebus and Teide) and synthetic samples were heated up from room temperature to 2000K with a CO2 laser and data were collected during all the heating stage with a FTIR spectrometer.Our results thus indicate that thermal emissivity of magmatic rock is affected by changes in composition and thermal history. The emissivity measurements show the important role of the iron and the cooling rate on the spectral response of the phonolite composition. These are important observations since different emissivity will lead to different temperature determinations and hence, an erroneous interpretation on the rheology and thermal efficiency of the magmatic body.

Solid state chemical storage of hydrogen in metals offers promising advantages over compressed hydrogen gas and condensed liquid hydrogen, especially for mobile applications with respect to safety and energy efficiency. However, no single metal hydride simultaneously satisfies the essential performance criteria for onboard hydrogen storage namely, high gravimetric and/or volumetric energy density, fast kinetics and favorable thermodynamics. Recently, a breakthrough achievement was made by the development of reactive hydride composites in which two metal hydride systems (e.g. NaBH₄ and MgH₂) are mixed together resulting in better sorption properties than the individual pure systems. In this approach, the formation of MgB₂ by exothermic reaction destabilizes the composite and consequently reduces the overall enthalpy and sorption temperature of the endothermic desorption reaction. In this work the thermodynamic and kinetic properties of reactions in 2NaH + MgB₂ + 4H₂ ↔ 2NaBH₄ + MgH₂ and 3NaH + MgB₂ + 4H₂ ↔ 2NaBH₄ + NaMgH₃ were established using multiple experimental techniques like volumetric measurements, ex-situ and in-situ X-ray diffraction, calorimetry, and especially electron microscopy. Under the applied experimental conditions of 50 bar hydrogen and 400 °C during the hydrogenation of 2NaH + MgB2 and 0.1 bar hydrogen and 450 °C during the dehydrogenation of 2NaBH₄ + MgH₂, both reactions were kinetically limited and proceeded in multisteps. The absorption reaction was partial, being restricted by the unexpected formation of NaMgH₃ which limits the formation of NaBH₄ while the desorption reaction was complete and limited by the growth of MgB₂ through some intermediate complexes at the Mg/NaBH₄ interface where the intermediate phase forms a barrier to diffusion. Conversely, in the 3NaH + MgB₂ system, absorption in 100 bar hydrogen and 300 °C was complete but slow, while in the 2NaBH₄ + NaMgH₃ system, complete desorption was achieved in multisteps under 0.1 bar hydrogen and 450 °C. The formation of intermediate and stable complexes during these reactions poses a significant restraint to hydrogen sorption reactions. However, lower onset sorption temperatures have been established in these systems than in the pure compounds due to their simultaneous destabilization in the composite state. This study have demonstrated the complexity of desorption and absorption mechanisms in these composite systems and the difficulty of obtaining such reactions at low temperatures required for mobile applications. This understanding of the rate limiting reaction steps in reactive hydride composites provides the basis for further optimization of these materials for efficient hydrogen storage applications.