Bertrand Chazallon

CO2 Capture Using Semi-Clathrates of Quaternary Ammonium Salt: Structure Change Induced by CO2 and N2 Enclathration

Semi-clathrates of tetrabutylammonium bromide (TBAB) are investigated for their potential application in the CO2 capture context based on hydrate technology. The three-phase lines of semi-clathrates of CO2-TBAB-H2O and N2-TBAB-H2O are established simultaneously with their structure using in situ Raman scattering performed at high pressure. The preferred crystal phase obtained at ambient pressure from solutions of 5 and 40 wt % TBAB initial concentrations is shown to change upon enclathration of CO2 or N2, or by applying a higher pressure on the system. Deep in the stability field, metastable hydrate phases are occurring at the onset of the formation and correspond to the ones expected under ambient pressure conditions. Depending on the pressure, they progressively transformed into the most stable ones when approaching equilibrium and dissociation points. Besides, it is shown that a 5 wt % TBAB original solution forms preferentially a mixed structure of both type B and type A at low gas pressure with CO2 as the guest gas. A new structure is spectroscopically characterized at pressures higher than ∼2 MPa CO2. Type A is demonstrated to be stable at 5 wt % initial TBAB concentration with N2 as the guest molecule and pressure between 8 and 12 MPa. These structural data address new insights on the relationship between the hydrophilic-anion and hydrophobic-cation intercalation with a guest gas producing hydrophobic interaction in a distorted water lattice.

Ice mixtures formed by simultaneous condensation of formaldehyde and water: an in situ study by micro-Raman scattering

Thin films of formaldehyde-water mixtures are co-deposited at 88 K and 10(-1) Torr from gas collected above formaldehyde aqueous solutions of different concentrations (5, 10, 15, 20, 30 mol%). They are analyzed in situ by micro-Raman scattering in the 2700-3800 cm(-1) spectral range. The spectral characteristic of H2CO distributed molecularly in amorphous solid water is obtained under vacuum conditions. As temperature is increased formaldehyde is released during the crystallization of ice between 118 and 138 K. On the other hand, under controlled nitrogen atmosphere, the deposits crystallize in hydrate phases (or solid H2CO(s)) during annealing. A new phase (metastable FOR-A) of H2CO(s) (or a low hydrate after rejection by crystallizing ice) can be spectroscopically identified at 138 K before transformation into a hydrate (with molecular H2CO distributed within the cages of the clathrate FOR-B) takes place at 148 K. This latter phase decomposes between ca. 180 and 200 K. The significant spectral differences between these hydrates and those formed in frozen formaldehyde aqueous solutions reflect the existence of H2CO-clusters of distinctive structural nature relative to those resulting from important oligomerization process in the liquid. Moreover, the structure, the gas distribution and relative gas population in the formaldehyde clathrate cages are influenced by the relative amount of trapped nitrogen at the surface, which moreover depends on the ice film morphology. The dependence on the crystallization temperature of the deposits is explained by the relative amounts of occluded H2CO/N2 and the external pressure conditions. The distinct behavior observed between vacuum and N2-atmosphere conditions certainly reflects a complex mechanism of surface mediated nucleation in which the transport of the reactants to the hydrate reaction zone is facilitated by the presence of a polar dopant.

Ice Particle Crystallization in the Presence of Ethanol: An In Situ Study by Raman and X-ray Diffraction

Two distinct ethanol aqueous solution droplets ((X(EtOH))L = 8.7 wt % and 46.5 wt %) are investigated by in situ Raman spectroscopy and X-ray diffraction between 253 and 88 K. Structural changes are identified by modifications in the O-H and C-H stretching modes (2800-3800 cm(-1) spectral region) during freezing and annealing events. They are attributed to the formation of ice and/or different hydrate structures in the EtOH-water system. At high initial ethanol concentration, the particle is found to be composed of a modified clathrate I (cubic structure) at 211 K on cooling and transformed into an ethanol hydrate II (monoclinic structure) on annealing between ∼143 and 173 K. This latter decomposes at ∼200 K and leaves an aqueous solution and ice Ih which further dissociates above ∼230 K. At low initial concentration, ice first forms on cooling and the particle consists of a crystalline ice core embedded in a liquid layer of high ethanol content at ~200 K (or an amorphous layer at lower T). A new hydrate (IV) of distinct structure (orthorhombic) is observed on annealing (from 100 K) between ∼123 K and ∼142 K (depending on initial composition), which transforms into the ethanol hydrate II at ∼160 K. The hydrate II decomposes at ∼200 K, and ice Ih remains (and dissociate above ∼220 K) in coexistence with the liquid layer of high ethanol content. It is proposed that the complex crystalline ice particles formed may have the potential to impact several atmospherical processes differently in comparison to the pure ice case.

Ethanol Hydrates and Solid Solution Formed by Gas Condensation: An in Situ Study by Micro-Raman Scattering and X-ray Diffraction

Thin films of ethanol-water solid mixtures formed by gas co-condensation are investigated in situ by micro-Raman scattering in the 800-1600 and 2800-3800 cm(-1) spectral regions. Information at the molecular level on the structure is derived from accompanying changes observed in band shapes and vibrational mode frequencies. Depending on the ethanol content, the formation of two distinct ethanol hydrates is spectroscopically characterized, and their structures are independently confirmed by X-ray diffraction measurements. The attribution of the different phases is made in comparison with literature data and in relation with the ethanol phase diagram. Raman characteristic spectral features of ethanol extremely diluted in ice and corresponding to a solid solution regime are reported.